TWI359878B

TWI359878B - Plasma cvd apparatus and film deposition method

Info

Publication number: TWI359878B
Application number: TW096149677A
Authority: TW
Inventors: Kazuhito Nishimura; Hideki Sasaoka
Original assignee: Kochi Ind Promotion Ct; Casio Computer Co Ltd
Priority date: 2007-03-12
Filing date: 2007-12-24
Publication date: 2012-03-11
Also published as: KR20080083560A; KR101010389B1; TW200905010A

Description

1359873 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。【先如技術】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2628404、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)期刊中"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 I35?878 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ΙΠ-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 1359878 $口’藉以由陰極朝向陽極產生氣體流動，並通過1 第37 A圖及第37 B圖爲用於解釋電漿化學氣相 ®之反應爐中氣體的流動圖。第37A圖爲該反應態’而第3 7 B圖爲在1 G之氣體流動之流動速率及方箭頭所示。在電漿化學氣相沈積裝置中，如第37A圖所示 GI的位置與氣體出口 GO的位置彼此相對，而 @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 G◦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。竈漿。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 1359878 在未審查日本專利申請早期公開編號H1 -9461 5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板的上表面，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：第一電極，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：及第一氣體供應噴嘴，係置於在該反應爐中該第一電極的高度與該第二電極的高度之間的高度處，並具有複數噴出埠，該些噴出埠係以環繞該第一電極與該第二電極間之產生電漿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 135,9878 .· * .—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。 1359878 分，以部極可央電間。中緣期値極周升流電的上電一分在或第部値壓該緣流電對周電間面的或之括極壓極包電電電可一的一極第間第電該極與數對電極複面一電 , 及第緣中-與周例極極於此電電高在央央成中中定的且設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- 1359878 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11置於處理室10中。由具有高導熱性及高熔點之材料製成的碟狀陽極11a，例如鉬或石墨，即安裝在平臺11上。陽極11a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llx 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12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11的底側，其可冷卻覆蓋的陽極11a，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12之上方側較佳地是應大於基板1，以在平面方向上均勻地冷卻基板1。 -11 - 135.9878 提供在陽極lla之下的空間lib被平臺11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lla之上。陰極13支撐在陰極支撐14上，並面對陽極1U。陰極13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，例如碳化矽。例如陰極1 3與陽極1 1 a之間的距離爲50mm。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15置於靠近陽極lla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lla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13的最大外徑之1.2倍。因爲絕緣單元15用於抑制陰極13與陽極lla之間的異常排放電（電弧放電、火花）之發生，絕緣單元15沿著陽極lla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lla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- 1359878 • ' < 室10的內部。隔熱玻璃安裝在觀視窗17中，以確室1 0內的氣密性。輻射蕰度計1 8經由例如觀視窗基板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；經由充氣管19供應含有反應氣體之來源氣體，排氣；示出），其經由排氣導管20自處理室10內部排出氣及電壓設定單兀21。充氣管19經由在處理室10中提供的孔洞插入室10中，且在反應爐中充氣管19之至少一部分由形成，例如氟化樹脂或矽膠。密合劑密封在處理室洞與充氣管1 9之外側表面之間，以確保處理室1 0 氣密度。在處理室10中，充氣管19連接至環狀噴其爲氣體供應噴嘴。當環狀噴嘴22較佳地是具有全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，所以該體在其中流動。具有相等孔洞的複數噴出埠22a係環狀噴嘴22之環狀內側表面上。噴出埠22a係提供 1 1 X或陽極1 la之中心軸爲相等距離，且個別的噴d 係提供成相對於做爲中心的軸1 1 X爲點對稱方式而對位置處》如下所述，噴出埠22a的形成方式係環電漿的區域，且該來源氣體由噴出埠22a朝向軸1 地噴出。環狀噴嘴22由附著於陰極支撐14之絕緣體噴保處理 1 7測量 ±1 )，其系統（未體，以到處理絕緣體 10之孔內部的嘴22， :圓形，來源氣配置在成與軸 ;!埠 2 2 a 位在相繞產生 1 X均勻嘴支撐 -13- 135,9878 23所支撐。環狀噴嘴22之噴出埠22 a設定成高於陽極Ua 之高度，其位置在低於陰極支撐14的最低位置（經由陰極支撐14暴露的陰極13之側面的最上方部分），以及位置在高於陽極11a與陰極13之間形成的正極柱PC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11a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22的內徑大於陰極13的外徑與陽極11a之外徑。環狀噴嘴22的中心位在陽極11a之軸llx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 0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1 1 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11a與陰極13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11a與陰極13。導線通過在處理室10中提供的孔洞而連接到陰極13與陽極11a。在有導線通過的處理室1〇中的孔洞由密封劑所密封。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18，及由導線連接至可變電源21b。當啓動時，控制單元2U代表由輻射溫度計18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- 1359878 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〇.34nm。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10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- 1359878 組成中的範圍在3 v 01 %到3 0 v 01 %之間。例如’甲烷的流速設定爲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11a 繞著軸llx以1 rPm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12大致與陽極11a區隔，以避免對於陽極11a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12向上移動而緊靠陽極11a。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10中做爲清洗氣體，以在處理室10中提供氮 -16- 1359878 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10中，來源氣體由噴出埠 22a朝向軸llx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11，來源氣體的流動相對於處理室10中軸llx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13之中心正下方，其爲軸 11 X所在之處，所以來.源氣體自基板1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勻。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。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- 1359878 » * . 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3B圖所示，例如環狀噴嘴22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15。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20集中，如第3B圖中兩串鏈線所示。因爲陰極13成爲對於來源氣體之流動有干擾，來源氣體變得很難環繞陰極1 3，以到達陽極1 空間擦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 la之 -18- 1359878 中心處的軸llx，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13與陽極11a更大時更加明顯。在如第3B圖所示修正的DC電漿化學氣相沈積裝置中，如第4A圖所示。在陰極13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DC電漿化學氣相沈積裝置中，利用對比，在陰極13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23上，以將環狀噴嘴22絕緣於電源或接地，來自陰極13或陽極11a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 13與陽極1 la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 22 a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- 1359878 (6)環狀噴嘴22置於與陰極13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22側向排出的來源氣體即被導引朝向下方的排氣導管20。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 13。因此其有可能防止活性物種沈積在陰極13 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1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11a之中央部分，周綠電極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 11a之周緣部分，及陶瓷或類似者製成的絕緣部分27 c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27a與周緣電極27b 之間的距離是充份地長。因爲此部分具有較少的離子轟 -20- 135.9878 擊，沈積物有可能沈積在此處。這種沈積物造成或火花。在此方面，絕緣部分27c被插入，以防積在彼此面對之中央電極27a之側壁上與周緣電側壁上。電壓設定單元28具有控制單元28a，及可變1 28c « 控制單元28a由導線連接至輻射溫度計18 » 28a具有能力來控制可變電源28b、28c，並個別極11a與中央電極27a之間的電壓或電流，及陽中央電極2 7 a之間的電壓或電流。其他的組態相圖中的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電漿化積裝置形成薄膜在基板1上時，基板1於電漿上 rpm的速率旋轉，平臺1 1與中央電極27a之間的電壓設定單元28之控制之下將會大於平臺11與 27b之間的電勢差，以設定陰極27與陽極11a之澤這種電壓施加在陽極11a與中央電極27a之間產極柱PC。此可防止電弧放電的發生，其經常發生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在基板1之中央部分的上部後，控制單元28a施或電流使得陽極11a與中央電極27a之間的電壓成爲小於陽極1 la與周緣電極27b之間的電壓或以將陽極1 la與中央電極27a之間的溫度近似於電弧放電止薄膜沈極27b的 I 源 28b、控制單元地設定陽極11a與同於第1 學氣相沈升時以1 電勢差在周緣電極 3的電壓。生小的正於開始時流而形成加該電壓或電流値電流値， •陽極1 1 a -21- 1359878 與周緣電極27b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 27a與周緣電極27b’及陽極11a與中央電極27a之間的電壓或電流値，陽極11a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11a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11a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PC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 30將基板1隔離外界空氣。柱狀鋼質平臺11置於處理室30中。由具有高導熱性及高熔點之材料製成的碟狀陽極11a，例如鉬或石墨，即安 -22- 裝在平臺11上。爲長方形的基板1固定在陽極11a之上方安裝面上。平臺11之設定使得平臺11可與陽極lla共同繞著軸1 lx旋轉。在陽極11a之下的平臺11具有封閉的空間llb，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12由具有高導熱性的金屬形成，例如銅。一種冷卻劑，例如冷卻水或氯化耗的冷卻溶液，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12向上移動時，冷卻構件12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 2 a來藉以循環。碟形的陰極13置於陽極11a之上方。陰極13支撐在陰極支撐14上，並面對陽極11a。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13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15置於靠近陽極Ha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’ 1359878 例如碳化矽等當中至少一項。形狀爲環形的絕緣單元15以與陽極lla相同的高度支撐，其由在處理室30之底部及環繞陽極11a之內側處立提供的支撐16所支撐。絕緣單元15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15沿著極lla之外側表面並相對於陰極13來放置，並配置成隱陽極lla之側面。在處理室30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17中，以確保處室30內的氣密性》輻射溫度計18可經由例如觀視窗17 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30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3 1之外側表面間’以確保處理室30之內的氣密性。在處理室30中，氣管31連接至環狀噴嘴33。環狀噴嘴33類似於第2圖所示的環狀噴嘴22。具有等孔洞之複數噴出埠33a以環狀的方式配置在環狀噴嘴來直於的陽藏理理測其系 y 20 提之充相 -24- 33 1359878 • . 之內側表面，並以與軸llx或陽極lla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 1 X 之點對稱方式提供在相對位置處，而自噴出埠33a朝向軸 llx均句地噴出該來源氣體。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14的最低部分的位置處（經由陰極支撐14暴露的陰極13之側面的最上方部分），以及位置在高於陽極11a 與陰極13之間形成的正極柱PC之最高點。因爲將環狀噴嘴33支撐在此範圍中，該反應氣體輕易地進入陰極丨3與陽極1U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33的中心位在陽極11a之軸llx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11a與陰極13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11a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1U。在有導線通過的處理室30中的孔洞由密封劑所密封。 -25- 1359878 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18，及由導線連接至可變電源21b。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。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32之外側表面之間，以確保處理室30之內的氣密性。在處理室30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llx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 電漿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33 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33之高度的驗證實驗。第7圖爲驗證實驗的簡略圖》 •26- 1359878 在該驗證實驗中，薄膜沈積之進行藉由將陽極lla與陰極13之直徑設定爲160mm，其厚度設定爲15mm，陽極 lla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0.25吋，氣體噴淋噴嘴34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1 la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1 la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llx 上的觀察點A，及與端面距離10 mm之距離L1並與相鄰於前述端面的兩個端面距離3 7.5 mm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圖及第9C圖爲斷層攝影SEM影像，所示分別爲 -27- 1359878 • « · 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33之噴出埠33a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，所不分別爲在觀察點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33之噴出埠33a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9B 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33a之直徑時觀察薄膜沈積之狀態的實驗》 -28- 135.9878 環狀噴嘴33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0.5mm、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矽基板上的情況下，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33a直徑爲0.5mm剛噴出之後的氣體之移動速率來設定等於500c 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125cm/s，設定利用噴出埠33a直徑爲1.5mm剛噴出之後的氣體之移動速率來設定等於55cm/s。第10A圖、第10B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0.5mm、 1.0mm及1.5mm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1 1圖所示爲利用噴出埠33a的直徑設定爲0.5mm、l.0mm及1.5mm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、噴出津33a的直徑爲.1.0mm、噴出填33a的直徑爲 1.5mm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，在當噴出埠 33a 之直徑爲 0.5 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A處的斷p攝影SEM影像可以瞭解，於Φ1.0及Φ1.5時垂直於基板的方向上奈米碳壁 -29- 135.9878 之成長大於在Φ〇.5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Φ 0.5與 Φ 1.0之間幾乎未改變並於1小時30分鍾之後到達該高原期，然而在Φ1.5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Φ1.0及φ 1.5時較低，所以側向成長的速率之比例似乎大於Φ1.0及Φ1.5的狀況。此代表當Φ0.5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Φ0.5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Φ0.5 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- 13598.78 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Φ1.5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33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- 1359878 • » 物有可能發生在陰極13及支撐陰極13之陰極支撐得電漿變成電弧放電或火花。本具體實施例之DC 學氣相沈積裝置獨立地引進基質氣體與反應氣體，應氣體之噴出位置相對高於基板1，並設定基質氣出位置高於反應氣體的噴出位置，所以朝向基板1 氣體的流動可由基質氣體之向下力量所操縱，藉以費排出的反應氣體量。此外，基質氣體的噴出位置陰極13與支撐陰極13之陰極支撐14之上，且反應噴出位置設定在陰極1 3之底側之下，所以該向下力質氣體到達排氣導管20時被施加，抑制反應氣體朝 1 3對抗基質氣體之流動的反向流動，並防止反應氣黏著到陰極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例之DC電漿化學氣相沈積裝置的組態圖。對於與第組件共用之第1 2A圖及第1 2B圖中的那些組件皆給的參照編號。此DC電漿化學氣相沈積裝置爲第1圖中DC電氣相沈積裝置，其陰極13改變成陰極35，且其電壓元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之分，周緣電極35b，其形狀爲環（參見第12B圖），環電極35a，其與中央電極35a同圓心，並面對陽極1 緣部分，及陶瓷或類似者製成的絕緣部分35c完全 14，使電漿化設定反體之噴之反應降低浪設定於氣體之量於基向陰極體成分體實施 6圖之與共用漿化學設定單中央部繞中央 1 a之周塡滿在 -32- 1359878 • * · 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 35b之間，則由活性物種成長的薄膜不僅沈積在基板1 亦在彼此面對的中央電極35a之側壁與周緣電極35b 壁上。在此方面，絕緣部分3 5c被插入，以防止薄膜在彼此面對之中央電極35a之側壁上與周緣電極35b 壁上。電壓設定單元36具有控制單元36a，及可變電源 3 6 c β 控制單元36a由導線連接至輻射溫度計1 8。控制 36a具有能力來控制可變電源36b、36c，並個別地設 ‘ 極11a與中央電極35a之間的電壓或電流，及陽極1 中央電極35b之間的電壓或電流。其他的組態相同於圖中的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 φ 沈積裝置形成薄膜在基板1上時，基板1於電漿上升 1 rpm的速率旋轉，陽極lla與中央電極35a之間的電電壓設定單元36的控制之下會大於陽極11a與周緣 35b之間的電壓，以設定陰極35與陽極lla之間的電這樣的施加電壓在陽極1 la與中央電極35a之間產生正極柱PC，並可防止在薄膜沈積的初始階段發生電電。在該穩定正極柱PC由施加這樣的電壓或電流而在基板1之中央部分的上部時，控制單元36a施加該電極上，之側沈積的側 36b、單元定陽 la與第6 氣相時以 1 壓在電極壓。小的弧放形成電壓 -33- 135.98.78 或電流使得陽極lla與中央電極35a之間的電壓或電流値成爲小於陽極1 1 a與周緣電極35b之間的電壓或電流値，以將陽極lla與中央電極35a之間的溫度近似於陽極lla 與周緣電極35b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35包含中央電極 35a與周緣電極35b，及陽極lla與中央電極35a之間的電壓或電流値，陽極lla與周緣電極3 5b之間的電壓或電流値可獨立地設定。在電漿上升時，陽極lla與中央電極35a 之間的電壓被設定高於陽極lla與周緣電極35b之間的電壓》因此，正極柱PC可利用將陽極lla與陰極35之間的距離變得較短來形成。要施加於陽極lla與陰極35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35b之電流會變成小於流過中央電極35a之電流，以產生在基板1之中央處集中的正極柱 PC，然後施加到周緣電極35b之功率即增加，以增加流過周緣電極35b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示意圖。 •34- 1359878 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52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5 2b，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51a之下的空間51b被平臺51區隔，所以 -35- 1359878 空間51b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54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53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相同的高度來支撐，其由在處理室50之底部及環繞陽極51a之內側處直立提供的支撐16所支撐。因爲絕緣單元55用於抑制陰極53與陽極51a之間的異常排放電（電弧放電、火花）之發生，絕緣單元55沿著陽極5 1a之外側表面並相對於陰極53來放置。絕緣單元55 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，以允許觀察處理室50的內部。隔熱玻璃安裝在觀視窗57中’以確保處理室5 0內的氣密性。輻射溫度計5 8可經由例如觀視窗5 7測 -36- 1359878 • · » 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 0 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5 0之孔洞與充氣管59之外側表面之間，以確保處理室50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、 62B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。複數噴出堤62a相對於軸53x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54的最低位置之下（陰極53之暴露側面的最上方部分）’以及位置在高於陽極51a與陰極53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- 135.98.78 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51a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53之間的電壓或電流之數値，並具有控制單元61a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50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- 135.9878 « 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使用排氣壓，且氫氣、反應氣體及在成份中含有碳的反應氣合物（含碳化合物），例如甲烷，即由充氣管59供應室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到之間進行，其設定爲基板1之形成奈米碳壁的該部度。此溫度由輻射溫度計5 8測量。此時，冷卻構β 致與陽極51a區隔，以避免對於陽極51a之溫度的輻射溫度計58之設定使得降低DC電漿化學氣相沈之電漿輻射，並僅由在基板1之上方表面處的熱輻得溫度。當含有多個鑽石粒子之鑽石層疊層在奈米碳壁在奈米碳壁沈積製程期間改變電子放電膜之薄膜特如冷卻構件52向上移動而緊靠陽極51a。因此，基溫度可顯著地降低而造成鑽'石層的積層。當鑽石時，棒形的sp2鍵結碳，其爲奈米碳壁的修正部分，是奈米碳管，其具有塡充的核心而成長。此棒狀的到自鑽石層的上方表面突出，而爲結構上可能集中部分且釋放電子。在薄膜沈積的末端平臺處，陽極51a與陰極53 施加電壓即停止，然後來源氣體之供應即停止，並氣到處理室50中做爲清洗氣體，以在處理室50中系統洩體之化到處理 1 100°C 分的溫 :52大影響。積裝置射來取上，而性，例板1之層成長且不像碳延伸電場的之間的供應氮提供氮 -39- 13598.78 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6 2A、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5 1 a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- 13598,78 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13圖所示之第五具體實施例的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65c，其完全塡滿在中央電極65a與周緣電極65b之間。若不將絕緣部分65c插入在中央電極65a與周緣電極 65b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65a之側壁與周緣電極65b之側壁上。在此方面，絕緣部分65 c被插入，以防止碳膜沈積在彼此面對之中央電極65a之側壁上與周緣電極65b的側壁上。電壓設定單元66具有控制單元66a，及可變電源66b、 66c 0 控制單元66a由導線連接至輻射溫度計1 8。控制單元 -41 - 1359878 • * . 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65a之間的電壓或電流。其他的組態相同於第13 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 rpm的速率旋轉，平臺51與中央電極65a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5 1 a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51a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65a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- 1359878 壓。因此，正極柱PC可利用將陽極51a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65b之電流會變成小於流過中央電極65 a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65 b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。 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7〇將基板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- 1359878 數正方基板1可放置在陽極5la上。在陽極51a之下的平臺51具有封閉的空間置有冷卻構件52。冷卻構件52係用於視需要片並建構成可以藉由移動機構（未示出）而如箭頭下移動。冷卻構件52由具有高導熱性的金屬銅。一種冷卻劑，例如冷卻水或氯化鈣的冷卻導管52a進入冷卻構件52中的流動通道52b，並排出而在冷卻構件5 2中循環，以冷卻整個冷卻當冷卻構件52向上移動時，冷卻構件52 靠在平臺51的底側，其冷卻位在上面的陽極5 熱量由基板1帶離。冷卻構件52的上方側爲長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 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。撐在陰極支撐14上，並面對陽極51a。陰極53 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，例如石英玻璃氮化物，例如氮化鋁或氮化矽，或隔熱碳化物矽等製成。冷卻劑流經的通道可在陰極5 3中形成。冷可抑制陰極5 3的過熱。較佳的冷卻劑爲水、氯 5 lb，其中 >卻基板1，所示般地上形成，例如溶液，其由 :由導管52c 構件5 2。的上方側緊 la，藉此將方形，並在出）冷卻，並區隔，所以陰極53支由鉬、石墨或鋁，隔熱，例如碳化卻劑的流動化鈣溶液及 -44- 135,9878 類似者，其由處理室70之外部供應。用於抑制電弧發生的絕緣單元55置於靠近陽極51a的外側表面。絕緣單元55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，例如碳化矽等當中至少一項。形狀爲環形的絕緣單元55以與陽極5U相同的高度來支撐，其由在處理室70之底部及環繞陽極51 a°之內側處直立提供的支撐16所支撐。因爲絕緣單元55用於抑制陰極53與陽極51a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 51a之外側表面並相對於陰極53來放置。絕緣單元55可配置成隱藏陽極5 1 a之側面》在處理室7 0的側面中形成觀視窗5 7，以允許觀察處理室70的內部。隔熱玻璃安裝在觀視窗57中，以確保處理室70內的氣密性。輻射溫度計58經由例如觀視窗57測量基板1之溫度，並置於處理室70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71經由在處理室70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 0之孔 -45- 13598.78 洞與充氣管71之外側表面之間，以確保處理室70內部的氣密度。在處理室70中，充氣管71連接至噴嘴73’其爲反應氣體供應噴嘴。噴嘴73具有一部分73A，其平行於每一個陽極51a與陰極53之長邊，及一部分73B平行於每一個陽極51a與陰極53之另一長邊。噴嘴73可爲整個環形，或部分73A、 73B可由與充氣管71的連接點分支出去。噴嘴73爲中空以傳送反應氣體。複數噴出埠73a以線性對稱方式以相等間距形成在噴嘴73的部分73A、73B中，所以來源氣體由噴出埠73a朝向基板1側向地噴出，即在側向向內方向上。噴嘴73由附著於陰極支撐54之絕緣噴嘴支撐63所支撐。噴嘴73之支撐高度設定的方式爲噴出埠73a低於陰極支撐54的最低位置之下（陰極53之暴露側面的最上方部分），以及位置在高於陽極51a與陰極53之間形成的正極柱PC之最高點。因爲噴嘴73支撐在此範圍中，該來源氣體輕易地進入陰極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73之部分73A、73B之間的間隔大於陰極53的寬度（短邊方向），而噴嘴73的部分73A、73B放置在長邊方向上陰極53之兩個側面之更外側。部分73A、73B在長邊方向上與陽極51a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。 -46 - 1359878 電壓設定單元61爲一種控制裝置，其設定陽極51a與陰極53之間的電壓或電流之數値，並具有控制單元61a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70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。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70之內的氣密性。在處理室70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53x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之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噴嘴73噴 -47- 1359878 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（10)。 (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稹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53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- 1359878 體成分黏著到陰極53及支撐陰極53的絕緣陰極支撐 [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例之DC電漿化學氣相沈積裝置的組態圖。對於與舞之組件共用之第22A圖及第22B圖中的那些組件皆用的參照編號。第23圖爲上述第22A圖之DC電漿化學氣相沈的陰極、反應氣體噴嘴、基質氣體噴嘴及排氣導管6 第21圖爲由側向之第22A圖的DC電漿化學氣裝置之剖視圖。此DC電漿化學氣相沈積裝置爲第19圖所示之體實施例的DC電漿化學氣相沈積裝置，其陰極53 陰極75，且其電壓設定單元61改變成電壓設定單方陰極75具有中央電極75a，其面對陽極51a之分，周緣電極75b，其形狀爲環形（參見第22B圖），央電極75a，其面對陽極51a之周緣部分，及陶瓷或製成的絕緣部分75c完全塡滿在中央電極75a與周 7 5 b之間。若不將絕緣部分75c插入在中央電極75a與周 7 5b之間，由活性物種成長的薄膜不僅沈積在基板1 在彼此面對的中央電極75a之側壁與周緣電極75b 上。在此方面，絕緣部分75c被插入，以防止碳膜彼此面對之中央電極75a之側壁上與周緣電極75b 上。 54上。體實施 19圖給與共積裝置圖。相沈積第七具改變成：76 ° 中央部環繞中類似者緣電極緣電極上，亦之側壁沈積在的側壁 -49- 1359878 • . 電壓設定單元76具有控制單元76a，及可變電源76b、 76c。控制單元76a由導線連接至輻射溫度計58。控制單元 7 6a具有能力來控制可變電源76b、76c，並個別地設定陽極51a與中央電極75a之間的電壓或電流，及陽極51a與中央電極75a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 75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51a與中央電極75a之間的電壓或電流値成爲小於陽極5 1a與周緣電極75b之間的電壓或電流値，以將陽極5 1 a與中央電極75a之間的溫度近似於陽極51a與周緣電極7 5b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- 1359878 値可獨立地設定。在電漿上升時，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 _。因此，正極柱PC可利用將陽極51a與陰極75之間的 gg離變得較短來形成。要施加於陽極51a與陰極75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75b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 PC，然後施加到周緣電極75b之電力即增加，以增加流過周緣電極7 5b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27、35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90b。'在此情況中，陽極1 1 a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 - 1359878 電極27a、35a與周緣電極27b、35b’類似於第28 之陰極93，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12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2 9A 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99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98。當三向閥98打開時，冷卻的氨氣及氮氣經由排氣孔1 2 X噴灑到平臺1 1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 .2的上在溝槽所示，流量控氮氣， ;96傳冷卻的以冷卻 -52- 1359878 [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釋5μιη左右。在陽極112之下的平臺111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113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113的上方端面爲面對相對於平臺111之電極安裝面1 1 la之面11 lc之相對面U3a(以下稱之爲“底面”），並具有大的外徑。當冷卻構件113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 0 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1 1 3 b自冷卻 -53- 1359878 • » 構件113的側面穿過，通過靠近相對面113a，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113,所以冷卻劑由冷卻單元115冷卻，並在流動通道11 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11 3e穿過冷卻構件11 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 3e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 3 e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111 c上的方法，一種利用將相對面1 1 3 a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122，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110中。用於排出該來源氣體之氣體排出管 -54- 1359878 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個別通理室110中提供的孔洞，及密封劑密封在每個孔洞氣體供應管路122與氣體排出管路123之外側表面以確保處理室110內部的氣密性。連接至氣體排出雙爲排氣系統（未示出），其由氣體排出管路123排出該體，以調整處理室110中的大氣壓力。在處理室1 10的側面上形成觀視窗125,以允許理室110的內部。在此例中，隔熱玻璃安裝在觀視中’以確保處理室110內部的氣密性。光譜輻射計由例如觀視窗1 25的隔熱玻璃測量基板1 〇 1之溫度於處理室110之外部。在使用DC電漿化學氣相沈積裝置進行基板1〇1 膜沈積時，首先，基板101置於陽極112的基板安裝上。當完成基板101的安裝時，接下來，處理室1: 部使用排氣系統洩壓，接著由氣體供應管路1 22供氣體到處理室110中。來源氣體爲要用於薄膜沈積的反應氣體（如甲烷）及基質氣體（載具氣體）（如氫負合物，其不會成爲由預定比例的薄膜沈積材料。在 101上沈積石墨、鑽石粒子或類似者的碳膜時，該反成爲含碳化合物的氣體。在處理室110內的壓力即設定爲預定値，或其藉由調整該來源氣體的供應量及排出量而使得其與値的變異落在可允許範圍內。平臺111可以例如以過在處與每個之間， :路 123 來源氣觀察處窗 125 126經，並置上的薄 ® 112a 0的內應來源之材料 U的混碳基板應氣體方式爲該預定 10 rpm -55- 1359878 旋轉，以旋轉基板101及陽極112»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101上開始薄膜沈積。旋轉基板101與陽極112降低根據基板101 位置之溫度變化，藉此防止在基板101上薄膜沈積的變異。爲了藉由抑制在基板101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113a可使其緊靠在底面111c上，而使得由冷卻單元115冷卻的冷卻劑在冷卻構件113的流動通道113b中流動，或該冷卻氣體可噴灑到底面11 lc上，而允許相對面1 13a接近到底面11 lc，或該冷卻氣體可被噴灑到底面111c，而允許相對面11 3a的 —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112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 20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 0 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101。接下來將說明DC電漿化學氣相沈積裝置的優點。 -56- 13598.78 當進行在基板ιοί上的薄膜沈積時，基板ιοί、陽極 112與陰極120即暴露於陽極112與陰極120之間產生的電漿而被加熱。當提供給基板101之一部分能量由熱輻射傳遞到處理室110時，能量大部分由基板101傳遞到陽極112 與平臺111，且在經由平臺111另傳遞到冷卻構件113。因爲傳遞的熱量與擴散的熱量平衡掉，基板101的溫度可保持恆定。薄膜沈積可同時在陽極112由石墨形成（以下此電極稱之爲“石墨電極”）以及陽極112由鉬形成（以下此電極稱之爲“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，沈積條件爲使得該來源氣體將在反應氣體中甲烷的流速設定爲50 seem，而在基質氣體中氫的流速設定爲500 seem，其被供應到處理室110 中，且一般壓力藉由調整排出速度而保持在7 999.3 2 Pa。此外，藉由施加電力產生電漿的方式爲陰極· 120與石墨電極及鉬電極之間的電流密度成爲〇_15 A/cm2(電流/電極面積）。鉬電極的表面之粗糙度平均値Ra爲1.5 μπί’大量移動的導熱度λ爲132 W.m·1·!^1。要做爲陽極Π2之石墨電極的表面之粗糙度平均値Ra爲5 μιη’大量移動的導熱度λ 爲 120 W · m —1 · Κ-1。厚度爲0.5mm之矽用於基板1〇1’且第31圖中平臺111 之相對面113a與底面111c之間的距離X設定爲60mm，約爲自薄膜沈積開始之後2個小時，藉以改變基板1〇1的溫 -57- 13598.78 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101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0,3 4nm» 然後，距離x接近於0.5mm。接著，做爲冷卻氣體之氦氣以500 seem經由排氣孔113e供應到平臺1 1 1之下方空間1 1 1 b中，以降低基板1 0 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1 μιη)，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 0 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 〇 1的溫度與其發射率藉由使用灰體近似（gray body approximation) 來評估。第32圖所示爲對於不同陽極112測量的基板101之溫度。如第32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30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- 1359878 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，基板丨01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101的溫度。比較對於不同電極而變化的基板101之溫度顯示在初始沈積區域中，基板101的溫度將大幅變化，在石墨電極上基板101的溫度要低於在鉬電極上基板101之溫度100°c 或更多。在後續狀態中，溫度變爲穩定，即使距離X爲 0.5mm，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112與陰極120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 101的溫度變高，周遭氣體溫度由基板101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101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- 13598.78 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100°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101的溫度較低。當基板101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101的溫度爲 T,，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…"可由下式表示。 -60- 1359878 • · , 公式 11359873 IX. Description of the Invention: [Technical Field] The present invention relates to a plasma chemical vapor deposition apparatus and a thin film deposition method. [Technology] 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 The gas supply is balanced with the exhaust rate 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 required to overcome irregular deposition and maintain a growth rate, for example, in Japanese Patent No. 2628404, Unexamined Japanese Patent Application Laid-Open No. H1-94615, and Yoshiyuki Abe et al. in Acta Astronautica (Great Britain) In the journal "DIAMOND SYNTHESIS BY HIGH GRAVITY DC PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE", 2001, Vol. 48, 2-3, pp. 121-127. The plasma chemical vapor deposition I35?878 device disclosed in Japanese Patent No. 2628404 supplies a reaction gas in a direction parallel or oblique to the upper surface of the substrate, and supplies a matrix gas from a direction substantially perpendicular to the upper surface of the substrate, and The reaction gas and the substrate gas are squeezed to 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. Hei No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No No. 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, a deposit is gradually formed on the cathode and stored in the nozzle, whereby the superimposed gas jet "if the deposit grows close to the nozzle and becomes a projection, the electric field is concentrated on the projection, Therefore, 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. The plasma chemical vapor deposition apparatus described in the paper "DIAMOND SYNTHESIS BY HIGH GRAVITY DC PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE" provides a gas inlet at the upper portion of the reactor and a gas at the lower portion thereof 1359878 The "port" is used 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 flowing at 1 G and the arrow. In the plasma chemical vapor deposition apparatus, as shown in Fig. 37A, the position of the GI and the position of the gas outlet GO are opposed to each other with the @ center axis in between. 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 G?, 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, so that part of the pressure of each active species is irregular according to its position, which causes uneven film deposition. SUMMARY OF THE INVENTION As described above, the vapor deposition apparatus disclosed in Japanese Patent No. 2628404 is a pyrochemical chemical vapor deposition apparatus, and a heater heats the crystal holder to generate a thermal plasma, unlike DC electrical phase deposition. A device that is difficult to form a uniform gas flow relative to the substrate when the electrodes are placed facing the location. Kitchen 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 slurry chemical substrate 1359878 in the early days of the unexamined Japanese patent application The plasma chemical vapor deposition apparatus disclosed in the publication No. H1 - 9461 5 is not technically satisfactory because it causes problems when the film is deposited, and may cause irregular film deposition. The plasma CVD apparatus disclosed in the paper "DIAMOND SYNTHESIS BY HIGH GRAVITY D.C. 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 substrate, and even when the electrode is placed at a position facing the substrate Ensure stable film deposition. 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 And being disposed above the first electrode and opposite to the first electrode, and generating a plasma with the first electrode: and a first gas supply nozzle disposed at a height of the first electrode in the reaction furnace At a height between the heights of the second electrodes, and having a plurality of ejection ports, the ejection channels are formed and arranged to surround a region between the first electrodes and the second electrodes that generates plasma. 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 No. 135, 9878. • 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, each of the plurality of ejection jets having the first gas supply nozzles is ejected from the ejection cartridges of the stack, and arranged so as 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 of the positive column from which 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 reaction furnace $. 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. 1359878 points, to the central office. The mid-edge bungee-cycled galvanic power-up is in the first part of the first or the first part of the spurt. The plurality of electrodes are electrically connected to the plurality of electrodes, and the first and the second ends of the electrodes are determined by the central portion and the plurality of electrodes may include a central electrode facing the central portion of the first electrode. And a peripheral electrode facing the peripheral portion of the first electrode, and after the positive electrode is formed between the central electrode and the first electrode, the voltage or current 之间 between the central electrode and the first electrode may be set to be smaller than the peripheral electrode And the voltage or current 第一 between the first electrodes. 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 electrode 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- 1359878 Fig. 1 is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a first embodiment of the present invention. A DC plasma chemical vapor deposition apparatus is to be processed on a substrate. A film is formed on the upper surface of the upper surface, and the processing chamber 10 is used as a reaction chamber. 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 llx. 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 - 135.9878 The space lib provided below the anode 11a is separated by the platform 11, so the interior of the space lib is filled with gas or open 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 1U. The cathode 13 is formed of molybdenum, graphite or the like, has a high melting point, and has a diameter of, for example, 80 mm and a thickness of 20 mm. The cathode support 14 is made of a thermally insulating oxide such as quartz glass or aluminum 'insulating nitride, such as aluminum nitride or tantalum nitride, or an insulating carbide such as tantalum carbide. For example, the distance between the cathode 13 and the anode 11a is 50 mm. 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. The 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 processing chamber 10 and provided vertically at the inner side of the anode 11a. The outer diameter of the insulating unit 15 is set to be equal to or greater than 1.2 times the maximum outer diameter of the cathode 13. Since the insulating unit 15 serves to suppress the occurrence of abnormal discharge electric power (arc discharge, spark) between the cathode 13 and the anode 11a, 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 processing -12- 1359878 • ' < The interior of the chamber 10. The insulating glass is installed in the viewing window 17 to ensure airtightness in the chamber 10. The radiation oximeter 18 is placed, for example, through the temperature of the window substrate 1, and placed outside the processing chamber 10. The DC plasma chemical vapor deposition apparatus has a source system (not shown; a source gas containing a reaction gas is supplied via an inflation tube 19, exhaust gas; shown), which is exhausted from the interior of the processing chamber 10 via an exhaust conduit 20 and a voltage setting Single 兀 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, for example, a fluorinated resin or silicone. The adhesive is sealed between the processing chamber and the outer side surface of the gas tube 1 9 to ensure the process chamber 10 gas density. In the process chamber 10, the inflation tube 19 is connected to the annular spray as a gas supply nozzle. When the annular nozzle 22 is preferably of a full shape, it may be a regular polygon. Fig. 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 ejection ports 22a having equal holes are formed on the annular inner side surface of the annular nozzle 22. The discharge port 22a provides an equal distance between the center axis of the 1 1 X or the anode 1 la , and the individual spray d is provided in a point symmetrical manner with respect to the axis 1 1 X as the center, and the position is as follows. The discharge port 22a is formed in a region of the ring plasma, and the source gas is ejected toward the shaft 1 by the discharge port 22a. The annular nozzle 22 is measured by an insulator spray treatment attached to the cathode support 14 (1), and its system (not body, to the nozzle 22 inside the hole of the processing insulator 10, : circular, source gas is arranged in The axis;!埠2 2 a position is supported by the phase winding to produce a 1 X uniform nozzle support-13-135,9878 23. The discharge port 22a of the annular nozzle 22 is set higher than the height of the anode Ua, and its position is lower than The lowest position 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 highest point of the positive electrode PC formed between the anode 11a and the cathode 13. Because the annular nozzle 22 is Supported in this range, the source gas easily enters between the cathode 13 and the anode 11a, and prevents 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 22 is larger than that of the cathode 13 The outer diameter is the outer diameter of the anode 11a. The center of the annular nozzle 22 is on the axis 11x of the anode 11a. The angle from the center of the anode 1 1 a toward the individual discharge ports 22a is substantially equal. Equal spacing through the processing chamber 1 Four holes are formed in the bottom side of 0 to surround the platform 1 Γ or the anode 1 1 a around the shaft 1 1 X. The sealant is sealed between each hole and the outer side surface of the associated exhaust duct 20. Voltage setting unit 21 is a control device which 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 holes provided in the chamber 10 are connected to the cathode 13 and the anode 11a. The holes in the processing chamber 1b through which the wires pass are sealed by a sealant. The voltage setting unit 21 has a control unit 21a connected to the radiation thermometer by wires 18, and connected by wires to the variable power source 21b. When activated, the control unit 2U represents the temperature of the substrate 1 measured by the radiation thermometer 18, and adjusts the voltage or current 阳极 between the anode 11a and the cathode 13 The temperature of the substrate 1 becomes a predetermined enthalpy. -14 - 1359878 Next, a deposition process for forming a thin film on the substrate 1 using the DC plasma chemical vapor deposition apparatus of Fig. 1 will be described. In the deposition process, the nanoparticle will be contained. A carbon walled electron discharge 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 is formed by several or tens of single-layer graphite sheets, each of which has a lattice spacing of 〇. 34nm. 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 when the upper surface of the substrate 1 is formed of metal, the active species generated by a part of the source gas is diffused in the substrate 1, the active species-oriented deposition is difficult to deposit on the upper surface of the substrate 1. 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 10 is next decompressed using an exhaust system, and hydrogen, a 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 19 It 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 0 v 01 % throughout the composition of -15 - 1359878. For example, the flow rate of methane is set to 50 seem, the flow rate of hydrogen is set to 500 seem, and the whole pressure is set to 0. 05 to 1. 5 atm' is preferably 0. 07 to 0. 1 atm. The anode 11a rotates the substrate 1 by 1 rPm around the axis 11x 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 a plasma 'and control the electricity The state of the slurry and the temperature of the substrate 1. When depositing the nanocarbon wall, 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 against 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 supply nitrogen in the processing chamber 10. -16- 1359878 Gas environment, then substrate 1 is removed when the temperature is restored 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 10, and the source gas is ejected laterally from the discharge port 22a toward the shaft llx, or in the laterally inward direction, and is discharged by the four exhaust ducts 20. 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 land 11, the flow of the source gas is symmetrically uniform with respect to the axis llx of the process chamber 10. Since the cathode 13 and the cathode support 14 do not interfere with the flow of the source gas, the source gas efficiently flows directly below the center of the cathode 13, which is where the shaft 11 X is located, so come. The source gas is uniformly distributed from the end to the center of the substrate 1, and the density of the active species generated by a part of the source gas in the positive electrode PC becomes uniform. 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 plasma 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 Figure 1 was changed in such a way that the flow of the source gas did not become relative to the axis -17-1359878 » * . The llx is symmetrical, and the cathode 13 is placed between the anode 11a and the nozzle to cause interference. As shown in FIG. 3B, for example, the annular nozzle 22 and the nozzle are removed from the inside of the processing chamber 10, and the gas tube 19 is connected to the gas shower nozzle 25 above the cathode support 14 in the processing chamber 1 so that the gas is vaporized. The nozzle 25 is sprayed downwardly, like 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 discharge from the exhaust duct 20 in which the stopper 24 is mounted. 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 15. 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 concentration of the exhaust duct 20 of the stopper 24, as shown by the two chain lines in Fig. 3B. Since the cathode 13 becomes disturbed by the flow of the source gas, the source gas becomes difficult to surround the cathode 13 to reach the anode 1 space and wipe the position 23 in the body spray conduit, so that it shows a flow velocity in the gas phase. The 13 ° device has a space at the center of the downstream flow toward the point, -18 - 1359878, at the center of the axis llx, 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 11a 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 indicates that the temperature distribution also has an inclination, so that film deposition on the substrate 1 is likely to change. In the DC 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 support 23 to insulate the annular nozzle 22 from the power source or the ground, a waste arc discharge from the cathode 13 or the anode 11a or the like That will not happen. (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, which has a high-density active species between the cathode 13 and the anode 1 la, Therefore, there is no plasma-based temperature rise at the portion where the crucible 22a is ejected, thereby suppressing deposition at the ejection crucible 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 temperature of the gas 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, so It does not 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- 1359878 (6) The annular nozzle 22 is placed at the same position as the electrode surface of the cathode 13, 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 guided. The exhaust duct 20 is directed downward. This prevents the highly reactive active species generated in the positive electrode column PC from being diffused into contact with the cathode 13. It is therefore possible to prevent the active species from depositing on the cathode 13, 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 Figure 1. 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 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 of the anode 11a, and a peripheral green electrode 27b having a ring shape (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 bomb -20- 135. At 9878, sediment may deposit here. This deposit causes or sparks. In this regard, the insulating portion 27c is inserted to be prevented from being on the side walls of the center electrode 27a facing each other and the peripheral side wall. The voltage setting unit 28 has a control unit 28a, and a variable 1 28c « The control unit 28a is connected by wires to the radiation thermometer 18 » 28a has the ability to control the variable power sources 28b, 28c and the voltage between the individual poles 11a and the center electrode 27a Or current, and the voltage or current between the central electrode 2 7 a. DC plasma chemical vapor deposition apparatus in other configuration phase diagrams. If the film is formed on the substrate 1 by using the DC plasma deposition apparatus in FIGS. 5A and 5B, the substrate 1 is rotated at a rate of rpm on the plasma, and the voltage setting unit 28 between the stage 1 1 and the center electrode 27a is rotated. The control will be greater than the potential difference between the stages 11 and 27b to set the voltage between the cathode 27 and the anode 11a to be applied between the anode 11a and the center electrode 27a. This prevents arcing from occurring, which often occurs when a large positive electrode column is produced. After the stable positive electrode PC is applied with such a voltage or electricity at the upper portion of the central portion of the substrate 1, the control unit 28a applies a current such that the voltage between the anode 11a and the central electrode 27a becomes smaller than that of the anode 1 la and the peripheral electrode 27b. The voltage between the anodes 11b and the central electrode 27a is similar to the I source 28b of the arc discharge arresting film sinking electrode 27b, and the control unit is set to the anode 11a and the same as the first vapor phase. The potential difference is at the voltage of the peripheral electrode 3. The small amount is formed at the beginning to add the voltage or current 値 current 値, • the temperature between the anode 1 1 a -21 - 1359878 and the peripheral electrode 27b or such that the temperature is substantially before the film deposition on the substrate 1 equal. In the present embodiment, as described above, the cathode 27 includes a voltage or current 中央 between the center electrode 27a and the peripheral electrode 27b' and between the anode 11a and the center electrode 27a, and a voltage or current between the anode 11a and the peripheral electrode 27b. Can be set independently. When the plasma rises, the voltage between the anode 11a 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 11a 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 PC 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 30 isolates the substrate 1 from outside air. A columnar steel platform 11 is placed in the processing chamber 30. A dish-shaped anode 11a made of a material having high thermal conductivity and a high melting point, such as molybdenum or graphite, i.e., an -22- is mounted on the stage 11. 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 1 lx. The platform 11 below the anode 11a has a closed space llb 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 cooling water or a chlorinated cooling solution, 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 is moved upward, the upper side of the cooling member 12 is adjacent to the bottom side of the platform 1 'the anode 1 1 a which is cooled thereon, 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 to be circulated. 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. The insulating unit 15 for suppressing the occurrence of an arc is placed near the outer surface of the anode Ha. . 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 ' 1359878 such as 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, and is supported by a support 16 provided at the bottom of the process 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 larger 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 placed along the outer side surface of the pole 11a and with respect to the cathode 13, and is disposed The side of the anode 11a is hidden. 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 mounted in the viewing window 17 to ensure that the airtightness within the chamber 30 the radiation thermometer 18 can measure the temperature of the substrate 1 via, for example, the viewing window 17 and be placed outside of the processing chamber 30. The DC plasma chemical vapor deposition apparatus has a source system (not shown) through which a reaction gas is supplied as a source of active species through a gas tube 31, and a source system (not shown) supplies a matrix gas through the gas tube 32 (carrier) Gas) An exhaust system (not shown) that exhausts gas from the inside of the processing chamber 30 via an exhaust conduit, and a voltage setting unit 21. The gas tube 31, which is made of an insulator, 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 1 to ensure airtightness within the processing chamber 30. In the process chamber 30, 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 ejecting ports 33a having equal holes are arranged in a ring shape in a ring-shaped nozzle to measure the yoke of the system y 20 - 24 - 33 1359878 . The inner side surface is provided at an equal distance from the central axis of the shaft llx or the anode 11a. The individual discharge ports 3 3 a are provided at opposite positions with respect to the point symmetry of the axis 1 1 X as the center, and the source gas is uniformly ejected from the discharge port 33a toward the axis llx. 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 is positioned higher than the anode 11a and the cathode The highest point of the positive electrode PC formed between 13. Since the annular nozzle 33 is supported in this range, the reaction gas easily enters between the cathode 丨3 and the anode 1U, and the disturbance of the symmetry of the positive electrode column PC due to the local cooling of the discharge 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 11x of the anode 11a. 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 1U 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. The -25- 1359878 voltage setting unit 21 has a control unit 21a which is connected to the radiation thermometer 18 by a wire and is connected to the variable power source 21b 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 之间 between the anode 11 a and the cathode 13 so that the temperature of the substrate 1 becomes a predetermined enthalpy. An inflation tube 32, which is made of an insulator, passes through a hole provided in the process chamber 30. The sealant is sealed between the hole and the outer side surface of the gas tube 32 to ensure airtightness within the process chamber 30. In the process chamber 30, the charge pipe 32 is connected to the gas spray nozzle 34». The gas spray 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 llx or the center of the gas spray nozzle 34. 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 plasma 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 33 in the lateral inward direction, and the matrix gas is self-contained. The gas shower 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. A verification experiment of the height of the annular nozzle 33 will be explained below. Fig. 7 is a simplified diagram of the verification experiment. • 26-1359878 In this verification experiment, the film deposition was carried out by setting the diameters of the anode 11a and the cathode 13 to 160 mm, and the thickness thereof was set to 15 mm, and the anode 11a and the cathode 13 were The distance between the two is set to 60 mm, the inner diameter of the annular nozzle 33 is set to 305 mm, and the pipe diameter is set to 0. 25吋, the distance between the bottom side where the discharge port of the gas shower nozzle 34 is located and the bottom side of the cathode 13 is set to 260 mm, and the flow rate of hydrogen gas in the matrix gas discharged from the gas shower nozzle 34 is 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, the gas pressure was set to 60 Torr, the current between the cathode 13 and the anode 1 la was set to 16 A, and the crucible substrate had a square shape. One side is 75mm, and its thickness is 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 a high position, and the position of the discharge port 33a positioned above the upper surface of the anode 1 la 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 at the center of the substrate 1 and on the axis 11x, and the distance L1 from the end face by 10 mm and the distance from the two end faces adjacent to the end face 3 7 . The observation point B of the distance L5 of 5 mm is observed in the case where the reaction gas is discharged from the high position, and in the case where the reaction gas is discharged from the low position, the carbon wall on the substrate 1 is observed. growing up. Fig. 9A and Fig. 9C are tomographic SEM images, shown as -27- 1359878 • « · Growth of nanocarbon wall at observation point A and observation point B' when using plasma chemical vapor deposition The discharge port 33a of the nozzle 33 is operated at the high position for two hours. Fig. 9B and Fig. 9D are tomographic SEM images, which are not the growth of the carbon wall at the observation point A and the observation point B respectively. When the plasma chemical vapor deposition is performed by the ejection nozzle 33a of the annular nozzle 33 The low position is performed for two hours. 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 will grow at the observation point B than at the observation point A. Larger. 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 column PC, so the temperature gradient in the gas is small' and non-uniform film deposition does not occur. The experiment of observing the state of film deposition when changing the diameter of the ejecting crucible 33a will now be described. -28-135. 9878 The position of the annular nozzle 33 is set to a high position as shown in Fig. 7, and when the diameter of the discharge port 33a is changed to 0. 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 tantalum substrate, the emissivity is substantially higher as the thickness of the film is increased. The flow rate of the reaction gas per unit time is set to 0 by the diameter of the discharge port 33a. The moving rate of the gas immediately after 5 mm is set to be equal to 500 cm/s, and the diameter of the discharge port 33a is set to 1. The moving rate of the gas immediately after the 0 mm ejection is set to be equal to 125 cm/s, and the diameter of the ejection opening 33a is set to 1. The moving rate of the gas immediately after the 5 mm ejection was set to be equal to 55 cm/s. 10A, 10B, 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, when by having the high position The diameter is set to 0. 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 1 shows the diameter of the ejection raft 33a set to 0. 5mm, l. 0mm and 1. The emissivity of 5 mm at the substrate 1. The tomographic SEM image shows that the diameter of the ejection port 33a is 0. The diameter of 5mm, sprayed out 33a is. 1. 0mm, the diameter of the spray fill 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. However, when the diameter of the squirt 33a is 0. 5 mm (φ〇. 5), 1. 0 mm (Φ1. 0) and 1. 5 mm (Φ 1. 5) Compare the broken p-photography SEM image at observation point A. It can be understood that Φ1. 0 and Φ1. At 5 o'clock, the carbon wall is perpendicular to the direction of the substrate -29- 135. The growth of 9878 is greater than that in Φ〇. 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 Φ 0. 5 and Φ 1. There is almost no change between 0 and the plateau is reached after 1 hour and 30 minutes, however at Φ1. 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 reached the plateau at a faster rate, and the height of the carbon wall of the nanometer was compared to Φ1. 0 and φ 1. At 5 o'clock, the ratio of lateral growth rate seems to be greater than Φ1. 0 and Φ1. 5 status. This represents Φ0. 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 the gas passing 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 Φ0. 5 and Φ1. The 0:2 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 is 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 Φ0. 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 slow 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- 13598. 78 The volume of the body is less 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, when Φ1. The carbon wall formed at 5 o'clock grew to a sufficient density when the deposition time reached 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 33 is about 125 cm/s (the nozzle is Φ1. 0), used for uniform growth of the carbon wall of the nanometer, and ideally, the moving 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- 1359878, it is possible that the cathode 13 and the cathode supporting the cathode 13 support the plasma to become an arc discharge or a spark. The DC vapor deposition apparatus of the present embodiment independently introduces a matrix gas and a reaction gas, and the gas is ejected at a position higher than the substrate 1, and the substrate gas out position is set higher than the discharge position of the reaction gas, so the gas is directed toward the substrate 1. The flow can be manipulated by the downward force of the matrix gas, thereby consuming the amount of reactive gas that is expelled. Further, the substrate gas is ejected from the cathode 13 and the cathode support 14 of the support cathode 13, and the reaction ejection position is set below the bottom side of the cathode 13, so that the downward force gas is applied when it reaches the exhaust duct 20. The reverse flow of the reaction gas toward the flow of the matrix gas is suppressed, and the reaction gas is prevented 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 example of the present invention. The reference numbers given to those components in Figures 12A and 12B shared with the first component. This DC plasma chemical vapor deposition apparatus is the DC vapor deposition apparatus of Fig. 1, in which the cathode 13 is changed to the cathode 35, and its voltage element 21 is changed to the voltage setting unit 36. The cathode 35 has a center electrode 35a facing the anode 11a, a peripheral electrode 35b having a ring shape (see Fig. 12B), and a ring electrode 35a which is concentric with the center electrode 35a and faces the anode 1 edge portion. And the insulating portion 35c made of ceramic or the like is completely 14, so that the reaction of the plasma-forming reaction body is reduced, and the amount of the gas is set in the center of the base cathode body composition and the common slurry chemical setting table is The circumference around the center 1 a is at -32 - 1359878 • * · 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 edge 35b, the film grown by the active species is deposited not only on the side wall of the substrate 1 but also on the side wall of the center electrode 35a and the peripheral electrode 35b facing each other. In this regard, the insulating portion 35c is inserted to prevent the film from being on the side walls of the center electrode 35a facing each other and the wall of the peripheral electrode 35b. The voltage setting unit 36 has a control unit 36a, and a variable power supply 3 6 c β control unit 36a is connected to the radiation thermometer 18 by a wire. The control 36a has the ability to control the variable power supplies 36b, 36c and individually set the voltage or current between the pole 11a and the center electrode 35a and the voltage or current between the anode 1 center electrode 35b. The other configuration is the same as the DC plasma chemical vapor deposition unit shown in the figure. If a film is formed on the substrate 1 using the DC plasma chemical φ deposition apparatus in FIGS. 12A and 12B, the substrate 1 is rotated at a rate at which the plasma rises by 1 rpm, and the electric voltage is set between the anode 11a and the center electrode 35a. The voltage under the control of the unit 36 is greater than the voltage between the anode 11a and the peripheral edge 35b to set an applied voltage between the cathode 35 and the anode 11a to generate a positive electrode PC between the anode 1 la and the central electrode 35a, and Prevents electrical current from occurring during the initial stages of film deposition. When the stabilized positive electrode PC is applied to the upper portion of the central portion of the substrate 1 by applying such a voltage or current, the control unit 36a applies the side 36b on which the electrode is deposited on the side, and the unit is set to the sixth gas phase. 1 Press on the electrode pressure. Small arcs form a voltage of -33- 135. 98. 78 or current causes the voltage or current 値 between the anode 11a and the center electrode 35a to be smaller than the voltage or current 之间 between the anode 11a and the peripheral electrode 35b to approximate the temperature between the anode 11a and the center electrode 35a to the anode. The temperature between lla and peripheral electrode 35b, or such temperatures are substantially equal before film deposition on substrate 1. In the present embodiment, as described above, the cathode 35 includes the center electrode 35a and the peripheral electrode 35b, and the voltage or current 値 between the anode 11a and the center electrode 35a, and the voltage or current 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 center electrode 35a is set higher than the voltage between the anode 11a and the peripheral electrode 35b. Therefore, the positive electrode PC can utilize the distance between the anode 11a and the cathode 35. Shorter to form. The voltage to be applied to the anode 11a and the cathode 35 can be lower, thereby suppressing frequent occurrence of arc discharge or spark. Furthermore, the current flowing through the peripheral electrode 35b becomes smaller than the current flowing through the center electrode 35a to generate the positive electrode PC concentrated at the center of the substrate 1, and then the power applied to the peripheral electrode 35b is increased to increase the flow. The current of the peripheral electrode 35b. This makes it possible to prevent local arc discharge occurring at the initial stage of film deposition, and then the positive electrode PC can be grown to a desired size. [Fifth Embodiment] Fig. 13 is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a fifth embodiment of the present invention. Fig. 14 is a view showing the cathode, the source gas nozzle and the exhaust duct of the DC plasma chemical vapor deposition apparatus of the above Fig. 13. • 34- 1359878 Figure 15 is a cross-sectional view of the DC plasma chemical vapor deposition apparatus of Figure 13 in a 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 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 51a made of a material having high thermal conductivity and high melting point, such as molybdenum or graphite, is mounted on the stage 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 in which a cooling member 52 is placed. The cooling member 52 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 52 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 52b in the cooling member 52 by the conduit 52a, and is discharged by the conduit 52c to circulate in the cooling member 52 to cool the entire cooling member 5 2. When the cooling member 52 moves upward, the upper side of the cooling member 52 abuts against the anode 51a on the bottom side of the platform 51, thereby cooling the heat from the substrate 1. The upper side of the cooling member 52 has a rectangular shape and cools the entire stage 51 in the longitudinal direction. The coolant discharged from the conduit 52c is cooled by a cooling unit (not shown) and again sent to the conduit 52a for recirculation. The space 51b provided below the anode 51a is partitioned by the platform 51, so that the inside of the -35-1359878 space 51b 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 faces the anode 51a. The cathode 53 is made of molybdenum. Graphite or a similar material with a high melting point. The cathode support 54 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 53. The flow of the coolant suppresses overheating of the cathode 53. Preferred coolants are water, calcium chloride solutions and the like which are supplied externally from 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 at least one of a heat insulating oxide such as quartz glass or aluminum, an insulating nitride such as aluminum nitride or tantalum nitride, and an insulating carbide such as tantalum carbide. The insulating unit 5 5 in the shape of a ring is supported at the same height as the anode 51a, which is supported by a support 16 provided at the bottom of the process chamber 50 and provided directly at the inner side of the anode 51a. Since the insulating unit 55 serves to suppress the occurrence of abnormal discharge electric power (arc discharge, spark) between the cathode 53 and the anode 51a, the insulating unit 55 is placed along the outer side surface of the anode 51a and with respect to the cathode 53. The insulating unit 55 may be configured to hide the side of the anode 51a. A viewing window 57 is formed on the side of the processing chamber 50 to allow viewing of the interior of the processing chamber 50. The insulating glass is mounted in the viewing window 57 to ensure airtightness in the processing chamber 50. The radiation thermometer 58 can measure the temperature of the substrate 1 via, for example, a viewing window 57 and is placed outside the processing chamber 50. The DC plasma chemical vapor deposition apparatus has a source system (not shown) that supplies a source gas containing a reactive gas via an inflation tube 59, an exhaust system (not shown) that passes from the processing chamber 50 via the exhaust conduit 60. The internal exhaust gas, and the voltage setting unit 61. The inflation tube 59 is inserted into the treatment chamber 50 via a hole provided in the treatment chamber 50, and at least a portion of the inflation tube 59 is formed of an insulator such as a fluorinated resin or silicone in the reaction furnace. The adhesive is sealed between the pores of the processing chamber 50 and the outer surface of the gas tube 59 to ensure the gas density inside the processing chamber 50. In the process chamber 50, the inflation tube 59 is connected to a nozzle 62 which is a gas supply nozzle. The nozzle 62 has a portion 62A which is parallel to the long sides of each of the anode 51a and the cathode 53, and a portion 62B which 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 the portions 62A, 62B can be branched from the point of attachment to the inflation tube 59. The nozzle 62 is hollow to deliver the source gas. The plurality of discharge banks 62a are linearly symmetrical with respect to the axis 53x or the central axis along the longitudinal direction of the long side of the cathode 533, and are formed at equal intervals in the portion 62A' 62B of the nozzle 62, so that the source gas is ejected by the hopper 6 2 a The substrate 1 is ejected laterally, that is, in a laterally 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 positive electrode column is formed between the anode 51a and the cathode 53. The highest point of the PC. Since the nozzle 62 is supported in this range, the source gas is -37-135. 98. The body easily enters between the cathode 53 and the anode 51a, and prevents the temperature of the gas in the positive electrode column PC from being locally cooled by the ejection of the source gas. The interval between the portions 62A, 62B of the nozzle 62 is larger than the width (short side direction) of the cathode 53, and the portions 62A, 62B of the nozzle 62 are placed outside the both sides of the cathode 53 in the long side direction. The portions 62A, 62B are substantially equidistant from the center line of the anode 51a in the longitudinal direction. The exhaust ducts 60 penetrate the plurality of holes formed in the bottom side of the process chamber 50, respectively, and are sealed at equal intervals around the platform 5 1 «* sealant between each of the holes and the outer side surfaces of the associated exhaust duct 60. The voltage setting unit 61 is a control device that sets the number of voltages or currents between the anode 51a and the cathode 53, and has a control unit 61a and a variable power source 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 61a of the voltage setting unit 61 is connected to the radiation thermometer 58 by a wire, and is connected to the variable power source 61b by a wire. When activated, the control unit 61 a represents the temperature of the substrate 1 measured by the radiation thermometer 58 and adjusts the voltage or current 之间 between the anode 5 1 a and the cathode 5 3 so that the temperature of the substrate 1 becomes a predetermined enthalpy. Next, a deposition process for forming a thin film on the substrate 1 using the DC plasma chemical vapor deposition apparatus of Fig. 13 will be explained. 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 is large 38-135. 9878 « To remove grease/ultrasonic cleaning with ethanol or acetone. This substrate 1 is placed on the anode 51a. When the mounting of the substrate 1 is completed, the processing chamber 50 is next subjected to exhaust pressure, and hydrogen gas, a reaction gas, and a reaction gas (carbonaceous compound) containing carbon in the composition, such as methane, are supplied into the chamber 50 from the gas tube 59. The source gas is ejected from the discharge port 62a of the nozzle 62. When depositing the nanocarbon wall, the film deposition is carried out at a temperature of 900 ° C to the extent that the substrate 1 forms the carbon nanotube wall. This temperature is measured by a radiation thermometer 58. At this time, the cooling structure β is separated from the anode 51a to avoid setting of the radiation thermometer 58 for the temperature of the anode 51a so as to lower the plasma radiation of the DC plasma chemical vapor, and only at the upper surface of the substrate 1. The heat is radiated to the temperature. When the diamond laminate layer containing a plurality of diamond particles is in the nanocarbon wall, the film of the electron discharge film is changed during the nanocarbon wall deposition process, for example, the cooling member 52 is moved upward to abut against the anode 51a. Therefore, the base temperature can be significantly reduced to cause a build-up of the stone layer. In the case of diamonds, the rod-shaped sp2 bonds carbon, which is a modified part of the nanocarbon wall, is a carbon nanotube that grows with a fused core. This rod-like shape protrudes from the upper surface of the diamond layer, and is structurally concentrated and releases electrons. At the end platform of the film deposition, the anode 51a and the cathode 53 are applied with a voltage to stop, and then the supply of the source gas is stopped, and the gas is supplied to the processing chamber 50 as a cleaning gas to be discharged into the processing chamber 50 to the system. Treatment of 1 100 ° C minutes of temperature: 52 large effects. The device is taken to take the upper, and the layer of the plate 1 grows and unlike the carbon extending electric field between the supply of nitrogen to provide nitrogen -39- 13598. 78 atmosphere, then substrate 1 is removed when the temperature is restored to normal temperature. The DC plasma chemical vapor deposition apparatus according to the present embodiment has the following advantages (8) and (9) ° (8) in addition to the advantages (1) to (6) of the first embodiment in order to have a large Thin film deposition is performed on the substrate 1 of the area, which requires an increase in 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 platform 11 and the cathode 13 may cause insufficient reaction gas to be supplied to the center of the platform 1, or may be. 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 stage 51 and the cathode 53 have a rectangular shape, and the portions 62 2A, 62B of the nozzle 62 are placed parallel to the longitudinal direction. This ensures that the supply of the source gas does not change in the long-side direction, thereby making it possible to suppress variations in film deposition in the long-side direction. Properly setting the length of the anode 5 1 a and the cathode 53 in the short-side direction ensures that the variability of film deposition is suppressed on the substrate 1 having a large area. (9) Since the stage 51 and the cathode 53 have a rectangular shape, the plurality of square substrates 1 can be placed in the longitudinal direction of the anode 51a and the cathode 53, so that simultaneous film deposition can be performed once on the plurality of substrates 1. This is suitable for mass production. In this case, the plurality of substrates 1 are subjected to thin film deposition in the same processing tank, so if film deposition is performed on the required number of substrates, it is not necessary to consider variations between the processing grooves. [Sixth embodiment] - 40 - 13598, 78 Fig. 16A is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a sixth embodiment of the present invention, and Fig. 16B is a view from below Plan view of the cathode. Fig. 17 is a view showing a cathode, a source gas nozzle and an exhaust duct of the DC plasma chemical vapor deposition apparatus of the above-mentioned 16A. Figure 18 is a cross-sectional view of the DC plasma chemical vapor deposition apparatus of Figure 16A in the lateral direction. The DC plasma chemical vapor deposition apparatus is the DC plasma chemical vapor deposition apparatus of the fifth embodiment shown in Fig. 13, wherein the cathode 53 is changed to the cathode 65, and the voltage setting unit 61 is changed to a voltage setting unit. 66. The cathode 65 has a central electrode 65a facing the central portion of the anode 51a, and a peripheral electrode 65b shaped like an annular ring (see Fig. 16B), surrounding the central electrode 65a, facing the peripheral portion of the anode 51a, and ceramic or the like The insulating portion 65c is formed to be completely filled between the center electrode 65a and the peripheral electrode 65b. If the insulating portion 65c is not inserted between the center electrode 65a and the peripheral electrode 65b, 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 65a and the side wall of the peripheral electrode 65b which face each other. In this regard, the insulating portion 65c is inserted to prevent the carbon film from being deposited on the side walls of the center electrode 65a facing each other and the side wall of the peripheral electrode 65b. The voltage setting unit 66 has a control unit 66a, and the variable power source 66b, 66c 0 The control unit 66a is connected to the radiation thermometer 18 by wires. Control unit -41 - 1359878 • * . 66a has the ability to control the variable power supplies 66b, 66c and individually set the voltage or current between the anode 51a and the center electrode 65a, and the 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 a 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 rpm as the plasma rises, and between the stage 51 and the center electrode 65a. The voltage difference will be greater than the voltage difference between the platform 51 and the peripheral electrode 65b under the control of the voltage setting unit 66 to set the voltage between the cathode 65 and the anode 51a. Such an applied voltage generates a small positive electrode PC between the anode 51a and the center electrode 65a, and arc discharge can be prevented from occurring at 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 66a applies the voltage or current so that the voltage or current between the anode 51a and the central electrode 65a becomes It is smaller than the voltage or current 之间 between the anode 51a and the peripheral electrode 65b to approximate the temperature between the anode 5 1 a and the center electrode 65a to the temperature between the anode 5 1 a and the peripheral electrode 65b, or to make those temperatures The substrate 1 is substantially equal before film deposition. In the present embodiment, as described above, the cathode 65 includes the center electrode 65a and the peripheral electrode 65b, and the voltage or current 値 between the anode 51a and the center electrode 65a, the voltage between the anode 51a and the peripheral electrode 65b or The current 値 can be set independently. When the plasma rises, the voltage between the anode 51a and the center electrode 65a is set higher than the voltage -42 - 1359878 between the anode 51a and the peripheral electrode 65b. 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 may be lower, thereby suppressing frequent occurrence of arc discharge or spark. Further, the current flowing through the peripheral electrode 65b becomes smaller than the current flowing through the center electrode 65a to generate the positive electrode PC concentrated at the center of the long side of the substrate 1, and then the electric power applied to the peripheral electrode 65b is increased to The current flowing through the peripheral electrode 65b is increased. This makes it possible to prevent local arc discharge occurring at the initial stage of film deposition, and then the positive electrode PC can be grown to a 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, which is shared with the components of Fig. 13 in Fig. 19. The component is given a shared reference number. Fig. 20 is a view showing the cathode, the reaction gas nozzle, the matrix gas shower nozzle, and the exhaust duct of the DC plasma chemical vapor deposition apparatus of the above-mentioned Fig. 19. Figure 21 is a cross-sectional view of the DC plasma chemical vapor deposition apparatus of Figure 19 in a 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 7 隔离 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, is mounted on the stage 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 multi-43- 1359878 number square substrate 1 may be placed on the anode 51a. The platform 51 below the anode 51a has a closed space with a cooling member 52. The cooling member 52 is used for the optional sheet and constructed to be moved downward by an arrow by a moving mechanism (not shown). The cooling member 52 is made of metallic copper having high thermal conductivity. A coolant such as cooling water or calcium chloride cooling duct 52a enters the flow passage 52b in the cooling member 52, and is discharged to circulate in the cooling member 52 to cool the entire cooling when the cooling member 52 moves upward, the cooling member 52 is placed against the bottom side of the platform 51, and the heat of the anode 5 on which the cooling is located is carried away by the substrate 1. The upper side of the cooling member 52 cools the entire stage 51 in the longitudinal direction. The coolant discharged from the conduit 52c is recirculated by a cooling unit (not shown to be re-circulated to the conduit 52a. The space 51b provided under the anode 51a is filled with gas or opened into the air by the interior of the space 51 1b of the platform 51. The cathode 53 is placed on the anode 51a. It is supported on the cathode support 14 and faces the anode 51a. The cathode 53 or a similar material having a high melting point is formed. The cathode support 54 is made of a heat insulating oxide such as quartz glass nitrogen. A compound, such as aluminum nitride or tantalum nitride, or an insulating carbide, etc. The passage through which the coolant flows can be formed in the cathode 53. The cold can suppress the overheating of the cathode 53. The preferred coolant is Water, chlorine 5 lb, wherein > is formed on the substrate 1, as shown, for example, by: the upper side of the member 52 2 of the conduit 52c is tightened, thereby cooling the square and cooling out, and Separated, so the cathode 53 is made of molybdenum, graphite or aluminum, insulated, such as a fluidized calcium solution of a carbonizing agent, and -44-135,9878, which 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 51a. The insulating unit 55 contains 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. The insulating unit 55, which is annular in shape, is supported at the same height as the anode 5U, and is supported by a support 16 provided at the bottom of the process chamber 70 and provided directly at the inner side of the anode 51 a. Since the insulating unit 55 serves to suppress the occurrence of abnormal discharge (arc discharge, spark) between the cathode 53 and the anode 51a, the insulating unit 55 is placed along the outer side surface of the anode 51a and with respect to the cathode 53. The insulating unit 55 can be configured to hide the side of the anode 5 1 a. A viewing window 57 is formed in the side of the processing chamber 70 to allow viewing of the interior of the processing chamber 70. The insulating glass is mounted 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, and is placed outside the processing chamber 70. The DC plasma chemical vapor deposition apparatus has a reaction gas system (not shown) that supplies a reaction gas through an inflation tube 71, a source system (not shown) that supplies a matrix gas through the inflation tube 72, and an exhaust system (not shown) The gas is discharged from the inside of the processing chamber 70 through the exhaust duct 60, and the voltage setting unit 61. 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 inflation tube 71 is formed of an insulator such as a fluorinated resin or silicone in the reaction furnace. The adhesive is sealed in the hole of the processing chamber 70 -45- 13598. The hole is between 78 holes and the outer side surface of the inflation tube 71 to ensure the gas density inside the processing chamber 70. In the process chamber 70, the inflation tube 71 is connected to the nozzle 73' which is a reaction gas supply nozzle. The nozzle 73 has a portion 73A which is parallel to the long sides of each of the anode 51a and the cathode 53, and a portion 73B which is parallel to the other long side of each of the anode 51a and the cathode 53. The nozzle 73 may be the entire ring shape, or the portions 73A, 73B may be branched by a connection point with the inflation tube 71. The nozzle 73 is hollow to transport the reaction gas. The plurality of discharge ports 73a are formed in the portions 73A, 73B of the nozzles 73 at equal intervals in a linearly symmetrical manner, so that the source gas is ejected laterally toward the substrate 1 by the discharge ports 73a, i.e., in the lateral inward direction. The nozzle 73 is supported by an insulating nozzle support 63 attached to the cathode support 54. The support height of the nozzle 73 is set in such a manner that the discharge port 73a is lower than the lowest position of the cathode support 54 (the uppermost portion of the exposed side of the cathode 53), and the positive electrode column is formed between the anode 51a and the cathode 53. The highest point of the PC. Since the nozzle 73 is supported in this range, the source gas easily enters between the cathode 53 and the anode 51a, and the temperature of the gas in the positive electrode column PC can be prevented from being locally cooled by the ejection of the source gas. The interval between the portions 73A, 73B of the nozzle 73 is larger than the width (short side direction) of the cathode 53, and the portions 73A, 73B of the nozzle 73 are placed outside the both sides of the cathode 53 in the long side direction. The portions 73A, 73B are substantially equidistant from the center line of the anode 51a in the longitudinal direction. The exhaust ducts 60 respectively penetrate the plurality of holes formed 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 associated and exhaust surfaces of the associated exhaust conduit 60. -46 - 1359878 The voltage setting unit 61 is a control device that sets the number of voltages or currents between the anode 51a and the cathode 53, and has a control unit 61a and a variable power source 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 is connected to the variable power source 61b by a wire. When activated, the control unit 61 a represents the temperature of the substrate 1 measured by the radiation thermometer 58 and adjusts the voltage or current 之间 between the anode 5 1 a and the cathode 5 3 so that the temperature of the substrate 1 becomes a predetermined enthalpy. An inflation tube 72, which is made of an insulator, passes through a hole provided in the processing chamber 70. A sealant is sealed between the hole and the outer side surface of the gas tube 72 to ensure airtightness within the process chamber 70. In the process chamber 70, an inflating pipe 72 is connected to the gas shower nozzle 74 for the matrix gas. A gas shower nozzle 74 having substantially the same length as the cathode 53 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 53x as a The central axis of the cathode 53 in the longitudinal direction is directed to eject a matrix gas downward, such as 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 DC plasma chemical vapor deposition apparatus of the fifth 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 sprayed from the nozzle 73 in the lateral inward direction -47-1359878, and 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 the present 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 the gas mixture is supplied to the substrate by a naturally generated convection, and the new gas mixture is sufficient to affect the film deposition on the substrate 1. The newly introduced gas mixture is discharged from the exhaust duct 60, which is sufficiently charged to the substrate 1 so that the reaction gas may be wasted wastefully. If the concentration of the reaction gas in the gas mixture is increased to prevent the reaction gas-directed precipitate from occurring, the cathode 53 and the insulating cathode support 54 supporting the cathode 53 may cause the plasma to become an arc discharge or a spark. The DC plasma chemical vapor deposition apparatus of the present embodiment independently introduces a matrix gas and a reaction gas, sets a discharge position of the reaction gas to be relatively higher than the substrate 1, and sets a discharge position of the matrix gas higher than a discharge position of the reaction gas, so The flow of the reaction gas toward the substrate 1 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 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, so that the downward force reaches the exhaust conduit of the matrix gas. At 60 o'clock, the reverse flow of the reaction gas toward the cathode 53 against the flow of the matrix gas is suppressed, and the insulating gas support of the reaction gas -48-1359878 body component is adhered to the cathode 53 and the support cathode 53. [Eighth embodiment] 22A and 22B are configuration diagrams of a DC plasma chemical vapor deposition apparatus according to an eighth example of the present invention. The reference numbers used for those components in Figures 22A and 22B that are shared with the dance components. Figure 23 is a diagram showing the cathode of the DC plasma chemical vapor deposition of the above-mentioned 22A, the reaction gas nozzle, the substrate gas nozzle and the exhaust conduit 6. Fig. 21 is a DC plasma chemical gas device of the 22A side of the lateral direction. Cutaway view. The DC plasma chemical vapor deposition apparatus is the DC plasma chemical vapor deposition apparatus of the body embodiment shown in Fig. 19, the cathode 53 of the cathode 75, and the voltage setting unit 61 is changed to a voltage setting. The single cathode 75 has a central portion. The electrode 75a, which faces the anode 51a, has a peripheral electrode 75b which is annular in shape (see Fig. 22B), a central electrode 75a which faces the peripheral portion of the anode 51a, and a ceramic or finished insulating portion 75c which is completely 塡It is between the center electrode 75a and the circumference 7 5 b. If the insulating portion 75c is not inserted between the center electrode 75a and the circumference 75b, the film grown by the active species is deposited not only on the side wall and the peripheral electrode 75b of the center electrode 75a where the substrate 1 faces each other. In this regard, the insulating portion 75c is inserted to prevent the carbon film from facing the side wall of the center electrode 75a and the peripheral electrode 75b. 54 on. Figure 19 shows the diagram of the co-product. The seventh phase of phase deposition is changed to : 76 ° central portion surrounded by a similar edge electrode on the edge electrode , also the side wall deposited on the side wall -49- 1359878 . The voltage setting unit 76 has a control unit 76a and variable power supplies 76b, 76c. Control unit 76a is connected by wires to radiation thermometer 58. The control unit 768 has the ability to control the variable power supplies 76b, 76c and individually set the voltage or current between the anode 51a and the center electrode 75a, and the voltage or current between the anode 51a and the center electrode 75a. 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 by using the DC plasma chemical vapor deposition apparatus in FIGS. 22A and 22B, the voltage between the anode 51a and the center electrode 75a is controlled by the voltage setting unit 76 when the plasma rises. Below it is greater than the voltage between the anode 51a and the peripheral electrode 75b to set the voltage between the cathode 75 and the anode 51a. Such an applied voltage generates a small positive electrode PC between the anode 51a and the center electrode 75a, and can prevent arcing from occurring at an 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 control unit 76a applies the voltage or current in such a manner that the voltage or current 値 between the anode 51a and the center electrode 75a becomes smaller than the voltage or current 之间 between the anode 51a and the peripheral electrode 75b to connect the anode 5 1 a with The temperature between the center electrodes 75a approximates the temperature between the anode 51a and the peripheral electrode 75b, or such that the temperatures are substantially equal before the film deposition on the substrate 1. In the present embodiment, as described above, the cathode 75 includes the center electrode 75a and the peripheral electrode 75b, and the voltage or current 之间 between the anode 51a and the center electrode 75a, and the voltage or current between the anode 51a and the peripheral electrode 75b - 50- 1359878 値 can be set independently. When the plasma rises, 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 gg separation between the anode 51a and the cathode 75 shorter. The voltage to be applied to the anode 51a and the cathode 75 may be lower, thereby suppressing frequent occurrence of arc discharge or spark. Further, the current flowing through the peripheral electrode 75b may become smaller than the current flowing through the center electrode 75a to concentrate on The power of the positive electrode PC at the center of the substrate 1 and then applied to the peripheral electrode 75b 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, and then the positive electrode PC can be grown to a desired size. The invention is not limited to the specific embodiments described above, and can be modified into a variety of other forms. The following are some possible modifications. (a) The structure of the cathodes 27, 35 including the plurality of electrodes can be appropriately changed depending on the size of the substrate 1 to be processed and the anode 11a. For example, 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 of the peripheral electrodes 90b. The insulating portion 90c of the ceramic is interposed between the center electrode 90a and the peripheral electrode 90b. Each of the cathodes 91, 92 as shown in Figs. 26 and 27 has a plurality of circular peripheral electrodes 91b, 92b which are designed to have the same size as the center electrode 91a' 92a. In each of the cathodes 91, 92, ceramic insulating portions 91c, 92c are filled between the peripheral electrodes 91b, 92b and the center electrodes 91a, 92a. (b) Although the cathodes 27, 35 are constructed to have the central-51 - 1359878 electrodes 27a, 35a and the peripheral electrodes 27b, 35b' having the same central arrangement similar to the cathode 93 of the 28th, the cathode can be constructed to have three concentric centers The center of the annular center electrode 93a surrounds the center electrode 93a and isolating the annular peripheral electrode 93b' and the second annular peripheral electrode 93c from the ring-shaped peripheral electrode 93b. (c) The cooling member 12 can also be modified. Fig. 29A is a top view showing another modification of the member 12 of the DC plasma chemical vapor deposition apparatus, and Fig. 29B is a schematic sectional view showing the cooling member 12 of the 29A line A-A. Fig. 30A is a top view of the cooling member 12 in Fig. 29B and Fig. 29B, and a cooling operation of the cooling member 12 along the line B-B in Fig. 30B 30A. In the plasma chemical vapor phase shown in Figs. 29A and 29B, the cooling member 12 has conduits 12a, 12b, and 12c in which the coolant supplied from the cooling unit 99 is supplied. Above the cooling member 12, a side groove 12y extending from the vent hole 1 2x to the cooling member 12 is formed. Therefore, as shown in Fig. 30B, even when the cooling member] side 12w abuts against the stage 11, the cooling gas passes through and moves the passage formed in the gap between the surface and the platform 1 1 as by the arrow Efficient exhaust and cooling. The helium gas, whose exhaust gas flow rate is adjusted by the controller 95, is sent to the three-way valve 98 by the helium gas charging unit 94. The exhaust flow rate is adjusted by the flow controller 97 and sent to the three-way valve 98 by the nitrogen charging unit. When the three-way valve 98 is opened, the cooled ammonia gas and nitrogen gas are sprayed onto the abutting surface of the stage 1 1 via the vent hole 1 2 X, the substrate 1. The first electrode shown in the figure, around the first cooling pattern, is shown in Fig. 29A as a cross-sectional view of the deposition device flowing through the side 1 2 w 12z . 2 is shown in the upper trench, the flow rate is controlled by nitrogen, and 96 is cooled to cool -52-1359878. [Ninth Embodiment] FIG. 31 is a DC plasma chemical vapor phase according to a ninth embodiment of the present invention. Configuration example of the deposition device. The DC plasma chemical vapor deposition apparatus forms a thin film on the upper surface of the substrate 101 to be processed, and has a 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, and is placed on the substrate mounting surface 112a above the anode 112. The anode 112 is formed of graphite, and the surface roughness 平均Ra is about 5 μηη. The stage 111 below the anode 112 has a closed columnar space 111b, and the electrode mounting surface 111a of the stage 111 has a flat shape. The columnar cooling member 1 1 3 is placed in the space 1 1 1 b of the platform 1 1 1 . The cooling member 1 1 3 is used to cool the substrate 101 and is formed of a metal having high thermal conductivity, such as copper. The cooling member 113 is constructed to be movable up and down by a moving mechanism (not shown) as indicated by an arrow. The upper end surface of the cooling member 113 is an opposite surface U3a (hereinafter referred to as "bottom surface") facing the surface 11 lc with respect to the electrode mounting surface 11 la of the stage 111, and has a large outer diameter. When the cooling member 113 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 0 the flow passage 1 1 3 b through which the coolant flows, for example, cooling A water or calcium chloride solution is formed in the cooling member 113. The flow passage 1 1 3 b self-cooling -53 - 1359878 • The side of the member 113 passes through, approaches the opposite surface 113a, and reaches the side of the cooling member 1 13 again. The flow passage 1 13b is connected to the cooling unit 113 via the conduits 1 13c, 1 13d, so the coolant is cooled by the cooling unit 115 and circulated between the flow passage 11 3b and the cooling unit 115. The vent hole 113e is formed at the center of the opposite surface 113a of the cooling member 113. The vent hole 11 3e passes through the lower side surface of the cooling member 113. At the lower side of the cooling member 113, the vent hole 1 1 3e 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 as a cooling gas. The cooling gas is filled in the space 111b but is not filled on the substrate mounting surface 112a side of the anode 112. It is apparent that the cooling member 113 has a mechanism for cooling the stage 1 1 1 with a coolant, and a mechanism for cooling the stage 111 by spraying a cooling gas from the vent hole 1 1 3 e onto the stage 1 1 1 . Therefore, when cooling the anode 112 and the substrate 101, a method of causing the opposite surface 113a to partially or entirely abut against the bottom surface 111c of the stage 1 1 1 may be selected, with a method of moving the opposite surface 1 1 3 a closer to the bottom surface 111c. A method of spraying a cooling gas onto the platform 111, 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 122 is provided at a location above the cathode 120 in the process chamber 110 for supplying a source gas that is supplied to the process chamber 110 by a source gas system (not shown). A gas discharge pipe - 54 - 1359878 for discharging the source gas is provided at the bottom of the process chamber 110. The gas supply line 122 and the gas discharge line 123 are provided in the pores provided in the individual treatment chamber 110, and the sealant is sealed on the outer surface of each of the hole gas supply line 122 and the gas discharge line 123 to ensure the inside of the processing chamber 110. Air tightness. The connection to the gas discharge double is an exhaust system (not shown) which is discharged from the gas discharge line 123 to adjust the atmospheric pressure in the process chamber 110. A viewing window 125 is formed on the side of the processing chamber 110 to allow the interior of the chamber 110. In this case, the insulating glass is mounted in view to ensure airtightness inside the processing chamber 110. The spectroradiometer measures the temperature of the substrate 1 〇 1 outside the processing chamber 110 by, for example, an insulating glass of the viewing window 125. When the substrate 1 〇 1 film deposition is performed using a DC plasma chemical vapor deposition apparatus, first, the substrate 101 is placed on the substrate mounting of the anode 112. When the mounting of the substrate 101 is completed, next, the processing chamber 1: is decompressed using the exhaust system, and then the gas is supplied from the gas supply line 12 to the processing chamber 110. The source gas is a reaction gas (such as methane) and a matrix gas (carrier gas) to be used for film deposition (such as a hydrogen hydride), which does not become a film deposition material in a predetermined ratio. Graphite, diamond particles are deposited on 101. Or a similar carbon film, the gas which becomes a carbon-containing compound. The pressure in the processing chamber 110 is set to a predetermined enthalpy, or it is adjusted by the supply amount and the discharge amount of the source gas. The variation falls within the allowable range. The platform 111 can be, for example, between the existing and the other, the road 123 source gas observation window 125 126, and the carbon mixed with the material U of the thin® 112a 0 The substrate is rotated in the gas mode by the predetermined 10 rpm -55 - 1359878 to rotate the substrate 101 and the anode 112». In this case, a DV voltage is applied between the anode 112 and the cathode 120 to generate plasma. When plasma is generated, The plasma generates an active species from the reaction gas, thereby starting film deposition on the substrate 101. The rotating substrate 101 and the anode 112 lower temperature changes according to the position of the substrate 101, thereby preventing on the substrate 101. Variation in film deposition. In order to ensure the desired film thickness by suppressing the rise in temperature of the substrate 101 due to deposition, or to change the film quality by changing the temperature of the substrate 101 during film deposition, in the cooling member 1 1 The cooling mechanism provided at 3 is appropriately selected and used. That is, the opposite surface 113a can be brought against the bottom surface 111c, so that the coolant cooled by the cooling unit 115 flows in the flow passage 113b of the cooling member 113. Or the cooling gas may be sprayed onto the bottom surface 11 lc to allow the opposite surface 1 13a to approach the bottom surface 11 lc, or the cooling gas may be sprayed onto the bottom surface 111c while allowing the portion of the opposing surface 11 3a to abut against the bottom surface 111c Since the surface temperature of the substrate 101 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. Control. When a predetermined time elapses from the start of film deposition, the film deposition proceeds to the end stage, between the anode 1 12 and the cathode 1 20 The voltage is stopped, then the supply of the source gas is stopped, and nitrogen gas is supplied to the processing chamber 1 1 0 as a cleaning gas to set the pressure therein to a normal pressure, and then the substrate 101 is removed. Next, the DC plasma chemical vapor phase will be explained. Advantages of the deposition device. -56- 13598. When the film deposition on the substrate ιοί is performed, the substrate ιοί, the anode 112 and the cathode 120 are exposed to the plasma generated between the anode 112 and the cathode 120 to be heated. When a portion of the energy supplied to the substrate 101 is transferred from the thermal radiation to the processing chamber 110, most of the energy is transferred from the substrate 101 to the anode 112 and the stage 111, and is further transmitted to the cooling member 113 via the stage 111. Since the transferred heat is balanced with the diffused heat, the temperature of the substrate 101 can be kept constant. The film deposition can be carried out simultaneously with the anode 112 being formed of graphite (hereinafter referred to as "graphite electrode") and the anode 112 being formed of molybdenum (hereinafter referred to as "molybdenum electrode"), and the results are compared. In the example of the graphite electrode and the molybdenum electrode, the deposition conditions are such that the source gas sets the flow rate of methane in the reaction gas to 50 seem, and the flow rate of hydrogen in the matrix gas is set to 500 seem, which is supplied to the process chamber 110. Medium, and the general pressure is maintained at 7 999 by adjusting the discharge speed. 3 2 Pa. Further, the plasma is generated by applying electric power so that the current density between the cathode 120 and the graphite electrode and the molybdenum electrode becomes 〇 15 A/cm 2 (current / electrode area). The roughness of the surface of the molybdenum electrode has an average 値Ra of 1. The thermal conductivity λ of 5 μπί' large movement is 132 W. m·1·!^1. The roughness of the surface of the graphite electrode to be the anode Π2 is 値Ra of 5 μηη. The thermal conductivity λ of a large amount of movement is 120 W · m -1 · Κ-1. The thickness is 0. 5 mm is used for the substrate 1〇1' and the distance X between the opposite surface 113a and the bottom surface 111c of the stage 111 in Fig. 31 is set to 60 mm, which is about 2 hours after the start of film deposition, thereby changing the substrate 1〇1 The temperature -57- 13598. 78 degrees. During this period, a nano-carbon wall is formed on the substrate 101 using a graphite electrode in a plasma chemical vapor deposition apparatus to form a plurality of parallelepiped (fan-shaped) thin carbon sheets having an upright curved surface in a random direction. Chained together. Each thin carbon sheet is formed by several or tens of single-layer graphite sheets each having a lattice spacing of 0, 3 4 nm » and then the distance x is close to zero. 5mm. Then, 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 113e at 500 seem to lower the temperature of the substrate 110. 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 grade (less than 1 μm) is deposited on the substrate 101. On the carbon wall of the nano-carbon, a part of the nano-carbon 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, which is formed by the crystallite The surface of the diamond film is prominent. This carbon rod is formed with carbon therein, and unlike 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 110 and perform an intensity spectrometer from the infrared radiation of the substrate 101, and the temperature of the substrate 1 〇1 and its emissivity are approximated by using gray body approximation. To evaluate. Figure 32 shows the temperature of substrate 101 measured for different anodes 112. As shown in Fig. 32, for any of the electrodes, the temperature of the substrate 1〇1 reaches the peak point within 30 minutes after the start of film deposition, and then the temperature of the substrate 1〇1 is lowered and the current density is constant. The reason why the temperature of the substrate 1〇1 has a downward trend of 58-1359878 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 丨01 rises, thereby increasing the substrate 101 from the substrate 101. The upper surface radiates heat transferred 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 101 which varies for different electrodes is shown in the initial deposition region, the temperature of the substrate 101 will vary greatly, and the temperature of the substrate 101 on the graphite electrode is lower than the temperature of the substrate 101 on the molybdenum electrode by 100 ° C or more. many. In the subsequent state, the temperature becomes stable even if the distance X is 0. 5 mm, the temperature of the substrate 101 when using the graphite electrode is 40 ° C lower than the temperature of the substrate 101 when the molybdenum electrode is 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 112 and the cathode 120 is controlled to be fixed at 0. 15 A/cm2, and the applied voltage is automatically changed according to 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 101 to become high, and the ambient gas temperature is increased by the substrate 101 and the electrode, and thus the density thereof is lowered, the voltage allowing the current having the same density to flow is lowered for the graphite electrode, The temperature of the substrate 101 is made lower. When the molybdenum electrode is used, the applied electric power is always lower than when the graphite electrode is used, so the amount of change in electric power is equal to or less than 1. 5%. -59- 13598. 78 Even if the applied power is hardly changed, there is always a difference of 100 °C in the temperature of the substrate 101 between the molybdenum electrode and the graphite electrode because the graphite electrode is more likely to escape heat in the temperature region than the molybdenum electrode. 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 0 due to surface reflection. 3 or so, compared to the emissivity of graphite 0. 9 or higher, so it can be easily interpreted as a graphite electrode such that the temperature of the substrate 101 is low. When the temperature of the substrate 101 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 may be changed in proportion to the temperature difference, but the radiant heat type 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 amount of the rapid discharge, 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 101 is T, 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... can be expressed by the following formula. -60- 1359878 • · , Formula 1

其中λ爲陽極材料的導熱性，r爲基板101與陽之間的外觀接觸面積與基板101與陽極112之間的觸面積的比例，而Ra爲該表面的粗糙度平均値。雖爲準確的公式中對於基板101與陽極112之間的間修正項，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，在基與陽極1 1 2之間的縫隙中有經由氣體傳遞的熱傳導熱傳遞簡化成藉由位在具有不同溫度之兩個平行板 • 靜態層的熱傳遞，在0.1或更低的壓力之環境中’ . 電漿化學氣相沈積在取得如第3 2圖所示之資料常，該平均自由路徑可視爲充份大於該基板底側的糙度。因此，傳遞熱量可視爲自由分子熱傳導°此遞熱量Wel可表示成下式。 • 公式2Where 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 to the contact area between the substrate 101 and the anode 112, and Ra is the roughness average of the surface. Although the correction term between the substrate 101 and the anode 112 in the accurate formula is omitted here for rough calculation. # In addition to the heat transfer caused by the contact between the solids, the heat transfer through the gas transfer in the gap between the base and the anode 1 12 is simplified to be achieved by two parallel plates with different temperatures. The heat transfer of the layer, in an environment of pressure of 0.1 or less. ' Plasma chemical vapor deposition is often obtained as shown in Fig. 3, and the mean free path can be considered to be sufficiently larger than the bottom side of the substrate. Roughness. Therefore, heat transfer can be regarded as free molecular heat conduction. This heat transfer Wel can be expressed as follows. • Formula 2

Wgi =(l-r)x« A·/7-(^-T2) 極112 真實接然在更距引入板101 。如果之間的其對於時很正表面粗時，傳 Λ = ίWgi = (l-r) x « A·/7-(^-T2) pole 112 is actually introduced into the board 101 at a greater distance. If there is a very rough surface between them, pass Λ = ί

χ + 1 ,r~1J kχ + 1 ,r~1J k

2nmT2nmT

T τ,+τ2 2 其中Λ爲自由分子熱導性爲可適化係數’ Ρ焦壓力， -61 - 1359878 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 10·27 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 _T τ, +τ2 2 where Λ is the thermal conductivity of the free molecule is the aptamability coefficient Ρ coke pressure, -61 - 1359878 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 the maximum 値1, and the specific heat rate is 7/5 and the mass of the gas molecule is 3.3 X 10·27 Kg, which is the hydrogen molecule of the plasma main gas. Hey. 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. Formula 3 _

Wn={\~r)xa^ -T24)~—~ί—— —I---1 ε\ S2 其中81與82分別爲平面y與平面ζ的發射率，σ爲史特凡·波茲曼（Stefan-Bolzmann)常數（5.67 X 10.8 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〇.6，鉬的發射率爲 0.3，石墨的發射率爲〇.9，基板1〇1與陽極112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。(：，陽極基板爲860。C，且基板面積爲。對於鉬電極，對基板1〇1之接觸熱導性成爲約5W，鉬電極與基板1〇1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101之接觸熱導性成爲約1W，石墨電極與基板101之間的自由分子導向的熱導性成爲約l〇W，而熱輻射熱成爲約11W。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- 135,9878 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況。即使基板與陽極之間的外觀接觸面積與基板間的真實接觸面積的比例r由於布局改變而變化丨對値很小，所以由該基板傳遞熱量到該陽極之改會根據輻射式的傳遞熱量，並僅取變正比於r改式傳遞熱量。此時，因爲輻射式傳遞熱量的貢獻拭在接觸式傳遞熱量中大部分的改變即正比於（T，4 可由相對於溫度變化爲大的輻射式傳遞熱量改變藉此使其有可能相對地降低ΊΊ的改變量。顯示有到輻射式傳遞熱的石墨電極可抑制相對於在具有之電極中的改變在基板溫度中的變化，藉此穩定沈積條件。對於陽極1 1 2使用石墨電極可防止不想要的沈積在陽極112上，如下所述。第34A圖及第34B圖所示分別爲薄膜沈積之與石墨電極之狀態的照片。將陽極1 1 2做爲鉬電極，如第3 4 A圖所示，積之後碳膜形成在並未安裝基板101的部分上。新的基板放置在具有形成碳膜的鉬電極上時，在膜的部分處的表面粗糙度進一步改變，所以接觸使得溫度控制更加困難。對於石墨電極，如第34B圖所示，幾乎沒有所以在表面粗糙度沒有變化的更爲穩定的溫度控小r的情及陽極之诗，r的絕變幾乎不變的接觸 t爲較大， TV)，並來補償，大的分布小發射率該等薄膜沈積物被後鉬電極於薄膜沈因此，當形成有碳式傳遞熱沈積物，制即成爲 -63- 1359878 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112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3 5圖所示，在容納基板1 0 1的凹處可形成在基板安裝面112a中，以加寬陽極112的熱輻射表面，以增加熱輻射。在此例中，較佳地是陽極112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111a中，以匹配於陽極Π2之突出且平臺Π1之底側爲突出’其突出來匹配電極安裝面 11U之凹處的深度，以使平臺U1的均勻度均勻，而使得平臺111的溫度均勻。然後較佳地是在相對面U3a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 〇 1的底側並非平滑，凹處 -64 - 13598,78 可形成爲匹配基板101的形狀，所以基板101可安裝在該凹處中。在此例中，較佳地是陽極112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 111a之凹處的深度，以使平臺111的均勻度均勻，而使得平臺111的溫度均勻。然後較佳地是在相對面113a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101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DC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- 1359878 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28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- 1359878 第31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32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33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 Γο*Τ · 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3 7 Α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- 上方側排氣孔溝槽側面陰極陰極支撐絕緣單元支撐觀視窗輻射溫度計充氣管排氣導管電壓設定單元控制單元可變電源環狀噴嘴噴出埠絕緣體噴嘴支撐停止器氣體噴淋噴嘴陰極中央電極周緣電極絕緣部分電壓設定單元 -69- 13598.78Wn={\~r)xa^ -T24)~—~ί—— —I---1 ε\ S2 where 81 and 82 are the emissivity of plane y and plane 分别, respectively, σ is Stefan Poz Stefan-Bolzmann constant (5.67 X 10.8 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 〇.6, the emissivity of molybdenum is 0.3, and the emissivity of graphite is 〇.9, the substrate. The ratio of the apparent contact area between the 1〇1 and the anode 112 to the true contact area between the substrate 101 and the anode 112 is 1/1000000, and the substrate temperature is 920. (: The anode substrate is 860 ° C, and the substrate area is. For the molybdenum electrode, the contact thermal conductivity to the substrate 1 〇 1 is about 5 W, and the thermal conductivity of the free molecular orientation between the molybdenum electrode and the substrate 1 〇 1 It becomes about 10 W, and the heat of radiant heat becomes about 5 W. However, the thermal conductivity of the contact with the substrate 101 for the graphite electrode is about 1 W, and the thermal conductivity of the free molecular orientation between the graphite electrode and the substrate 101 becomes about 10 W. The heat of radiant heat is about 11 W. When no stress is applied to the interface and r becomes very small, the thermal radiation that does not fluctuate with r and the thermal conductivity of the free molecule - 62- 135,9878 heat ratio becomes We consider that when the heat transfer from the plasma to the substrate is fixed, even if the ratio of the apparent contact area between the substrate and the anode to the real contact area between the substrates varies due to the layout change, the confrontation is small, so The heat transfer from the substrate to the anode will be based on the radiant heat transfer, and only the change is proportional to the r-transfer heat transfer. At this time, because the contribution of the radiant heat transfer wipes most of the contact heat transfer The change is proportional to (T, 4 can be changed by radiant heat transfer with a large change with respect to temperature, thereby making it possible to relatively reduce the amount of change of yttrium. It is shown that the graphite electrode to radiant heat transfer can suppress relative to There is a change in the electrode in the temperature of the substrate, thereby stabilizing the deposition conditions. The use of a graphite electrode for the anode 112 prevents undesired deposition on the anode 112, as described below. Figures 34A and 34B A photograph showing the state of the film deposition and the graphite electrode, respectively. The anode 1 1 2 is used as a molybdenum electrode, as shown in Fig. 3 A, and the carbon film is formed on the portion where the substrate 101 is not mounted. When the substrate is placed on the molybdenum electrode having the carbon film formed, the surface roughness at the portion of the film is further changed, so the contact makes temperature control more difficult. For the graphite electrode, as shown in Fig. 34B, there is almost no rough surface. The degree of stability is not stable, the temperature is controlled by the small r and the poem of the anode, the absolute change of r is almost constant, the contact t is larger, TV), and compensates, the large distribution is small. The film thickness of the film deposits is deposited by the post-molybdenum electrode in the film. Therefore, when a carbon-transfer thermal deposit is formed, it becomes possible to become -63-1359878. Although the carbon film of the molybdenum electrode and the bottom side of the molybdenum electrode Impedance and thin film deposition between the upper surface of the graphite electrode (the portion where the substrate is placed or the portion where the substrate is not placed) and the bottom when the impedance is 3 Ω or higher and the voltage applied between the anode and the cathode itself changes. There is no change before, and the voltage applied between the upper surface of the anode and the cathode can be uniform in the plane. Since the graphite electrode is used for the anode 112, the carbon film which becomes the insulator hardly deposits on the anode 112, so the anode 112 The general shape does not change during film deposition. This prevents changes in the shape of the plasma, where film deposition can be expected to 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. 5, a recess in the accommodating substrate 110 may be formed in the substrate mounting surface 112a to widen the heat radiating surface of the anode 112 to increase heat radiation. In this case, it is preferable that the bottom side of the anode 112 is protruded to protrude to match the depth of the recess of the anode 112 to make the uniformity of the anode 112 uniform, so that the temperature of the anode 112 is uniform, and it is preferable. The ground is formed in the electrode mounting surface 111a of the platform 111 to match the protrusion of the anode Π2 and the bottom side of the platform Π1 is protruded 'it protrudes to match the depth of the recess of the electrode mounting surface 11U so that the platform U1 The uniformity is uniform, and the temperature of the platform 111 is uniform. It is then preferably mounted in the bottom side of the platform 111 in a recess formed in the opposite side U3a. As shown in Fig. 3-6, even if the bottom side of the substrate 1 〇 1 is not smooth, the recesses -64 - 13598, 78 can be formed to match the shape of the substrate 101, so that the substrate 101 can be mounted in the recess. In this case, it is preferable that the bottom side of the anode 112 is protruded to protrude to match the depth of the recess of the anode 112 to make the uniformity of the anode 112 uniform, so that the temperature of the anode 112 is uniform, and it is preferable. The ground is 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 protruded to protrude to match the depth of the recess of the electrode mounting surface 111a to make the platform 111 The uniformity is uniform, and the temperature of the platform 111 is uniform. It is then preferably mounted in the bottom side of the platform 111 in a recess formed in the opposite face 113a. 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, graphite is used to cool the substrate 101 for the electrode to cool the substrate having heat radiation, and the film deposition can be stabilized. 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- 1359878 Figs. 16A and 16B are configuration diagrams of a DC plasma chemical vapor deposition apparatus according to a sixth embodiment of the present invention; and Fig. 17 is a DC plasma chemical vapor deposition of the above 16A FIG. 18 is a cross-sectional view of a DC plasma chemical vapor deposition apparatus according to a side view of FIG. 16A; FIG. 19 is a seventh embodiment of the present invention. A configuration diagram of a DC plasma chemical vapor deposition apparatus; Fig. 20 is a diagram of a cathode, a reaction gas nozzle, a matrix gas nozzle, and an exhaust conduit of the DC plasma chemical vapor deposition apparatus of the above-mentioned FIG. 19: Fig. 21 FIG. 22A and 22B are configuration diagrams of a DC plasma chemical vapor deposition apparatus according to an eighth embodiment of the present invention; FIG. 22A and FIG. 22B are cross-sectional views of the DC plasma chemical vapor deposition apparatus; Figure 23 is a DC plasma chemical vapor deposition apparatus of the above 22A FIG. 24 is a cross-sectional view of the DC plasma chemical vapor deposition apparatus in a lateral direction of FIG. 22A; FIG. 25 is a modified view of the cathode; Figure 26 is a correction diagram of the cathode; Figure 27 is a correction diagram of the cathode; Figure 28 is a correction diagram of the cathode; Figures 29A and 29B are correction diagrams of the cooling member; 30A and 30B The figure is a modified view of the cooling member; -67-1359878 Fig. 31 is a configuration diagram of a plasma chemical vapor deposition apparatus according to a ninth embodiment of the present invention; and Fig. 32 is a graphite electrode and molybdenum during film deposition Fig. 33 is a graph showing the change in power applied to the plasma; Fig. 34A and Fig. 34B are diagrams showing the state of the anode after film deposition; and Fig. 35 is the plasma chemical vapor deposition of the plasma. A brief configuration of the correction of the device Γο*Τ · Fig. Fig. 3 is a simplified configuration diagram of the correction of the plasma chemical vapor deposition device, and Fig. 37 is a conventional plasma chemical vapor deposition device. Configuration diagram; and Figure 37B is used to explain the habit of Figure 37A A flow diagram of a gas in a reaction furnace in a plasma chemical vapor deposition apparatus. [Main component symbol description] 1 substrate 10 processing chamber 11 platform 11a anode lib space llx shaft 12 cooling member 12a conduit 12b flow channel 12c conduit-68- upper side vent hole side cathode cathode support insulating unit support window radiation thermometer Inflatable tube exhaust conduit voltage setting unit control unit variable power supply annular nozzle ejection 埠 insulator nozzle support stopper gas shower nozzle cathode central electrode peripheral edge electrode insulation portion voltage setting unit -69- 13598.78

28a 28b 28c 30 31 32 33 33a 34 35 35a 控制單元可變電源可變電源處理室充氣管充氣管環狀噴嘴噴出埠氣體噴淋噴嘴陰極中央電極 35b 周緣電極 35c 絕緣部分28a 28b 28c 30 31 32 33 33a 34 35 35a Control unit Variable power supply Variable power supply chamber Processing chamber Inflator tube Inflatable tube Annular nozzle Exhaust 埠 Gas spray nozzle Cathode Central electrode 35b Peripheral electrode 35c Insulation

36 36a 36b 36c 50 51 電壓設定單元控制單元可變電源可變電源處理室平臺· 51a 陽極 51b 52 52a 52b 52c 空間冷卻構件導管流動通道導管 -70 13598.7836 36a 36b 36c 50 51 Voltage setting unit Control unit Variable power supply Variable power supply processing chamber Platform · 51a Anode 51b 52 52a 52b 52c Space Cooling member Conduit Flow path Catheter -70 13598.78

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 噴嘴 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 135987853 Cathode 53x Axis 54 Cathode support 55 Insulation unit 57 View window 58 Radiation thermometer 59 Inflator tube 60 Exhaust duct 61 Voltage setting unit 61a Control unit 61b Variable power source 62 Nozzle 62a Ejection 埠 62A Part 62B Part 63 Insulated nozzle support 65 Cathode 65a Central electrode 65b Peripheral electrode 65c Insulation portion 66 Voltage setting unit 66a Control unit 66b Variable power supply 66c Variable power supply 70 Processing chamber 1359878

71 72 73 73a 73A 73B 74 75 75a 75b 75c 76a 76b 76c 90b 90c 充氣管充氣管噴出埠部分部分氣體噴淋噴嘴陰極中央電極周緣電極絕緣部分電壓設定單元控制單元可變電源可變電源陰極中央電極周緣電極絕緣部分 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 1359878 171 72 73 73a 73A 73B 74 75 75a 75b 75c 76a 76b 76c 90b 90c Inflatable tube inflation tube ejection 埠 part of gas spray nozzle cathode central electrode peripheral edge electrode insulation part voltage setting unit control unit variable power supply variable power supply cathode central electrode circumference Electrode insulating portion 91 cathode 91a central electrode 91b peripheral electrode 91c insulating portion 92 cathode 92a central electrode 1359878 1

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 導管排氣孔冷卻單元導管閥流量控制器圓筒陰極電源氣體供應管路氣體排出管路觀視窗光譜輻射計正極柱氣體入口氣體出口觀察點觀察點 -74-92b circular peripheral electrode 92c insulating portion 93 cathode 93a central electrode 93b first annular peripheral electrode 93c second annular peripheral electrode 94 helium gas charging unit 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 path 113c Conduit-73 Conduit vent cooling unit Conduit valve flow controller Cylinder cathode power supply gas supply line gas discharge pipe view window spectroradiometer positive electrode gas inlet gas outlet observation point observation point -74-

Claims

1359878 Amendment to the Patent No. 0961, 677, "Plasma Chemical Vapor Deposition Apparatus and Thin Film Deposition Method" (Amended on November 15, 2011) X. Patent Application Range: 1. A plasma chemical vapor deposition apparatus, The method includes: a reaction furnace; a first electrode is disposed in the reaction furnace, and a substrate is mounted on the first electrode; a second electrode is disposed above the first electrode and opposite to the first electrode, and Producing a plasma with the first electrode; and a first gas supply nozzle 'in the reactor at a height between the height of the first electrode and the height of the second electrode' and having a plurality of ejection ports, The ejection enthalpy is formed and disposed around a region between the first electrode and the second electrode that generates plasma; the second electrode includes a central electrode facing a central portion of the first electrode and faces the surface a peripheral electrode of a peripheral portion of the first electrode; the voltage or current between the central electrode and the first electrode is set to be higher than the voltage or electricity between the peripheral electrode and the first electrode The enthalpy of the flow: or after the positive electrode column is formed between the central electrode and the first electrode, the voltage or current between the central electrode and the first electrode is set lower than the peripheral electrode and the The voltage or current between the first electrodes is 値1359878 V ^_______ The date of the correction is replaced by the correction of the machine 11. 1 5- 2. The plasma chemical vapor deposition apparatus of claim 1 of the patent scope, wherein the The source gas system in which the plasma forms an active species is introduced by the first gas supply nozzle. 3. The plasma chemical vapor deposition apparatus of claim 1, wherein the source gas and the carrier gas for forming the active species using the plasma are introduced by the first gas supply nozzle. 4. The plasma chemical vapor deposition apparatus of claim 1, wherein the first gas supply nozzle ejects gas laterally from the plurality of discharge ports toward a central axis of the first electrode. 5. The plasma chemical vapor deposition apparatus of claim 1, wherein the first gas supply nozzle is disposed to surround the first electrode. 6. The plasma chemical vapor deposition apparatus of claim 1, wherein the plurality of discharge ports of the first gas supply nozzle are arranged at equal intervals. 7. The plasma chemical vapor deposition apparatus of claim 1, wherein the plurality of ejection ports of the first gas supply nozzle have a distance equal to a central axis of the first electrode. 8. The plasma chemical vapor deposition apparatus of claim 1, wherein each of the plurality of ejection enthalpy of each of the ejection groups is arranged to face each other with the central axis of the first electrode as a center, and each of The plurality of ejecting ports of the ejecting crucible group comprise two of the plurality of ejection ports of the first gas supply nozzle. 9. The plasma chemical vapor deposition apparatus of claim 1, wherein the height of the plurality of jetting nozzles of the first gas supply nozzle is set to be high -2- 1359878. Corrected this year's monthly correction replacement page LlOO- J,! 15_ is the highest point in the area where the positive electrode column of the plasma is generated. 10. The plasma chemical vapor deposition apparatus of claim 1, wherein the first gas supply nozzle has a ring shape. 11. The plasma chemical vapor deposition apparatus of claim 1, wherein the first gas supply nozzles are a plurality of tubes facing each other along a side of the second electrode. 12. The plasma chemical vapor deposition apparatus of claim 1, further comprising a second gas supply nozzle that ejects a carrier gas from above the second electrode toward the gas ejected by the first gas supply nozzle. 13. The plasma chemical vapor deposition apparatus of claim 1, further comprising a plurality of exhaust ducts disposed below the first electrode, wherein the gas is discharged from the reactor. 14. The plasma chemical vapor deposition apparatus of claim 1, further comprising a plurality of exhaust ducts disposed below the first electrode, thereby surrounding the first electrode and discharging gas from the reactor . 15. The plasma chemical vapor deposition apparatus of claim 1, wherein an insulator is disposed between the plurality of electrodes. 16. A plasma chemical vapor deposition apparatus comprising: a reaction furnace; a first electrode disposed in the reactor, having a surface formed of graphite, and mounting a substrate to be processed on the graphite; a second electrode is disposed above the first electrode and opposite to the first electrode, and generates an electric current with the first electrode; and -3- 1359878 ', the date of the correction is replaced by the page 1 correction 1〇n 11 ι κ_I a first gas supply nozzle disposed in the reaction furnace at a height between a height of the first electrode and a height of the second electrode, and having a plurality of ejection rafts surrounding the Forming and arranging a region between the first electrode and the second electrode that generates plasma; the second electrode includes a central electrode facing a central portion of the first electrode and a periphery of a peripheral portion facing the first electrode The electrode or the voltage or current between the central electrode and the first electrode is set to be higher than the voltage or current between the peripheral electrode and the first electrode; or the positive electrode column is formed therein. central After the electrode and the first electrode, the voltage or current between the central electrode and the first electrode is set to be lower than the voltage or current between the peripheral electrode and the first electrode. A plasma chemical vapor deposition apparatus according to claim 16 of the patent application, further comprising a platform supporting the electrode; and a cooling unit that cools the platform to cool the electrode, thereby lowering the temperature of the substrate. A plasma chemical vapor deposition apparatus according to claim 17, wherein the cooling unit starts to cool the substrate when film deposition is performed on the substrate. 19. A plasma chemical vapor deposition apparatus as claimed in claim 16 wherein the predetermined process carried out by the plasma generating unit is performed by using hydrocarbon as a plasma of a reaction gas. Film -4- 1359878 "1 correction of this 4 m positive replacement page i deposition. 20. A film deposition method comprising: a reaction furnace; a first electrode is placed in the reactor, and a first electrode is mounted with a substrate to be processed; and a second electrode includes a central electrode facing a central portion of the first electrode and a peripheral electrode facing a peripheral portion of the first electrode: the thin film deposition method comprises : when a plasma is generated between the first electrode and the second electrode, the voltage or current between the central electrode and the first electrode is set to be higher than the peripheral electrode and the first电压 of the voltage or current between the electrodes; or after the positive electrode column is formed between the central electrode and the first electrode, the voltage or current between the central electrode and the first electrode is set to be low The peripheral edge of the electrode and between the first electrode of the Zhi voltage or current.