200407275 (1) 玖、發明說明 【發明所屬之技術領域】 本發明有關一種供CVD (化學氣相沉積）裝置使用 之玻璃樣碳組件。雖然本發明主要有關供C V D裝置使用 之內管，本發明亦涵蓋各種欲排列於C V D裝置內部之各 種組件。 【先前技術】 半導體裝置之製造大體上與所謂之CVD方法有關， 該方法涉及反應物氣體於矽晶圓上沉積薄膜形式之矽、氮 化矽等的氣相化學反應。此方法中，矽晶圓係放置於一內 管（圖1中所示）中，以進行均勻加熱且控制反應物氣體 流動。 供CVD裝置使用之內管需於一般CVD條件下具有良 好之耐用性（於5 00 °C或以上之耐熱性及抗反應物氣體之 抗腐蝕性）。亦需儘可能釋出較少之塵粉及雜質氣體。傳 統上係以石英所製之內管滿足此等要求。 CVD方法係基於經加熱之反應物氣體（作爲原料） 於矽晶圓上分解或彼此反應以形成薄膜（諸如多晶矽薄膜 及氮化矽薄膜）之原理。在CVD過程中，反應物氣體之 分解或反應產物沉積於該內管之表面上。帶有該沉積物（ 多晶矽、氮化矽等）之內管在未置換下重複使用，以保持 產能。連續使用之後，該內管變成覆有厚厚的沉積物，最 後自內管剝落而產生細粒。該細粒黏著於矽晶圓上，而降 -4- (2) (2)200407275 低良率。而「粒子」係表示在藉光學測試器檢測晶圓時所 偵測之微粒缺陷。 消除因爲自內管剝離之沉積物而產生的粒子的一種方 法係定期拆卸及淸洗內管，以移除CVD沉積物。淸洗係 採用化學溶液，諸如氫氟酸及硝酸。 然而，該種淸洗操作降低產能且增加製造成本。因此 ，該內管應使CVD沉積物牢牢黏著，使得所累積之CVD 沉積物不會產生粒子。CVD沉積物對於內管之黏著性受 到該內管之尺寸變化所影響，該尺寸變化係發生在該 CVD槽進行冷卻及加熱以個別卸除及裝上晶圓之時。該 內管應確定即使因爲該冷卻/加熱循環而有尺寸變化，仍 具有良好之黏著性。而且，因爲無法避免用以移除CVD 沉積物之淸洗過程，故內管需對前述淸洗溶液具有良好之 抗腐蝕性。不幸的是由石英製得之習用內管對於CVD沉 積物之黏著性及對抗淸洗溶液之抗腐蝕性不足。 此等情況下，本發明者預先發展一種防止產生粒子、 抵抗淸洗溶液之腐蝕、且符合其他前述要求之供C V D裝 置使用的新穎玻璃樣碳內管，且申請專利（日本公開專利 序號 3 5 04 / 2 00 1 )。 有另一種改善玻璃樣碳組件或塗覆有玻璃樣碳之石墨 組件對於CVD沉積物之黏著性的方法。藉著噴砂處理將 組件表面粗糙化而達到其目的。（日本公開專利序號 342068/2001及日本專利公告序號86662 / 1994)。 亦已知供C V D裝置使用之內管及其他組件可能含有 200407275 C3) 雜質’而在CVD過程中污染晶圓，所產生之污染 形成之裝置故障。因此，組件表面中之金屬雜質濃 大於1 0 X 1 0 1G原子/厘米2，以不大於5 x丨〇 1G原 米2爲佳。實際上，由在適當控制之條件下製備之 碳製得之市售模擬晶圓已達到低於5 X 1 0 1 G原子/ 之値。此種模擬晶圓具有經鏡面處理之表面，表面 大於〇·1微米。就此模擬晶圓而言，供CVD裝置 玻璃樣碳內管需具有不高於5 X 1 0 1 G原子/厘米2 金屬濃度。 而表面金屬濃度係依測定碳晶圓表面上之金屬 測量。該方法係始自使用2 %氫氟酸與2 %過氧化 合溶液自試樣萃取金屬。之後藉I C P — M S (感應親 質譜）分析該萃取液。所測定之金屬量係以用於萃 單位面積試樣的原子數表示（原子/厘米2 )。 如此，藉由製備樹脂管，之後於惰性氛圍中力口 製得玻璃樣碳管。該加熱溫度通常高於8 00 °C，J 至1200 °C爲佳，1300至2500 °C更佳。在加熱碳化 該樹脂管大幅收縮（約2 0體積％ )。此收縮使其 到完全圓形之玻璃樣碳管。 已有人提出一種達到圓北之方法，其係於碳化 樹脂管中或在高溫熱處理之前於玻璃樣碳管中插入 石墨芯，如同日本公開專利序號189470/1999及 利公告1 8 94 71 / 1 99中所揭示。因爲該樹脂管於碳 收縮，故該芯具有等於該玻璃樣碳管之外徑。 導致所 度應不 子/厘 玻璃樣 厘米2 糙度不 使用之 之表面 的方法 氫之混 合電漿 取之每 熱，而 I 1000 期間， 難以得 之前在 圓柱形 曰本專 化之後 -6- (4) (4)200407275 然而，其證明前述習用方法採用圓柱形內芯並非始終 產生圓形玻璃樣碳管。 【發明內容】 曰本公開專利序號3 3 2 5 04 / 2 0 0 1 (前述）中所揭示 之技術可有效地防止生成粒子且降低淸洗程序之頻率。此 技術採用噴砂處理將供CVD裝置使用之玻璃樣碳內管表 面粗糙化，以變善CVD沉積物之黏著性，但無法將粒子 降低至所需之水平。此因表面粗糙化增加金屬雜質含量。 目前，需要一種產生雜質少於前述技術者之供CVD裝置 使用的內管。 雜質（諸如粒子）係發生於CVD沉積物自內管表面 剝落，如同前文所述。本發明者進行硏究顯示CVD沉積 物薄膜在剝落之前變厚而導致龜裂。CVD沉積物薄膜表 面中之裂紋係出示於圖5中（掃描式電子顯微鏡所得之相 片）。 而CVD沉積物薄膜不僅形成於內管表面，亦形成於 各種組件於C V D裝置中曝露於C V D環境下之表面上。因 此，亦需抑制自C V D沉積物薄膜形成之雜質（粒子）形 成於除內管以外之組件的表面上。 已知含碳材料（諸如玻璃樣碳）可藉著於高溫（通常 2 000 °C或以上）下於含鹵素氛圍中加熱，使得鹵素滲入碳 中，且自碳蒸發金屬雜質而純化。此方法似乎可用於降低 可能已於表面糙化時污染內管表面之金屬雜質。 -7- (5) (5)200407275 另一方面，純化方法可能導致含碳材料之尺寸畸變。 然而，供C V D裝置使用之內管即使在純化方法之後亦應 保持充分之圓度。玻璃樣碳管之尺寸準確性不夠高之可能 因素係爲其反常之體積變化性質。即，其於最高達約 1 2 00 °C下收縮，之後於稍高溫下稍微膨脹。 就前述CVD沉積物薄膜而言，金屬雜質不僅存在於 內管表面，亦存在於CVD裝置之CVD環境中的各種組件 表面上。因此，需降低存在於除內管以外之組件的表面上 之金屬雜質的量，以抑制因爲金屬雜質形成粒子。 是故，本發明之目的係提供一種具有下列優點之供 CVD裝置使用的玻璃樣碳組件，及其製造方法。改良之 對CVD沉積物的黏著性。於裂開之後使CVD沉積物薄膜 長得夠厚，以抑制因爲CVD沉積物薄膜剝落而產生雜質 (粒子）之能力。製得經適當之粗糙化的表面，而不增加 會產生粒子的金屬雜質。防止釋出麈粉之能力。本發明另 一目的係提出一種製造具有高度糙度之玻璃樣碳管的方法 〇 本發明之要旨在於供CVD裝置用之玻璃樣碳組件， 其特徵爲具有由0.1至10微米（根據JIS B 060 1測量）之 表面糙度（Ra)値，且表面含有含量各低於5xl〇1C)原子 /厘米2之鐵、銅、鉻、鈉、鉀、鈣、鎂、及鋁。本發明 所列示之表面糙度（Ra )係爲根據JIS S 060 1測量之値， 除非另有陳述。 根據本發明，供CVD裝置使用之玻璃樣碳組件之表 ~ 8 - (6) (6)200407275 面經處理’使得在放大]〇〇〇倍之掃描式電子顯微鏡下觀 察之5 0 X 5 0微米視野中有至少五個1至1 〇微米直徑之坑 洞’或表面經處理使得在放大1 000倍之掃描式電子顯微 鏡下觀察之5 0 X 5 0微米視野中存有總長度至少5 0微米而 寬度〇 · 5至5微米之細長凹陷。而「總長度」意指存在於 視野中之細長凹陷的長度總和値（〇. 5至5微米寬度）。 根據本發明，供CVD裝置使用之玻璃樣碳組件係爲 內管、晶圓皿、晶座、及供CVD裝置使用之噴嘴中之任 一者。 根據本發明，製造供CVD裝置使用之玻璃樣碳組件 之方法的特徵爲表面糙化步驟及後續純化步驟。該表面糙 化步驟可爲機械步驟，諸如噴砂及硏磨。該純化步驟可爲 於含鹵素氛圍中之高溫熱處理。 若供CVD裝置使用之玻璃樣碳組件係爲玻璃樣碳管 ’則期望於內表面及外表面上皆進行機械表面糙化，之後 進行純化步驟。 根據本發明，製造供CVD裝置使用之玻璃樣碳組件 的方法之特徵爲機械表面糙化及化學表面蝕刻，其可連續 (依所述順序）或同時進行。 該機械表面糙化可藉噴砂或硏磨達成，而該化學表面 蝕刻可藉熱氧化或電解氧化達成。 根據本發明，供CVD裝置使用之玻璃樣碳圓管係藉 著將原料樹脂模製成管，於800至1 3 0 0 t加熱所形成之 樹脂’之後將其轉化成玻璃樣碳管，在該玻璃樣碳管外套 -9 - (7) (7)200407275 上圓度修正夾，而於高於1 5 0 0 °C之溫度下加熱該玻璃樣 碳管。 【實施方式】 根據本發明，供CVD裝置使用之玻璃樣碳內管的特 徵爲具有內表面及外表面糙度，使其因爲表面不規則所產 生之錨接效應而對C V D沉積物具有改良之黏著性。根據 本發明，供CVD裝置使用之玻璃樣碳內管應具有由〇·1 至1〇微米之表面糙度値（Ra )(根據JIS B 06 0 1測量） 〇 當表面糙度値低於〇. 1微米時，玻璃樣碳內管對於 CVD沉積物之黏著性不足，使得CVD沉積物易在變得夠 厚之前有細微龜裂。此種細微龜裂釋出大量粒子，故需經 常置換內管。表面糙度値大於10微米時，玻璃樣碳內管 易喪失其表層 ° 根據本發明，供CVD裝置使用之玻璃樣碳內管藉表 面粗糙化處理將其內表面及外表面粗糙化（Ra係由0. 1至 1 〇微米）。該表面粗糙化處理應以機械化處理爲佳。以 細粉噴砂有助於硏磨，因其可在不造成表面缺陷（諸如微 裂紋）之情況下達到表面粗糙化。 根據本發明，供CVD裝置使用之玻璃樣碳內管係由 玻璃樣碳製得，故其具有約略3 X 1 (Γ6之熱膨脹係數。此 値接近氮化矽（3·4 XI (Γ6 )。意爲該內管與氮化矽沉積物 之間不會在形成氮化矽薄膜過程中因爲加熱而有大幅尺寸 -10- (8) (8)200407275 變化（及因而產生之應力）。該低値應力使得該內管與氮 化矽沉積物之間的黏著性得到改善。 根據本發明，供C V D裝置使用之玻璃樣碳內管的特 徵爲其表面含有量各低於5 X 1 0 1G原子/厘米2之鐵、銅 、鉻、鈉、鉀、鈣、鎂、及鋁。此等金屬係存在於該內管 表面中之雜質。若此等金屬中任一者之濃度超過5xl01[ 原子/厘米2，則該內管易釋出大量來自此等金屬之粒子 〇 本發明者持續針對雜質（諸如粒子）起因進行硏究。 結果，發現供CVD裝置使用之玻璃樣碳內管即使內表面 及外表面經粗糙化至0.1至10微米之平均糙度（Ra)( 根據JIS B060 1測量），仍無法令人滿意。詳言之，發現 藉噴砂法粗糙化之表面無法充分改善針對CVD沉積物薄 膜之黏著性。亦發現噴砂法在表面上留下陶瓷細粉或金屬 細粉（作爲磨蝕介質）或碳細粉（因噴砂而釋出）或應力 (於噴砂期間生成）。其係爲掉落於晶圓上之粒子的起因 〇 前文建議在爲了完全消除雜質（諸如粒子）的情況下 ，需設計一種可較噴砂法更有效地改善對於CVD沉積物 薄膜之黏著性的方法，及一種防止因爲內管本身產生塵粉 的方法。 本發明者進一步硏究顯示若藉機械表面粗糙化（諸如 產生輕度表面不規則之噴砂）且確定化學表面蝕刻（形成 極小之表面不規則，而表面糙度（Ra )幾乎不變）增進前 -11 - 200407275 Ο) 述錨接效應，則可大幅改善該內管與CVD沉積物薄膜之 間的黏著性。下文中，「黏著性」有時表示介於該內管表 面與CVD沉積物薄膜之間的黏著性。 本發明內管應如前文所述般於表面上具有極小之表面 不規則爲佳。該表面不規則係分類爲以下第（1 )或（2 ) 項，以改善介於該內管與該CVD沉積物薄膜之間的黏著 性。改善之黏著性使得CVD沉積物薄膜在裂開之前具有 充分厚度。而防止產生雜質，諸如粒子。 (1) 該內管表面在放大1000倍之SEM下觀察時， 於5 0 X 5 0微米視野中具有至少五個1至1 〇微米直徑之坑 洞。 (2) 該內管表面在放大1〇〇〇倍之SEM下觀察時， 於5 0 X 5 0微米視野中具有總長度至少5 〇微米而寬度0 · 5 至5微米之細長凹陷。 前述第（1 )項中之「坑洞」係表示存在於內管表面 上而約略圓形之凹陷，如圖3中之S EM相片所示。其係 以圖3 ( b )中之箭號表示。其深度不重要。（「坑洞」 有時可稱爲「表面孔洞」）。 前述第（2 )項中之「細長凹陷」係爲在形成「坑洞 」之前形成者。其係出示於圖4所示之SEM相片中。圖 4 ( c )中，其以粗線標示，以供辨識。 坑洞（表面孔洞）之數量及細長凹陷之總長度（本發 明所定義）係爲在前述放大倍率下自5 0 X 5 0微米視野所 得之三個測量値的平均値。 -12- (10) (10)200407275 前述第（1 )項所列之表面結構係在前文定義之視野 中存在至少五個直徑爲1至10微米之坑洞。該坑洞大幅 改善該內管與C V D沉積物薄膜之間的黏著性。 視野中坑洞少於五個不足以產生令人滿意之錨接效應 (以建立該內管與CVD沉積物薄膜之間的黏著）。坑洞 之數量應以不多於1 0個爲佳。 視野中坑洞之數目不特別限制；然而，根據下列因素 應以小於1 0 0爲佳。形成1 〇 〇以上的坑洞需有長時間進行 表面化學蝕刻。而且，坑洞數量增加時，內管變薄，且末 大幅改善黏著性。因此，就工業觀點而言，·不期望過度的 增加坑洞數量。 根據下述因素，位於表面上之坑洞應具有如前述第（ 1 )項所述之1至1 〇微米直徑。當直徑小於1微米時，坑 洞未產生用以改善對於C V D沉積物薄膜之黏著性的錨接 效應。另一方面，直徑大於1 0微米之坑洞對於黏著性產 生負面影響。推測此因各坑洞皆具有相對平滑之表面，因 此大型坑洞無法產生所需之錨接效應。 位於該表面上之細長凹陷（〇. 5至5微米寬度）具有 如前述第（2 )項所述之至少5 0微米總長度。若總長度大 於5 0微米，則細長凹陷大幅改善該內管與CVD沉積物薄 膜之間的黏著性。 •若總長度小於5 0微米，則細長凹陷無法充分改善該 內管與CVD沉積物薄膜之間的黏著性（因錨接效應所致 )。該總長度應以大於1 0 0微米爲佳。 -13- (11) (11)200407275 細長凹陷之總長度不具有特別公認可改善黏著性的上 限。然而，總長度超過5 〇 〇微米之細長凹陷未產生任何明 顯之附加效果。因此，就工業觀點而言，細長凹陷之總長 度應小於5 0 0微米。 細長凹陷因下列因素而應具有如前述第（2 )項所列 之〇. 5至5微米寬度。寬度小於0.5微米之細長凹陷太窄 ，而無法產生用以改善對CVD沉積物薄膜之黏著性的錨 接效應。另一方面，寬度大於5微米之細長凹陷導致內管 表面釋出細粉。 如前文所述，本發明內管應具有前述第（1)及（2) 項所述之表面結構中之一或兩種。 本發明內管係藉由下文所說明之方法製得。於本發明 中作爲內管之管狀玻璃樣碳可藉一般方法製得，包括模製 原料樹脂之步驟及將形成之模製物碳化之步驟。碳化步驟 可藉由預先加熱步驟以避免變形而進行。若使用熱固性樹 脂（下文所述）作爲原料樹脂，則固化處理可作爲預先加 熱步驟。如此，可將構成模製物之樹脂固化，之後將樹脂 碳化，而不會有嚴重之熱變形。 爲製得玻璃樣碳管，進行模製步驟以將原料樹脂製成 中空圓柱形。此情況下之模製方法不特別限制；包括離心 模製、注射模製、及擠出塑製。此等模製方法中，因下列 因素而特別期望離心模製。離心模製使熔融樹脂於模具內 流動且固化；因此，可輕易產生具有高度尺寸準確度之管 狀產物’且可完全脫氣（因爲在模製時模具兩端皆開放） -14 - (12) (12)200407275 。該原料樹脂可包括任何已知熱固性樹脂，諸如酚醛樹脂 及呋喃樹脂。 有關原料樹脂之離心模製的細節係揭示於日本公開專 利序號3 3 2 5 0 4 / 2 0 0 1中。 前述產生模製物（或樹脂管）之模製步驟之後係爲碳 化步驟，其將樹脂管轉化成玻璃樣碳管。碳化通常係於惰 性氣體氛圍（或非氧化氛圍）中於8 00至2 5 00 °C下加熱 而完成。該碳化步驟應進行至使該玻璃樣碳管保持其圓形 剖面。此目的係藉由使用日本公開專利序號 17946 3/2002及日本專利申請案序號347393/2001所揭 示之圓柱內芯而達成。改善圓度之方法係描述於下文。 若使用熱固性樹脂作爲原料樹脂，則期望提供前述固 化步驟。該固化條件係依樹脂而異；酚醛樹脂通常於空氣 中於1 8 0至3 5 0 °C下固化1 0至1 0 0小時。 本發明內管可藉由一種除了模製及碳化步驟之外亦包 括機械表面糙化步驟及純化步驟之方法而製得。 該機械表面糙化步驟係用以藉任何已知之機械機構於 該玻璃樣碳管表面上形成微小不規則。此步驟可於該模製 步驟與該碳化步驟之間的任何階段進行。機械表面糙化可 在固化之前或之後於原料樹脂模製物件上或在碳化之後於 玻璃樣碳管上進行。碳化可分兩階段於約9 0 0 °C及約1 2 0 0 °C下達成。此情況下，機械表面糙化可在第一階段或第二 階段之後完成。 機械表面糙化之方法係包括噴砂及硏磨。以噴砂爲佳 -15- (13) (13)200407275 噴砂使用之磨蝕粉不特別限制，可使用任何已知者。 包括陶瓷粉末（諸如氧化鋁粉及碳化矽粉）、金屬粉、及 玻璃珠。磨蝕粉之晶粒大小及噴砂條件（壓力及噴嘴作用 距離）可根據所需之表面糙度而適當地選擇。磨蝕粉通常 係爲晶粒大小約#220至800之細粉。 硏磨可使用砂紙（# 1 5 0至1 0 〇 〇 )達成。晶粒大小及 其他條件（硏磨壓力等）可根據所需表面糙度而適當地選 擇。 機械表面糙化應同時於該管之內側及外側上進行爲佳 ，以使因爲稍後進行之純化步驟所致之尺寸變化減至最少 。若機械表面糙化係個別於內側及外側上進行，則後續純 化步驟中產生相對大之應力，而難以得到具有足以使用於 CVD裝置中之糙度的內管（此原因未知）。 根據另一較佳實施例，機械表面糙化係藉由或後續進 行化學表面蝕刻而達成。化學表面蝕刻係移除該玻璃樣碳 管之部分表面，以形成微小之表面不規則。此種處理移除 因爲機械表面糙化所形成之細粉及傷痕（諸如裂紋）。因 此，防止該內管釋出塵粉。 化學表面蝕刻通常係於機械表面糙化之後進行。若此 次序顛倒，則藉化學表面蝕刻形成之微小不規則被機械表 面糙化而破壞。詳言之，化學表面蝕刻係於任何階段中， 於已藉機械表面糙化形成微小不規則之玻璃樣碳管上進行 。然而，可於供化學表面糙化使用之環境中（例如，於熱 •16- (14) (14)200407275 氧化使用之環境中）於玻璃樣碳管（尙未進行機械表面糙 化）上進行機械表面糙化（諸如噴砂）。此情況下之結果 係爲同時進行機械表面糙化及化學表面f造化。 化學表面糙化處理係包括熱氧化、電解氧化、及化學 蝕刻。 熱氧化之進行方式係使該玻璃樣碳管表面氧化，以產 生可前述第（1 )或（2 )項所定義之表面結構。通常係藉 著於600至800 °C下於氧化氛圍（空氣或氧）中熱處理 0.5至1 0小時而達成。 電解氧化係藉著施加跨經該玻璃樣碳管（作爲陽極） 及鉑、不銹鋼、或鎳之陰極（浸於電解質中）的電流而達 成。該電解質係爲氫氧化鈉、氫氧化銘、或氨之水溶液。 電解質（NaOH溶液）之濃度係爲〇. 1至2M。 電解氧化可在任何不受限制之條件下進行，其先決條 件爲形成之玻璃樣碳管具有如前述第（1 )項或第（2 )項 所定義之表面結構。蝕刻程度係藉著調整電流量（通常爲 5至5 00 C/ cm2 )而控制。 化學蝕刻係藉著將該玻璃樣碳管浸於可溶解其表面之 化學溶液中而達成。該化學溶液之實例有重鉻酸鉀或重鉻 酸鈉水溶液及鉻酸混合物。 電解氧化較佳之原因係可輕易控制蝕刻程度。 此外’根據本發明’已單只進行機械表面糙化或已同 時進行化學表面蝕刻之玻璃樣碳管應具有由〇 · 1至1 〇微 米之表面糙度，以由0.3至3微米爲佳。 •17- (15) (15)200407275 已進行表面糙化之玻璃樣碳管隨之藉著於含鹵素之氣 體環境中於高溫下加熱，而進行純化處理。此純化處理降 低已於機械表面糙化時進入該玻璃樣碳管表面之金屬雜質 的含量。在此純化處理之後進行表面淸洗處理，表面中鐵 、銅、鉻、鈉、鉀、鈣、鎂、及鋁之各個濃度皆降低至5 xl〇1()原子/厘米2以下。 本發明者之硏究顯示若內管之表面糙度超過10微米 ，則純化處理無法將金屬濃度降低至5 X 1 0 1G原子/厘米 2以下，即使在表面淸洗處理之後亦然。可能原因爲過度 表面糙化增加有效表面積，因此該內管幾何表面之每單位 面積的金屬濃度增加。因此，就降低表面中金屬濃度之觀 點而言，供CVD裝置使用之內管的內表面及外表面應經 糙化至特定極限（1 〇微米）。另外，在純化處理之後， 該內管應依一般方式以氫氟酸、鹽酸、或過氧化氫洗滌。 根據本發明，採用以下方法以改善該玻璃樣碳管之糙 度。本發明方法包括將原料樹脂模製成管，藉著於惰性氛 圍中於8 0 0至1 3 0 0 °C下加熱將該樹脂管碳化之步驟。碳 化步驟中，該樹脂管收縮且玻璃化以產生玻璃樣碳管，其 隨之進行高溫熱處理。該碳化步驟應在將一圓柱形內芯放 置於樹脂管內部之情況下進行，使該管於熱處理期間保持 圓形。之後，將圓度修正夾套於該玻璃樣碳管外側（其尙 未進行高溫熱處理）。該玻璃樣碳管及圓度修正夾係於高 溫（即1 5 00 °C或以上）下於惰性氛圍中一起加熱。於該 高溫下熱處理期間，該圓度修正夾進行熱膨脹，該玻璃樣 -18- (16) (16)200407275 碳管亦進行熱膨脹及因碳之結構變化所致之膨脹。結果， 該玻璃樣碳管（已進行高溫熱處理）保持高度圓度，外表 面套貼於該圓度修正夾之內表面。 圖6係爲出示該玻璃樣碳試樣（尙未進行高溫熱處理 )在加熱時，溫度與長度變化之間的關係之圖。加熱速率 係爲2 0 0 °C /小時。該玻璃樣碳試樣係爲2毫米厚、2毫 米寬、20毫米長之矩形，已藉著於90(TC下加熱而碳化。 如圖6所示，玻璃樣碳之模製試樣膨脹至其加熱至約 9 5 0 °C，在自9 5 0 °C加熱至1 2 0 0 °C時收縮，而加熱至丨2 〇 〇 t以上時再次膨脹。該二次膨脹（於1 2 0 0 t及以上）的 斜率較一次膨脹（0至9 0 0 °C )陡。於〇至9 0 0 °C下，玻 璃樣碳之模製試樣具有約3 x 1 〇_6 ( K_1 )之線性膨脹係數 ，而於1 200至1 5 00 °C下時，其具有約10 X 1 〇·6 ( Κ·ι )之 熱膨脹係數。兩係數間之差値導致在1 2 0 〇至1 5 0 0 °C #生 結構改變。換言之，玻璃樣碳之模製試樣（此實例中已於 9 0 0 °C下碳化）在自1 2 0 0 °C加熱至1 5 0 〇 °c時膨脹。膨脹機 制並未完全明瞭；可能係因爲碳結構改變所致。 前文建議產生玻璃樣碳管之碳化（其隨之進行高溫熱 處理）應於低於1 2 0 0 °c下進行，使得該玻璃樣碳管於 1 2 0 0至1 5 00 °C下於高溫熱處理中長時間加熱。將原料樹 脂之可能變化列入考慮時，碳化溫度之上限應爲】3 〇〇 t 。fe化溫度之下限應爲8 〇 〇 C，此時樹脂管玻璃化。此下 限應以儘可能接近1 2 0 0 °C爲佳’該材料於此溫度下幾乎 完全收縮。（己於900 °c下加熱之玻璃樣碳模製物係於 -19- (17) (17)200407275 9 5 0至1 2 0 (TC下收縮）。原因是若該玻璃樣碳管於9 5 〇至 1 2 0 0 C溫度範圍下加熱時大幅收縮，則該玻璃樣碳管與套 於外側之圓度修正夾過度分離，導致因膨脹降低後續圓度 1W正效果。此外，g局溫熱處理應於1 5 〇 〇 或以上進行 之原因係若其溫度低於所示値，則因膨脹（因前述結構變 化）而無法充分產生圓度修正效果。高溫熱處理之溫度上 限通常係爲2 5 00 °c ’唯其視所需之玻璃樣碳管的品質及 使用溫度而定。 使用於本發明之圓度修正夾應自具有良好耐熱性且熱 膨脹係數接近玻璃樣碳管（進行高溫熱處理）之材料形成 。該材料係包括石墨、玻璃樣碳、及碳纖維，以第一種爲 佳。 前文描述主要係針對供CVD裝置使用之玻璃樣碳管 。本發明範圍不僅涵蓋內管，亦涵蓋其他供C V D裝置使 用之組件’諸如支撐晶圓之舟皿、晶架、噴嘴等。其係藉 模製、碳化、表面糙化、及表面化學蝕刻自原料樹脂製備 ，如同內管。 如前文針對內管所說明，此等供CVD裝置使用之玻 璃樣碳組件具有因機械表面糙化所致之極細表面不規則及 因化學表面蝕刻所致之極小表面不規則。此種表面結構產 生錨接效應，改善其對CVD沉積物薄膜之黏著性。此外 ，該化學表面蝕刻防止組件本身釋出塵粉。此等性質極有 助於製造半導體裝置。 •20- (18) (18)200407275 實施例 參照以下實施例更詳細地描.述本發明，此等實施例不 限制本發明範圍，可在不偏離該範圍之情況下進行改變及 修飾。 圖2係爲出示本發明之一實施例中使用之離心模製用 模具的實例之示意剖面圖。供離心模製用之模具1 〇係由 模具本體1 1、底板1 2、及凸緣擋板1 3所構成。該模具本 體係爲不銹鋼圓柱體，內徑325毫米且長度1600毫米 。其一末端具有一可卸底板1 2，藉由電動機經由皮帶驅 動°其另一末端亦具有可卸環狀凸緣擋板1 3，防止熱固 性樹脂漏出。此凸綠擋板1 3具有一開口，可使反應氣體 逸出。該模具本體11係爲可分離式（由兩部分構成）， 以方便脫模。離心模製係藉著於該模具本體1 1中置入熱 固性樹脂’之後旋轉該模具組合體丨〇 (同時於熱固化溫 度下加熱）而達成。加熱係藉由環繞該模具本體n之電 熱器達成。 實施例1 [玻璃樣碳管之製備] 原料樹脂：供玻璃樣碳使用之較佳樹脂係爲熱固性樹 脂’諸如酚醛樹脂及呋喃樹脂。此實施例採用市售酚醛樹 脂 Gun.ei Kagaku Kogyo Co·，Ltd.所售之「PL4804」，其 預先於1 0托耳低壓下於6 5 °C下真空乾燥（低於5重量％ 水含量）6小時。酚醛樹脂管之製備：酚醛樹脂管係如下 -21 - (19) 200407275 文使用裝置有模具1 0之離心模製機形成。該| 預定量之酚醛樹脂。該模具1 0於6 0轉每分鐘 時，其表面溫度保持1 0 0 °c。該模具冷卻至室 模。因此得到3毫米厚、3 2 0毫米外徑、及J 之酚醛樹脂管。重複此方法以製備數個試樣。 固化：所得之酚醛樹脂管係藉著於3 0 0 °C 小時而固化。此固化係用以防止該酚醛樹脂管 變形；因此，若無變形之可能，則可省略。 碳化：該酚醛樹脂管係藉著於惰性氣體（ 於1 6 0 0 °C下加熱而碳化。因此得到2.5毫米厚 外徑、及1 2 6 5毫米長之玻璃樣碳管。 噴砂：所得之玻璃樣碳管曝露於碳化矽於 噴射流下，該噴射流係朝向其內側及外側，同 粗糙化。此方法中，各試樣係以不同晶粒大小 糙化，其他條件（壓力及噴嘴-表面距離）不變 電解氧化：玻璃樣碳管表面藉著浸漬於氫 液（〇. 1莫耳/公升）中’於試樣與鉑板相對 )之間施加電流，進行電解氧化而粗糙化。此 依一般方式洗滌及乾燥。 純化方法：已進行電解氧化之玻璃樣碳售 下於含氯氛圍中加熱（以進行純化）。經純化 %氫氟酸與2 %過氧化氫之混合物淸洗’之後 水淋洗，並於淸潔室中乾燥。 I具10置入 下旋轉5小 溫以進行脫 5 0 0毫米長 下加熱200 於碳化期間 氮）氛圍中 、268毫米 水中之漿液 時將兩側面 之碳化矽粗 〇 氧化鈉水溶 電極（陰極 步驟之後係 ί 於 2 2 0 0 °C 之試樣以2 重複以超純 -22- (20) (20)200407275 實驗編號1至4 供C V D裝置使用之內管的四個試樣（編號1至4 ) 係依下列順序進行前述步驟而製備。製備酚醛樹脂管—固 化—碳化—噴砂―電解氧化一純化。 實驗編號5及6 供C V D裝置使用之內管的四個試樣（編號1至4 ) 係依下列順序進行前述步驟而製備。製備酚醛樹脂管-固 化-碳化-> 純化—噴砂—電解氧化。（編號5及編號6所 使用之噴砂係於個別與編號1及編號2相同之條件下進行 )。編號5及6所使用之方法係與編號1及2者相同，不 同處係純化步驟係於噴砂及電解氧化步驟之前進行。 實驗編號7及8 試樣編號7係藉與試樣編號1至4相同之方法製備， 不同處係表面粗糙化所使用之噴砂步驟係採用較細之碳化 矽粒子。試樣編號8係藉與試樣編號1至4相同之方法製 備’不同處係表面粗糙化所使用之噴砂步驟係採用較粗之 碳化砂粒子。 貫驗編5虎9 試樣編號9係藉與試樣編號1至4相同之方法製備， 不同處係該噴砂步驟係分兩階段進行，第一階段係進行內 邰’而桌一階段係進行外部。 -23- (21) (21)200407275 所得之試樣編號1至9係測試下列項目。結果出示於 表1中。 (1 )表面糙度： 在表面糙化之後，供CVD裝置使用之內管的內表面 及外表面使用接觸探針型糙度測試機（Rank Tailor Co.， Ltd·製造）依JIS B 0 60 1所述測試表面糙度（Ra )。該表 面糙度（Ra )係以兩個沒有因爲操作產生刮痕的區域（各 爲內表面及外表面）之測量値的平均値表示。 (2 )粒子數： 依下述方式計數供CVD裝置使用之內管所釋放之粒 子數目。該內管置入已送入矽晶圓之垂直CVD裝置中。 該CVD裝置於減壓下於770 °C下送入二氯矽烷（SiCl2H2 )與氨（N Η 3 )之混合氣體。於各矽晶圓上形成氮化矽薄 膜（150奈米厚度）之步驟重複100次。在第一程及第 1 〇 〇程之後，計數大於0 · 2微米之粒子數目。此方法係使 用 Surfscan (WH-1700 型，Topcon 製造）達成。 (3 )金屬濃度： 試樣中之金屬濃度係依下述方式藉1 C P質譜測定。將 少量2 %氫氟酸與2 %過氧化氫之5 0 : 5 0混合物滴於欲分 析之矽晶圓表面上。表面上之溶液放置約1 〇分鐘，之以 回收。藉ICP-MS分析金屬濃度，數値以每單位矽晶圓面 (22) (22)200407275 積之金屬原子數目表示。用於分析之化學品係爲Kantc Kagaku Co.5 Ltd·製造之超純試劑。ICP質譜使用之裝置係 爲 Seiko Instruments Co·，Ltd·製造之 SPQ9000SE。該裝 置係於條件（a )下測定鐵、鉻、鈉、鉀、鈣、鎂及鋁， 而於條件（b )下測定銅。 (a )高頻輸出·· 0.8仟瓦，取樣深度：8毫米，載體 氣體：0.9公升/分鐘，使用PFA微流噴霧器，艙中氣體 :0 · 3 3公升/分鐘。 (b )高頻輸出：1 .3仟瓦，取樣深度：8毫米，載體 氣體：0.9公升/分鐘，使用PFA微流噴霧器，艙中氣體 ·· &E 〇 (4 )圓度： 外徑之最大及最小値係於供CVD裝置使用之內管的 頂端測得。圓度係以最大外徑與最小外徑之間的差値表示 (23)200407275 \〇 00 as U\ UJ A 實驗編號 K) 10.9 0.08 0.32 NJ Os 匚 0.13 表面糙度 Ra(微米） Lk) k) H—^ o bo o bo o o bo o 圓度 (毫米） o bo u> <0.2 bo <0.2 <0.2 <0.2 <0.2 表面中之金屬濃度(xl〇l°原子/厘米2) δ t-J <0.2 K) h—^ •私 <0.2 <0.2 <0.2 <0.2 ρ <0.2 <0.2 <0.2 s: <0.2 <0.2 <0.2 <0.2 〇 s 15.8 <0.2 13.7 10.6 o *4^ <0.2 o <0.2 10.5 11.2 〇 lyi o <0.2 13.4 s 12.1 13.5 to Lj o o K) to 16.1 i—^ bs 16.3 S； A o Ln o LO o \o 13.8 Lk) bo 16.2 13.9 LO to )—k > 1 442 415 336 矣 L»J ^r\ Lk) oo 第1程 之後 粒子數 1 1 1 1 1 00 K) LT\ oo 第100 程之後200407275 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a glass-like carbon assembly for use in a CVD (chemical vapor deposition) apparatus. Although the present invention is mainly related to an inner tube for a C V D device, the present invention also covers various components to be arranged inside the C V D device. [Previous technology] The manufacture of semiconductor devices is generally related to the so-called CVD method, which involves a gas-phase chemical reaction in which a reactant gas deposits silicon, silicon nitride, etc. in the form of a thin film on a silicon wafer. In this method, a silicon wafer is placed in an inner tube (shown in Figure 1) to uniformly heat and control the flow of reactant gases. The inner tube used for the CVD device needs to have good durability under general CVD conditions (heat resistance at 500 ° C or above and corrosion resistance of reactant gas). It is also necessary to release as little dust and impurity gases as possible. Traditionally, inner tubes made of quartz meet these requirements. The CVD method is based on the principle that heated reactant gases (as raw materials) are decomposed on silicon wafers or react with each other to form thin films such as polycrystalline silicon films and silicon nitride films. During the CVD process, decomposition of the reactant gas or reaction products are deposited on the surface of the inner tube. The inner tube with this deposit (polycrystalline silicon, silicon nitride, etc.) is reused without replacement to maintain capacity. After continuous use, the inner tube becomes covered with thick deposits, and finally peels off from the inner tube to produce fine particles. The fine particles are adhered to the silicon wafer, and the yield is low (4) (2) (2) 200407275. "Particle" means particle defects detected when the wafer is inspected by an optical tester. One method of eliminating particles due to deposits peeled from the inner tube is to periodically disassemble and rinse the inner tube to remove the CVD deposits. Washing systems use chemical solutions such as hydrofluoric acid and nitric acid. However, this cleaning operation reduces production capacity and increases manufacturing costs. Therefore, the inner tube should firmly adhere the CVD deposits so that the accumulated CVD deposits do not generate particles. The adhesion of the CVD deposit to the inner tube is affected by the dimensional change of the inner tube, which occurs when the CVD tank is cooled and heated to individually remove and mount the wafer. The inner tube should be determined to have good adhesion even if there is a dimensional change due to the cooling / heating cycle. Moreover, since the rinsing process used to remove the CVD deposits cannot be avoided, the inner tube must have good corrosion resistance to the aforementioned rinsing solution. Unfortunately, the customary inner tube made of quartz has insufficient adhesion to CVD deposits and insufficient corrosion resistance to scrubbing solutions. Under these circumstances, the present inventors have previously developed a novel glass-like carbon inner tube for use in a CVD apparatus that prevents particle generation, resists corrosion of the cleaning solution, and meets other aforementioned requirements, and has applied for a patent (Japanese Published Patent No. 3 5 04/2 00 1). There is another method to improve the adhesion of glass-like carbon components or glass-like carbon-coated graphite components to CVD deposits. The surface of the module is roughened by sandblasting to achieve its purpose. (Japanese Published Patent No. 342068/2001 and Japanese Patent Publication No. 86662/1994). It is also known that inner tubes and other components for CVD devices may contain 200407275 C3) impurities' and contaminate the wafer during the CVD process, resulting in device failure due to contamination. Therefore, the concentration of metal impurities in the surface of the module is more than 10 X 1 0 1G atoms / cm 2, and preferably not more than 5 x 1 0 m 2. In fact, commercially available analog wafers made from carbon prepared under appropriately controlled conditions have reached less than 5 X 1 0 1 G atoms per atom. This analog wafer has a mirror-finished surface with a surface greater than 0.1 micron. For this simulated wafer, the glass-like carbon inner tube for the CVD device needs to have a metal concentration of not higher than 5 X 1 0 1 G atoms / cm 2. The surface metal concentration is measured by measuring the metal on the surface of the carbon wafer. This method begins with the extraction of metals from samples using 2% hydrofluoric acid and 2% peroxide solution. The extract was then analyzed by I C P — M S (inductive affinity mass spectrometry). The amount of metal measured is expressed in terms of the number of atoms used to extract a unit area sample (atoms / cm2). In this manner, a glass-like carbon tube was prepared by preparing a resin tube, and then in an inert atmosphere. This heating temperature is usually higher than 800 ° C, preferably J to 1200 ° C, and more preferably 1300 to 2500 ° C. During heating and carbonization, the resin tube shrank significantly (about 20% by volume). This shrinkage brings it to a completely round glass-like carbon tube. A method for reaching the North has been proposed, which is to insert a graphite core in a carbonized resin tube or a glass-like carbon tube before high temperature heat treatment, as in Japanese Laid-Open Patent No. 189470/1999 and Profit Publication 1 8 94 71/1 99 Revealed. Because the resin tube shrinks with carbon, the core has an outer diameter equal to that of the glass-like carbon tube. The method that leads to the surface should not be used per centimeter of glass-like roughness. The roughness of the surface is not used. The mixed plasma of hydrogen takes every heat, and during I 1000, it is difficult to obtain before the cylindrical Japanese specialization. (4) (4) 200407275 However, it proves that the cylindrical core used in the aforementioned conventional method does not always produce a round glass-like carbon tube. [Summary of the Invention] The technology disclosed in the patent No. 3 3 2 5 04/2 0 0 1 (mentioned above) can effectively prevent the generation of particles and reduce the frequency of the washing process. This technology uses sandblasting to roughen the surface of the glass-like carbon inner tube used in the CVD device to improve the adhesion of the CVD deposits, but it cannot reduce the particles to the required level. This increases the content of metallic impurities due to surface roughening. At present, there is a need for an inner tube for a CVD apparatus which generates less impurities than the aforementioned technicians. Impurities (such as particles) occur as the CVD deposits peel off from the inner tube surface, as described earlier. The inventors conducted investigations to show that the CVD deposit film became thick before peeling off, causing cracking. The cracks in the surface of the CVD deposited film are shown in Fig. 5 (photographs obtained by a scanning electron microscope). The CVD deposition film is not only formed on the inner tube surface, but also on the surface of various components exposed to the C V D environment in the C V D device. Therefore, it is also necessary to suppress the formation of impurities (particles) formed from the CVD deposit film on the surface of components other than the inner tube. It is known that carbonaceous materials, such as glassy carbon, can be purified by heating the halogen-containing atmosphere at high temperatures (typically 2 000 ° C or above), allowing the halogen to penetrate the carbon and evaporating metallic impurities from the carbon. This method seems to be useful for reducing metallic impurities that may have contaminated the surface of the inner tube when the surface was roughened. -7- (5) (5) 200407275 On the other hand, the purification method may cause the size distortion of the carbonaceous material. However, the inner tube for the C V D unit should maintain sufficient roundness even after the purification method. The possible factor that the glass-like carbon tube's dimensional accuracy is not high enough is its abnormal volume change property. That is, it shrinks up to about 1200 ° C, and then expands slightly at a slightly higher temperature. With the aforementioned CVD deposited film, metal impurities exist not only on the inner tube surface but also on the surfaces of various components in the CVD environment of the CVD apparatus. Therefore, it is necessary to reduce the amount of metal impurities existing on the surface of components other than the inner pipe to suppress the formation of particles due to the metal impurities. Therefore, an object of the present invention is to provide a glass-like carbon module for a CVD apparatus having the following advantages, and a method for manufacturing the same. Improved adhesion to CVD deposits. After the cracking, the CVD deposit film is grown thick enough to suppress the ability to generate impurities (particles) due to peeling of the CVD deposit film. Properly roughened surfaces are obtained without adding metallic impurities that would generate particles. The ability to prevent the release of coriander powder. Another object of the present invention is to propose a method for manufacturing a glass-like carbon tube having a high degree of roughness. The main purpose of the present invention is to provide a glass-like carbon component for a CVD apparatus, which is characterized by Surface roughness (Ra) 値 of 1 to 10 microns (measured according to JIS B 060 1), and the surface contains less than 5 × 10C) atoms / cm 2 of iron, copper, chromium, sodium, potassium, calcium, magnesium , And aluminum. The surface roughness (Ra) listed in the present invention is the one measured in accordance with JIS S 060 1 unless otherwise stated. According to the present invention, the table of glass-like carbon components for use in CVD devices ~ 8-(6) (6) 200,407,275 surfaces are treated so that they are observed under a scanning electron microscope at a magnification of 0.000 times 50 x 50 There are at least five 1 to 10 micron diameter pits in the micron field of view or the surface has been treated so that a total length of at least 50 in a 50 x 50 micron field of view observed under a scanning electron microscope at a magnification of 1,000 times Micrometers and elongated depressions with a width of 0.5 to 5 micrometers. The `` total length '' means the sum of the lengths of the elongated depressions present in the field of view 値 (0. 5 to 5 microns width). According to the present invention, the glass-like carbon assembly for use in a CVD apparatus is any one of an inner tube, a wafer dish, a crystal holder, and a nozzle for use in a CVD apparatus. According to the present invention, a method of manufacturing a glass-like carbon module for use in a CVD apparatus is characterized by a surface roughening step and a subsequent purification step. This surface roughening step may be a mechanical step such as sandblasting and honing. This purification step may be a high temperature heat treatment in a halogen-containing atmosphere. If the glass-like carbon component used for the CVD apparatus is a glass-like carbon tube, it is desirable to perform mechanical surface roughening on both the inner surface and the outer surface, and then perform a purification step. According to the present invention, the method of manufacturing a glass-like carbon component for use in a CVD apparatus is characterized by mechanical surface roughening and chemical surface etching, which can be performed continuously (in the order described) or simultaneously. The mechanical surface roughening can be achieved by sandblasting or honing, and the chemical surface etching can be achieved by thermal oxidation or electrolytic oxidation. According to the present invention, a glass-like carbon tube for a CVD device is formed by molding a raw resin into a tube, and heating the formed resin after 800 to 1,300 t to convert it into a glass-like carbon tube. The glass-like carbon tube jacket -9-(7) (7) 200407275 is provided with a roundness correction clip, and the glass-like carbon tube is heated at a temperature higher than 150 ° C. [Embodiment] According to the present invention, a glass-like carbon inner tube for a CVD device is characterized by having inner and outer surface roughness, which improves the CVD deposits due to the anchoring effect caused by surface irregularities. Adhesiveness. According to the present invention, a glass-like carbon inner tube for use in a CVD apparatus should have a surface roughness Ra (Ra) (measured according to JIS B 06 01) of 0.1 to 10 μm. When the surface roughness 値 is lower than 0 . At 1 micron, the glass-like carbon inner tube has insufficient adhesion to the CVD deposits, making the CVD deposits susceptible to microcracking before becoming thick enough. Such small cracks release a large number of particles, so the inner tube needs to be replaced frequently. When the surface roughness 値 is greater than 10 micrometers, the glass-like carbon inner tube easily loses its surface layer. According to the present invention, the glass-like carbon inner tube for a CVD apparatus roughens its inner surface and outer surface (Ra system By 0. 1 to 10 microns). The surface roughening treatment should preferably be a mechanized treatment. Sandblasting with fine powder helps honing because it can achieve surface roughening without causing surface defects such as microcracks. According to the present invention, the glass-like carbon inner tube used for the CVD apparatus is made of glass-like carbon, so it has a thermal expansion coefficient of approximately 3 X 1 (Γ6. This is close to silicon nitride (3.4 XI (Γ6)). It means that there will not be a large size change (and the resulting stress) between the inner tube and the silicon nitride deposit due to heating during the formation of the silicon nitride film. -10- (8) (8) 200407275. The low The rubidium stress improves the adhesion between the inner tube and the silicon nitride deposit. According to the present invention, the glass-like carbon inner tube for a CVD device is characterized in that its surface content is less than 5 X 1 0 1G atoms each / Cm2 of iron, copper, chromium, sodium, potassium, calcium, magnesium, and aluminum. These metals are impurities present in the surface of the inner tube. If the concentration of any of these metals exceeds 5xl01 [atomic / Cm2, the inner tube easily releases a large number of particles from these metals. The inventors continue to investigate the cause of impurities (such as particles). As a result, it was found that even if the inner surface of The outer surface is roughened to 0. An average roughness (Ra) of 1 to 10 microns (measured according to JIS B060 1) is still unsatisfactory. In detail, it was found that the surface roughened by the sandblasting method cannot sufficiently improve the adhesion to the CVD deposited film. It has also been found that sandblasting leaves ceramic fines or metal fines (as abrasive media) or carbon fines (released by sandblasting) or stress (generated during sandblasting) on the surface. It is the cause of particles falling on the wafer. The previous proposal suggested that in order to completely eliminate impurities (such as particles), it is necessary to design a method that can more effectively improve the adhesion to the CVD deposited film than the sandblasting , And a method for preventing dust due to the inner tube itself. The present inventors further investigated that if mechanical surface roughening (such as sandblasting that produces mild surface irregularities) and chemical surface etching (formation of very small surface irregularities, with almost unchanged surface roughness (Ra)) are determined, -11-200407275 〇) The anchoring effect can significantly improve the adhesion between the inner tube and the CVD deposited film. In the following, "adhesiveness" sometimes means the adhesiveness between the inner tube surface and the CVD deposit film. The inner tube of the present invention should preferably have extremely small surface irregularities on the surface as described above. The surface irregularity is classified into the following item (1) or (2) to improve the adhesion between the inner tube and the CVD deposit film. The improved adhesion allows the CVD deposit film to have a sufficient thickness before cracking. It prevents impurities, such as particles. (1) The surface of the inner tube has at least five pits having a diameter of 1 to 10 micrometers in a field of view of 50 × 50 micrometers when viewed under a SEM magnification of 1000 times. (2) The surface of the inner tube has an elongated depression having a total length of at least 50 μm and a width of 0.5 to 5 μm in a field of view of 50 × 50 μm when viewed under a SEM magnified at 1000 ×. The “pit” in the aforementioned item (1) refers to an approximately circular depression existing on the surface of the inner tube, as shown in the S EM photograph in FIG. 3. It is indicated by the arrow in Figure 3 (b). Its depth is not important. ("Pits" are sometimes called "surface holes"). The "slender depression" in the aforementioned item (2) is the one formed before the "pits" are formed. It is shown in the SEM photograph shown in FIG. 4. In Figure 4 (c), it is marked with a thick line for identification. The number of potholes (surface holes) and the total length of the slender depressions (as defined in the present invention) are the average 値 of three measurements 値 obtained from a field of view of 50 × 50 μm at the aforementioned magnification. -12- (10) (10) 200407275 The surface structure listed in item (1) above has at least five pits with a diameter of 1 to 10 microns in the field of vision defined above. The pit significantly improves the adhesion between the inner tube and the CVD deposit film. Fewer than five pits in the field of view are not sufficient to produce a satisfactory anchoring effect (to establish adhesion between the inner tube and the CVD deposit film). The number of potholes should be no more than 10. The number of potholes in the field of view is not particularly limited; however, it should preferably be less than 100 according to the following factors. It takes a long time to chemically etch the surface to form pits above 1,000. Furthermore, as the number of potholes increases, the inner tube becomes thinner, and the adhesion is not greatly improved. Therefore, from an industrial standpoint, it is not expected to increase the number of potholes excessively. The pits on the surface should have a diameter of 1 to 10 microns as described in the aforementioned item (1), based on the following factors. When the diameter is less than 1 micron, the pit does not produce an anchoring effect to improve the adhesion to the C V D deposit film. On the other hand, pits with a diameter greater than 10 microns have a negative effect on adhesion. It is presumed that each pit has a relatively smooth surface, so large pits cannot produce the required anchoring effect. An elongated depression (0. 5 to 5 micron width) has a total length of at least 50 micron as described in item (2) above. If the total length is greater than 50 micrometers, the slender depression greatly improves the adhesion between the inner tube and the CVD deposited film. • If the total length is less than 50 microns, the slender depression cannot sufficiently improve the adhesion between the inner tube and the CVD deposit film (due to the anchoring effect). The total length should preferably be greater than 100 microns. -13- (11) (11) 200407275 The total length of the slender depressions does not have a particularly recognized upper limit for improving adhesion. However, slender depressions with a total length of more than 500 microns did not produce any significant additional effects. Therefore, from an industrial standpoint, the total length of the elongated depressions should be less than 500 microns. The slender depression should have the same as listed in item (2) above due to the following factors. 5 to 5 microns width. The width is less than 0. The 5 micron slender depression is too narrow to produce an anchoring effect to improve adhesion to the CVD deposited film. On the other hand, elongated depressions with a width greater than 5 microns cause fine powder to be released from the inner tube surface. As mentioned above, the inner tube of the present invention should have one or both of the surface structures described in the aforementioned items (1) and (2). The inner tube of the present invention is produced by the method described below. The tubular glass-like carbon used as the inner tube in the present invention can be produced by a general method, including a step of molding the raw resin and a step of carbonizing the formed molding. The carbonization step can be performed by a pre-heating step to avoid deformation. If a thermosetting resin (described below) is used as the raw resin, the curing process can be used as a pre-heating step. In this way, the resin constituting the molded article can be cured, and thereafter the resin can be carbonized without severe thermal deformation. To obtain a glass-like carbon tube, a molding step is performed to make the raw resin into a hollow cylindrical shape. The molding method in this case is not particularly limited; including centrifugal molding, injection molding, and extrusion molding. Among these molding methods, centrifugal molding is particularly desirable because of the following factors. Centrifugal molding allows the molten resin to flow and solidify in the mold; therefore, it can easily produce a tubular product with high dimensional accuracy and can be completely degassed (because both ends of the mold are open during molding) -14-(12) (12) 200407275. The base resin may include any known thermosetting resin such as a phenol resin and a furan resin. Details of the centrifugal molding of the raw resin are disclosed in Japanese Patent Publication No. 3 3 2 5 4/2 01. The aforementioned molding step for producing a molded article (or a resin tube) is followed by a carbonization step, which converts the resin tube into a glass-like carbon tube. Carbonization is usually accomplished by heating in an inert gas atmosphere (or non-oxidizing atmosphere) at 8000 to 2500 ° C. The carbonization step should be performed until the glass-like carbon tube maintains its circular cross section. This object is achieved by using a cylindrical core disclosed in Japanese Published Patent No. 17946 3/2002 and Japanese Patent Application No. 347393/2001. Methods for improving roundness are described below. If a thermosetting resin is used as the raw resin, it is desirable to provide the aforementioned curing step. The curing conditions vary depending on the resin; phenolic resins are usually cured in air at 180 to 350 ° C for 10 to 100 hours. The inner tube of the present invention can be produced by a method including a mechanical surface roughening step and a purification step in addition to the molding and carbonizing steps. The mechanical surface roughening step is used to form minute irregularities on the surface of the glass-like carbon tube by any known mechanical mechanism. This step can be performed at any stage between the molding step and the carbonization step. The mechanical surface roughening can be performed on the raw resin molded article before or after curing or on a glass-like carbon tube after carbonization. Carbonization can be achieved in two stages at about 900 ° C and about 120 ° C. In this case, the mechanical surface roughening can be completed after the first stage or the second stage. Mechanical surface roughening methods include sandblasting and honing. Sand blasting is preferred -15- (13) (13) 200407275 The abrasive powder used for sand blasting is not particularly limited, and any known one can be used. Including ceramic powders (such as alumina powder and silicon carbide powder), metal powder, and glass beads. The grain size and blasting conditions (pressure and nozzle distance) of the abrasive powder can be appropriately selected according to the required surface roughness. The abrasive powder is usually a fine powder having a grain size of about # 220 to 800. Honing can be achieved using sandpaper (# 150 to 100). The grain size and other conditions (honing pressure, etc.) can be appropriately selected according to the required surface roughness. The mechanical surface roughening should preferably be performed on the inside and outside of the tube at the same time to minimize dimensional changes due to later purification steps. If the mechanical surface roughening is performed on the inner side and the outer side individually, relatively large stress is generated in the subsequent purification step, and it is difficult to obtain an inner tube having a roughness sufficient for use in a CVD apparatus (the reason is unknown). According to another preferred embodiment, the mechanical surface roughening is achieved by or subsequent to chemical surface etching. Chemical surface etching removes part of the surface of the glass-like carbon tube to form minute surface irregularities. This treatment removes fines and scars (such as cracks) that are formed by roughening the mechanical surface. Therefore, the inner tube is prevented from releasing dust. Chemical surface etching is usually performed after mechanical surface roughening. If this order is reversed, minute irregularities formed by chemical surface etching are roughened and damaged by the mechanical surface. In detail, chemical surface etching is performed at any stage on glass-like carbon tubes that have been formed by mechanical surface roughening to form minute irregularities. However, it can be performed on a glass-like carbon tube (without mechanical surface roughening) in an environment for chemical surface roughening (for example, in a thermal • 16- (14) (14) 200407275 oxidation environment) Roughening of mechanical surfaces (such as sandblasting). The result in this case is the simultaneous mechanical surface roughening and chemical surface f modification. Chemical surface roughening treatments include thermal oxidation, electrolytic oxidation, and chemical etching. Thermal oxidation is performed by oxidizing the surface of the glass-like carbon tube to produce a surface structure that can be defined by the aforementioned item (1) or (2). It is usually heat-treated at 600 to 800 ° C in an oxidizing atmosphere (air or oxygen). 5 to 10 hours. Electrolytic oxidation is achieved by applying a current across the glass-like carbon tube (as an anode) and a cathode of platinum, stainless steel, or nickel (immersed in an electrolyte). The electrolyte is an aqueous solution of sodium hydroxide, hydroxide, or ammonia. The concentration of the electrolyte (NaOH solution) is 0. 1 to 2M. Electrolytic oxidation can be performed under any unrestricted conditions. The prerequisite is that the glass-like carbon tube formed has a surface structure as defined in the foregoing item (1) or (2). The degree of etching is controlled by adjusting the amount of current (typically 5 to 500 C / cm2). Chemical etching is achieved by immersing the glass-like carbon tube in a chemical solution that can dissolve its surface. Examples of the chemical solution are potassium dichromate or sodium dichromate aqueous solution and chromic acid mixture. The reason why electrolytic oxidation is better is that the degree of etching can be easily controlled. In addition, according to the present invention, the glass-like carbon tube that has been subjected to mechanical surface roughening alone or chemical surface etching at the same time should have a surface roughness ranging from 0.1 to 10 micrometers, from 0.1 3 to 3 microns is preferred. • 17- (15) (15) 200407275 The glass-like carbon tube whose surface has been roughened is then purified by heating it at a high temperature in a halogen-containing gas environment. This purification treatment reduces the content of metallic impurities that have entered the surface of the glass-like carbon tube when the mechanical surface has been roughened. After this purification treatment, a surface rinsing treatment was performed, and the respective concentrations of iron, copper, chromium, sodium, potassium, calcium, magnesium, and aluminum in the surface were reduced to less than 5 x 101 () atoms / cm2. The inventor's research has shown that if the surface roughness of the inner tube exceeds 10 micrometers, the purification treatment cannot reduce the metal concentration to less than 5 × 10 1 G atoms / cm 2, even after the surface washing treatment. The possible reason is that excessive surface roughening increases the effective surface area, and thus the metal concentration per unit area of the geometric surface of the inner tube increases. Therefore, from the viewpoint of reducing the metal concentration in the surface, the inner surface and the outer surface of the inner tube used for the CVD apparatus should be roughened to a specific limit (10 microns). In addition, after the purification treatment, the inner tube should be washed with hydrofluoric acid, hydrochloric acid, or hydrogen peroxide in a general manner. According to the present invention, the following method is adopted to improve the roughness of the glass-like carbon tube. The method of the present invention includes the steps of molding a raw resin into a tube, and carbonizing the resin tube by heating in an inert atmosphere at 800 to 130 ° C. In the carbonization step, the resin tube is shrunk and vitrified to produce a glass-like carbon tube, which is subsequently subjected to a high-temperature heat treatment. The carbonization step should be performed with a cylindrical core placed inside the resin tube so that the tube remains round during the heat treatment. Thereafter, the roundness correction jacket was sheathed outside the glass-like carbon tube (the 尙 was not subjected to high-temperature heat treatment). The glass-like carbon tube and the roundness correction clip are heated together in an inert atmosphere at a high temperature (ie, 15 00 ° C or above). During the heat treatment at high temperature, the roundness correction clip undergoes thermal expansion, and the glass-like -18- (16) (16) 200407275 carbon tube also undergoes thermal expansion and expansion due to structural changes in carbon. As a result, the glass-like carbon tube (having been subjected to high-temperature heat treatment) maintains a high degree of roundness, and the outer surface sleeve is stuck on the inner surface of the roundness correction clip. FIG. 6 is a graph showing the relationship between temperature and length change of the glassy carbon sample (without high temperature heat treatment) during heating. The heating rate is 200 ° C / hour. The glassy carbon sample is a rectangle 2 mm thick, 2 mm wide, and 20 mm long, which has been carbonized by heating at 90 ° C. As shown in FIG. 6, the molded sample of glassy carbon expands to It heats to about 950 ° C, shrinks when heated from 950 ° C to 1200 ° C, and expands again when heated above 2,000 t. This secondary expansion (at 1200 0 t and above) has a steeper slope than the primary expansion (0 to 900 ° C). At 0 to 900 ° C, the molded sample of glassy carbon has about 3 x 1 0_6 (K_1) Coefficient of linear expansion, and at 1 200 to 1 500 ° C, it has a thermal expansion coefficient of about 10 X 1 0. 6 (K · ι). The difference between the two coefficients results in 1 2 0 0 to 1 5 0 0 ° C # The raw structure changes. In other words, a glass-like carbon molded sample (carbonized at 900 ° C in this example) is heated from 1 200 ° C to 15 0 ° C The expansion mechanism is not fully understood; it may be due to the change in the carbon structure. The previous suggestion is that the carbonization of the glass-like carbon tube (which is subsequently subjected to high-temperature heat treatment) should be performed below 1 200 ° C, so that The glass-like carbon tube 1 2 0 0 to 1 500 ° C in the high temperature heat treatment for a long time. When taking into account the possible changes in the raw resin, the upper limit of the carbonization temperature should be 3,000 t. The lower limit of the fetification temperature should be 8 〇〇C, at this time the resin tube vitrified. This lower limit should be as close as possible to 12 0 ° C 'The material almost completely shrinks at this temperature. (Glass-like carbon mold heated at 900 ° c The product is -19- (17) (17) 200 407 275 9 50 to 1 2 0 (shrink at TC). The reason is that if the glass-like carbon tube is heated in the temperature range of 9 50 to 12 0 0 C Significant shrinkage, the glass-like carbon tube is excessively separated from the roundness correction clip sleeved on the outer side, which results in a positive effect of the subsequent roundness reduction of 1W due to expansion. In addition, the reason why the local temperature heat treatment should be performed at 15,000 or more If its temperature is lower than that shown, the roundness correction effect cannot be fully produced due to the expansion (because of the aforementioned structural change). The upper limit of the temperature for high temperature heat treatment is usually 2 500 ° c. The quality of the carbon tube and the use temperature depend on the roundness correction clip used in the present invention. It is formed of a material with good heat resistance and a coefficient of thermal expansion close to that of glass-like carbon tubes (for high-temperature heat treatment). The material includes graphite, glass-like carbon, and carbon fiber, the first type is preferred. Glass-like carbon tube. The scope of the present invention not only covers the inner tube, but also other components used for the CVD device, such as a boat, a wafer holder, a nozzle, and the like for supporting a wafer. It is made from raw resin by molding, carbonization, surface roughening, and surface chemical etching, just like the inner tube. As explained above for the inner tube, these glassy carbon components for CVD devices have extremely fine surface irregularities due to mechanical surface roughening and extremely small surface irregularities due to chemical surface etching. This surface structure produces an anchoring effect and improves its adhesion to CVD deposited films. In addition, the chemical surface etch prevents the component itself from releasing dust. These properties are extremely useful for manufacturing semiconductor devices. • 20- (18) (18) 200407275 Examples are described in more detail with reference to the following examples. In describing the present invention, these examples do not limit the scope of the present invention, and changes and modifications can be made without departing from the scope. Fig. 2 is a schematic sectional view showing an example of a mold for centrifugal molding used in an embodiment of the present invention. The mold 10 for centrifugal molding is composed of a mold body 11, a bottom plate 1 2, and a flange baffle plate 13. The mold is a stainless steel cylinder with an internal diameter of 325 mm and a length of 1600 mm. One end has a detachable bottom plate 12 which is driven by a motor through a belt. The other end also has a detachable ring-shaped flange baffle 13 to prevent the thermosetting resin from leaking out. The convex green baffle 13 has an opening through which the reaction gas can escape. The mold body 11 is detachable (consisting of two parts) to facilitate demolding. Centrifugal molding is achieved by inserting a thermosetting resin 'in the mold body 11 and then rotating the mold assembly (while heating at a thermosetting temperature). Heating is achieved by an electric heater surrounding the mold body n. Example 1 [Preparation of glass-like carbon tube] Raw resin: A preferred resin for glass-like carbon is a thermosetting resin 'such as a phenol resin and a furan resin. This example uses a commercially available phenolic resin Gun. ei Kagaku Kogyo Co ·, Ltd. The "PL4804" sold was vacuum-dried in advance (under 5 wt% water content) at 65 ° C under a low pressure of 10 Torr for 6 hours. Preparation of phenolic resin tube: The phenolic resin tube system is as follows-(19) 200407275 The text is formed by a centrifugal molding machine equipped with a mold 10. The | predetermined amount of phenolic resin. The surface temperature of the mold was maintained at 100 ° C at 60 rpm. The mold was cooled to the chamber mold. Thus, a phenol resin tube having a thickness of 3 mm, an outer diameter of 320 mm, and J was obtained. This method was repeated to prepare several samples. Curing: The obtained phenolic resin tube is cured by 300 ° C hours. This curing is used to prevent deformation of the phenol resin tube; therefore, it can be omitted if there is no possibility of deformation. Carbonization: The phenolic resin tube is carbonized by heating under an inert gas (at 1600 ° C. Therefore, 2. 5 mm thick glass-like carbon tube with an outer diameter of 1 2 6 5 mm. Sandblasting: The obtained glass-like carbon tube is exposed to silicon carbide under a jet stream, and the jet stream is roughened toward the inside and the outside thereof. In this method, each sample is roughened with different grain sizes, and other conditions (pressure and nozzle-surface distance) remain unchanged. Electrolytic oxidation: The surface of the glass-like carbon tube is immersed in a hydrogen solution (0. 1 mol / litre), a current was applied between the sample and the platinum plate, and electrolytic oxidation was performed to roughen it. This is washed and dried in the usual manner. Purification method: Glassy carbon that has undergone electrolytic oxidation is sold and heated in a chlorine-containing atmosphere (for purification). After purifying the mixture of purified% hydrofluoric acid and 2% hydrogen peroxide, it was rinsed with water and dried in a clean room. I set 10 with a rotation of 5 hours to remove 200 mm long and heat 200 nitrogen during carbonization) atmosphere, slurry in 268 mm water in both sides, coarse silicon carbide on both sides, sodium oxide water-soluble electrode (cathode step) Afterwards, the samples at 2 2 0 ° C were repeated with 2 ultra-pure -22- (20) (20) 200407275 Experiment No. 1 to 4 Four samples of the inner tube for the CVD device (No. 1 to 4) Prepared according to the following steps in the following order. Preparation of phenolic resin tube-curing-carbonization-sandblasting-electrolytic oxidation-purification. Experiment Nos. 5 and 6 Four samples of inner tubes for CVD devices (Nos. 1 to 4) ) Prepared by carrying out the aforementioned steps in the following order. Preparation of phenolic resin tube-curing-carbonization-> purification-sandblasting-electrolytic oxidation. Under the conditions). The methods used in No. 5 and 6 are the same as those in No. 1 and 2, except that the purification step is performed before the sandblasting and electrolytic oxidation steps. Experiment No. 7 and 8 Sample No. 7 is borrowed and tested Same method as sample numbers 1 to 4 Preparation, the sandblasting steps used for surface roughening in different places are using finer silicon carbide particles. Sample No. 8 is prepared by the same method as sample numbers 1 to 4 'Sandblasting used for surface roughening in different places The steps are made of coarser carbonized sand particles. The test series 5 tiger 9 sample number 9 is prepared by the same method as sample numbers 1 to 4, except that the sandblasting step is performed in two stages, the first stage is The internal stage is performed, and the first stage of the table is performed externally. -23- (21) (21) 200407275 The sample numbers 1 to 9 obtained are tested for the following items. The results are shown in Table 1. (1) Surface roughness: in After the surface was roughened, a contact probe type roughness tester (Rank Tailor Co. , Ltd.) was tested for surface roughness (Ra) according to JIS B 0 60 1. The surface roughness (Ra) is expressed as an average value of the measurement values of two areas (each of which is an inner surface and an outer surface) which are not scratched due to operation. (2) Number of particles: The number of particles released from the inner tube for use in the CVD apparatus was counted in the following manner. The inner tube is placed in a vertical CVD apparatus that has been fed into a silicon wafer. The CVD device feeds a mixed gas of dichlorosilane (SiCl2H2) and ammonia (NΗ3) at 770 ° C under reduced pressure. The process of forming a silicon nitride film (150 nm thickness) on each silicon wafer was repeated 100 times. After the first pass and the 100th pass, the number of particles larger than 0.2 µm was counted. This method was achieved using Surfscan (WH-1700, manufactured by Topcon). (3) Metal concentration: The metal concentration in the sample was measured by 1 C P mass spectrometry in the following manner. A small 50:50 mixture of 2% hydrofluoric acid and 2% hydrogen peroxide was dropped on the surface of the silicon wafer to be analyzed. The solution on the surface was left for about 10 minutes and recovered. The metal concentration is analyzed by ICP-MS, and the number is expressed as the number of metal atoms per unit of silicon wafer surface (22) (22) 200407275. The chemical used for the analysis was Kantec Kagaku Co. 5 Ltd. manufactured ultra-pure reagents. The device used for ICP mass spectrometry was SPQ9000SE manufactured by Seiko Instruments Co., Ltd. This device measures iron, chromium, sodium, potassium, calcium, magnesium, and aluminum under condition (a), and measures copper under condition (b). (a) High frequency output ... 8 仟 W, sampling depth: 8mm, carrier gas: 0. 9 liters / minute using a PFA microflow sprayer, gas in the cabin: 0 · 3 3 liters / minute. (b) High frequency output: 1. 3 仟 W, sampling depth: 8 mm, carrier gas: 0. 9 liters / minute, using PFA micro-flow sprayer, gas in the cabin. &Amp; E 0 (4) Roundness: The maximum and minimum of the outer diameter are measured at the top of the inner tube for the CVD device. Roundness is expressed as the difference between the maximum outer diameter and the minimum outer diameter (23) 200407275 \ 〇 00 as U \ UJ A Experiment No. K) 10. 9 0. 08 0. 32 NJ Os 匚 0. 13 Surface roughness Ra (micron) Lk) k) H— ^ o bo o bo o o bo o Roundness (mm) o bo u > < 0.2 bo < 0.2 < 0.2 < 0.2 < 0.2 Metal concentration in the surface (xl01 ° atoms / cm2) δ t-J < 0.2 K) h— ^ • Private < 0.2 < 0.2 < 0.2 < 0.2 ρ < 0.2 < 0.2 < 0.2 s: < 0.2 < 0.2 < 0.2 < 0.2 〇 s 15.8 < 0.2 13.7 10.6 o * 4 ^ < 0.2 o < 0.2 10.5 11.2 〇 lyi o < 0.2 13.4 s 12.1 13.5 to Lj oo K) to 16.1 i— ^ bs 16.3 S; A o Ln o LO o \ o 13.8 Lk) bo 16.2 13.9 LO to) —k > 1 442 415 336 矣 L »J ^ r \ Lk) oo Number of particles after 1st pass 1 1 1 1 1 00 K) LT \ oo After 100th pass
-26- (24) (24)200407275 如表1所示，若爲具有本發明界定範圍內之表面糙度 及表面金屬濃度之試樣編號1至4，則在薄膜形成操作第 一程之後的粒子數少於60個，即使在累積薄膜厚度達到 1 5微米之薄膜形成操作的第一百程之後亦然。結果產生 令人滿意之裝置良率。 相反地，已發現在純化步驟之後進行噴砂及電解氧化 之試樣編號5及6具有在藉噴砂進行表面粗糙化期間進入 玻璃樣碳管表面之殘留金屬雜質。因此，其無法符合本發 明對表面金屬濃度之要求。於整個薄膜形成過程中釋出大 量粒子（推測來自金屬雜質）。不適於製造半導體裝置。 使用碳化矽砂進行噴砂之試樣編號7具有低於本發明 所述之表面糙度値。其於薄膜形成過程初期釋出少量粒子 ;然而，在重複薄膜形成過程時，粒子數增加。因爲粒子 多於所示範圍，故薄膜形成過程無法重複1 〇 〇次。此等大 量粒子來自CVD沉積物薄膜（在重複薄膜形成過程之後 變厚）中之微裂紋。使用碳化矽粗砂進行噴砂之試樣編號 8具有高於本發明所示之表面糙度値。因爲其超過上限（ 1〇微米）之高表面糙度（1〇·9微米），其具有超過5χ 1 〇 1 G原子/厘米2之表面金屬濃度，而與純化過程無關。 因其於第一程薄膜形成過程中釋出大量粒子，故無法用於 製造半導體裝置。 因爲在純化過程中具有相對高應變而具有較差圓度（ 管頂之最大及最小外徑間之差値3 · 2毫米）的試樣編號9 不適於作爲C V D裝置內管，因其花費極長時間方能機械 •27- (25) (25)200407275 加工成適當之尺寸。 實施例2 [玻璃樣碳管之製備] 玻璃樣碳管係如下自購自Gunei Kagaku Kogy。d L t d ·之巾售醛樹脂「p l 4 8 0 4」（其預先於1 〇托耳減壓 下於100 °C下乾燥真空乾燥（低於5重量％水含量）1小 時）製備。酚醛樹脂係使用裝置有模具1 〇之離心模製機 製成管。置入7公斤酚醛樹脂，模具1〇於6 0 0轉每分鐘 下轉動1 〇小時，表面溫度保持於1 2 0 °C，以熔化醒樹 脂。該模具冷卻至室溫以進行脫模。因而得到尺寸爲3毫 米厚、323毫米外徑、及1 5 90毫米長之酚醛樹脂管。 該酚醛樹脂管係藉著於25(TC下於空氣中加熱10小 時而固化。經固化之酚醛樹脂管藉著於惰性氣體（氮）氛 圍中於1 60 0 °C下加熱而碳化。因而得到尺寸爲2.5毫米厚 、26 8毫米外徑及1 2 65毫米長之玻璃樣碳管。 實驗編號1 前述玻璃樣碳管之試樣以#400氧化鋁粉進行噴砂， 以將其內表面及外表面機械粗糙化。在噴砂之後，該試樣 具有〇·6微米表面糙度値。 之後，試樣於表2所示條件下於.0 . 1 Μ氫氧化鈉水溶 液中進行電解氧化（化學表面蝕刻），該試樣與鉑板相對 電極（陰極）之間施加電流。此步驟之後係依一般方式洗 -28- (26) (26)200407275 滌及乾燥。發現經處理之試樣具有0 · 6微米之表面f造度値 。換言之，該化學表面飽刻未改變表面縫度。 已進行電解氧化之試樣係藉著於2 2 0 (TC下於含氯氣 體中加熱而純化。經純化之試樣以2 %氫氟酸與2 %過氧 化氫之混合物洗滌，之後重複以超純水淋洗。最後於淸潔 室中乾燥。因而得到所需之供c V D裝置使用的內管。依 實施例1方式檢測表面金屬濃度。結果，所有試樣皆不大 於5 X 1 0 1Q原子/厘米2。 實驗編號2至7 試樣依與實驗編號1相同之方式進行噴砂。噴砂之後 ’發現試樣具有0.6微米之表面糙度値。試樣依與實驗編 號1之方式進行電解氧化，不同處係條件如表2中所示般 改變。電解氧化之後進行洗·、乾燥及純化。因而得到供 CVD裝置用之內管。發現其具有〇·6微米表面糙度値。此 表不化學表面蝕刻（電解氧化）不改變表面縫度。亦依實 施例1之方式檢測表面金屬濃度。結果所有試樣皆不大於 5χΐ〇1()原子/厘米2。 所得之供CVD裝置使用的內管（編號1至7)進行 下列項目之測試。結果出示於表2。 (1 )表面糙度： 醫式樣依實施例1之方式測試表面糙度。 -29- (27) 200407275 (2 )坑洞及細長凹陷·· 於SEM ( X 1 000 )下觀察以檢測試樣表面。將 任意視野（5 0 X 5 0微米）照相。計數各視野中之坑洞 徑1至1 0微米），且測量各視野中細長凹陷（〇 · 5至 米寬）之總長度。計算每個視野之平均値。 (3 ) CVD沉積物薄膜（氮化物薄膜）中產生表面裂 厚度： 將小片內管放置於垂直型低壓CVD裝置中。該 裝置於7 8 0 °C下送入NH3與SiCl2H2之混合氣體，以 內管表面上形成氮化物薄膜。形成於該片上之氮化物 的表面係於SEM ( X 5 0 0 0 )下於任意十個視野中在 時隔下進行觀察。記錄開始產生裂紋之薄膜厚度。 (4 )粒子數目： 自供CVD裝置使用之內管釋出之粒子數目係依 方式計數。該內管放置於已送入矽晶圓之垂直CVD 中。該CVD裝置於減壓下加熱至800 °C，而不送入 物氣體。該晶圓自CVD裝置取出，計數其上之粒子 〇 此外，圖3係爲出示供CVD裝置使用之內管（ 樣編號4之條件下製得）表面的SEM相片。圖.3 ( 2 兩部分構成。虛線下之部分表示在化學表面蝕刻時被 之表面，其實質上僅進行機械表面粗糙化（噴砂）。 三個 (直 5微 紋之 CVD 於該 薄膜 特定 下述 裝置 反應 數目 於試 )由 遮蓋 虛線 -30 (28) 200407275 上方之部分表示進行機械表面粗糙化及後續化學表面蝕刻 之表面。圖3(b)係爲表示圖3(a)中之一視野（50x 5 0微米）的部分放大圖。圖3 ( b )中之箭號係表示表面 坑洞。 圖4係爲出示供CVD裝置使用之內管的表面之SEM 相片’其係於如同試樣編號3所示之條件下製得。圖4 ( b )係爲出示圖4 ( a )中之一視野（5 0 X 5 0微米）的部分 放大圖。明白顯現長形凹陷。圖4 ( c )中，長形凹陷係 以粗線標示，以易於辨識。 表2 實驗 編號 施加電流量 (C/cm2) 表面中之 坑洞數目 長形凹陷之 總長度(微米） 產生表面裂紋 之厚度(微米） 粒子數目 (每晶圓） 1 10 4 55 10 115 2 40 7 60 12 97 3 80 10 260 18 53 4 100 17 22 62 5 200 32 38 49 6 0 0 0 0.4 233 7 5 3 20 1.3 196 註：因過度蝕刻而無法測量。-26- (24) (24) 200407275 As shown in Table 1, if the sample numbers 1 to 4 have surface roughness and surface metal concentration within the scope of the present invention, the The number of particles is less than 60, even after the 100th pass of a film formation operation with a cumulative film thickness of 15 microns. The result is a satisfactory device yield. In contrast, Sample Nos. 5 and 6 subjected to sandblasting and electrolytic oxidation after the purification step have been found to have residual metal impurities entering the surface of the glass-like carbon tube during surface roughening by sandblasting. Therefore, it cannot meet the surface metal concentration requirements of the present invention. A large number of particles were released throughout the film formation process (presumably from metallic impurities). Not suitable for manufacturing semiconductor devices. Sample No. 7 using silicon carbide sand for blasting has a surface roughness 低于 lower than that described in the present invention. It releases a small amount of particles early in the film formation process; however, the number of particles increases when the film formation process is repeated. Because there are more particles than shown, the film formation process cannot be repeated 1,000 times. These large particles come from microcracks in a CVD deposit film that thickens after repeating the film formation process. Sample No. 8 blasted with silicon carbide grit has a surface roughness 高于 higher than that shown in the present invention. Because of its high surface roughness (10.9 micrometers) above the upper limit (10 micrometers), it has a surface metal concentration of more than 5 x 10 G atoms / cm2, regardless of the purification process. Because it releases a large number of particles during the first pass of thin film formation, it cannot be used to manufacture semiconductor devices. Sample No. 9 due to its relatively high strain during purification and its poor roundness (the difference between the maximum and minimum outer diameters of the tube top 毫米 3 mm) is not suitable for use as an inner tube of a CVD device, as it takes a long time Only time machine • 27- (25) (25) 200407275 Processed to the appropriate size. Example 2 [Preparation of a glass-like carbon tube] A glass-like carbon tube was purchased from Gunei Kagaku Kogy as follows. d L t d. The aldehyde-selling resin "p l 4 8 0 4" (which was previously dried at 100 ° C under a reduced pressure of 10 Torr and vacuum dried (less than 5% by weight water content) for 1 hour) was prepared. Phenolic resin was made into a tube using a centrifugal molding machine equipped with a mold 10. 7 kg of phenolic resin was placed, and the mold was rotated at 600 revolutions per minute for 10 hours. The surface temperature was maintained at 120 ° C to melt the resin. The mold was cooled to room temperature for demolding. Thus, a phenol resin tube having a size of 3 mm thick, an outer diameter of 323 mm, and a length of 15 to 90 mm was obtained. The phenolic resin tube was cured by heating in air at 25 ° C for 10 hours. The cured phenolic resin tube was carbonized by heating at 1 60 ° C in an inert gas (nitrogen) atmosphere. Thus obtained A glass-like carbon tube with a size of 2.5 mm thick, an outer diameter of 26 8 mm, and a length of 1 2 65 mm. Experiment No. 1 The sample of the aforementioned glass-like carbon tube was sandblasted with # 400 alumina powder to make its inner surface and outer The surface is mechanically roughened. After sandblasting, the sample has a surface roughness of 0.6 micron. After that, the sample was electrolytically oxidized in a 0.1 M sodium hydroxide aqueous solution under the conditions shown in Table 2 (chemical surface Etching), a current is applied between the sample and the opposite electrode (cathode) of the platinum plate. After this step, it is washed and dried in the usual way. -28- (26) (26) 200407275 was washed and dried. The treated sample was found to have 0 · The 6-micron surface f is 値. In other words, the chemical surface is saturated without changing the surface seam. The sample that has undergone electrolytic oxidation is purified by heating in a chlorine-containing gas at 220 ° C. Purified The sample is a mixture of 2% hydrofluoric acid and 2% hydrogen peroxide After washing, repeated rinsing with ultrapure water. Finally, drying in a clean room. Therefore, the required inner tube for the c VD device was obtained. The surface metal concentration was measured in the same manner as in Example 1. As a result, all the samples were not Greater than 5 X 1 0 1Q atoms / cm2. Experiments Nos. 2 to 7 The specimens were sandblasted in the same manner as Experiment No. 1. After sandblasting, the specimens were found to have a surface roughness of 0.6 microns. The electrolytic oxidation method was carried out in the first method, and the different conditions were changed as shown in Table 2. After electrolytic oxidation, washing, drying and purification were performed. Thus, an inner tube for a CVD device was obtained. Degree. This table shows that chemical surface etching (electrolytic oxidation) does not change the surface seam. The surface metal concentration was also measured in the same manner as in Example 1. As a result, all samples were not greater than 5χΐ〇1 () atoms / cm2. The inner tube (numbers 1 to 7) for the CVD device was tested for the following items. The results are shown in Table 2. (1) Surface roughness: The medical specifications were used to test the surface roughness according to the method of Example 1. -29- (27 200407275 (2) Hang And slender depressions · Observe the surface of the sample under SEM (X 1 000). Take a photo of any field of view (50 X 50 microns). Count the diameter of the pits in each field of view (1 to 10 microns) and measure The total length of the slender depressions (0.5 to meters wide) in each field of view. Calculate the average 値 for each field of view. (3) The thickness of the surface crack in the CVD deposition film (nitride film): Place the small inner tube in a vertical position In a low pressure CVD device, the device sends a mixed gas of NH3 and SiCl2H2 at 78 ° C to form a nitride film on the inner tube surface. The surface of the nitride formed on the sheet was observed under a SEM (X5000) in any ten fields of view at time intervals. Record the thickness of the film where cracking started. (4) Number of particles: The number of particles released from the inner tube used for the CVD device is counted in a manner. The inner tube is placed in a vertical CVD that has been fed into a silicon wafer. The CVD device was heated to 800 ° C under reduced pressure without feeding gas. The wafer was taken out of the CVD apparatus, and the particles thereon were counted. In addition, FIG. 3 is a SEM photograph showing the surface of the inner tube (made under the condition of sample number 4) for the CVD apparatus. Fig. 3 (2). The part below the dotted line indicates the surface that was used during the chemical surface etching, which is essentially only mechanical surface roughening (sand blasting). Three (straight 5 microstripe CVD under this film specific) The number of device reactions described above is tested. The part above the dotted line -30 (28) 200407275 indicates the surface where mechanical surface roughening and subsequent chemical surface etching are performed. Figure 3 (b) is a view showing a field of view in Figure 3 (a) (50x50 micron) part of the enlarged view. The arrows in Figure 3 (b) indicate surface pits. Figure 4 is a SEM photograph showing the surface of the inner tube used in the CVD device, which is similar to the sample It is made under the conditions shown in number 3. Fig. 4 (b) is a partially enlarged view showing a field of view (50 x 50 micron) in Fig. 4 (a). The long depression is clearly shown. Fig. 4 (c ), The long depressions are marked with thick lines for easy identification. Table 2 Experiment Number Applied Current (C / cm2) Number of Pits in the Surface Total Length of Long Depressions (microns) Thickness of Surface Cracks (microns) ) Number of particles (per wafer) 1 10 4 55 10 115 2 40 7 60 12 97 3 80 10 260 18 53 4 100 17 22 62 5 200 32 38 49 6 0 0 0 0.4 233 7 5 3 20 1.3 196 Note: It cannot be measured due to excessive etching.
符合表面坑洞數目及細長凹陷總長度之要求的試樣編 號1至5使氮化物薄膜於產生表面裂紋之前生長至實質厚 -31 - (29) (29)200407275 度。意指其可連續使用而不釋出粉塵，直至其上層形成厚 氮化物薄膜。此外，其於操作期間釋出之粒子極少。 相反地，不符合表面坑洞數目及細長凹陷總長度之要 求的試樣編號6及7具有下列缺點。 未進行化學表面蝕刻（電解氧化）之試樣編號6導致 氮化物薄膜在開始操作之後迅速裂開。氮化物薄膜之裂開 使得必需早期置換及淸洗內管，亦於操作期間釋出大量粒 子。 使用低量電流進行電解氧化之試樣編號7具有較少坑 洞及較小之長形凹陷總長度。因此，其導致氮化物薄膜於 開始操作之後迅速裂開。氮化物薄膜之裂開使得必需早期 置換及淸洗內管，亦於操作期間釋出大量粒子。 實驗編號8 前述玻璃樣碳管以砂紙（#24 0 )進行硏磨，以於其內 表面及外表面上進行機械表面粗糙化。此處理產生2 · 1微 米之表面糙度。 之後，該玻璃樣碳管於空氣中於圖3所示之不同溫度 下進行熱氧化1小時。此方法不改變表面糙度（2 · 1微米 )0 已經熱氧化之玻璃樣碳管進行純化處理，之後淸洗且 乾燥（依實驗編號1至7之方式）。形成之供CVD使甩 的內管依實施例1之方式測試表面金屬濃度。結果所有試 樣皆低於5xl01()原子/厘米2。 -32- (30) 200407275 實驗編號9至1 2 使用硏磨處理之玻璃樣碳管的試樣係依實驗編號8之 方式製備。發現其具有2 . 1微米表面糙度値。其依實驗編 號8之方式進行熱氧化及純化程序’不同處係溫度係如表 3所示般變化。發現所形成之供CVD裝置使用的內管具 有2 . 1微米之表面糙度値。顯示化學表面蝕刻（熱氧化） 不改變表面糙度。亦依實施例1方式測試其表面金屬濃度 。結果所有試樣皆低於5 X 1 0 1G原子/厘米2。 所得之供CVD裝置使用的內管進行實驗編號1至7 中的項目之測試。結果出示於表3中。 表3 實驗 熱氧化之溫度 表面中之 長形凹陷之 產生表面裂紋 粒子數目 編號 (°C) 坑洞數目 總長度(微米） 之厚度(微米） (每晶圓） 8 650 6 58 8 92 9 675 21 114 16 87 10 700 29 —* 26 89 11 •攀 0 0 0.6 325 12 600 5 42 1.5 126 註：因過度蝕刻而無法測量 符合表面坑洞數目及細長凹陷之總長度的要求之試樣 編號8至1 0使氮化物薄膜在產生表面裂紋之前生長至實 -33- (31) (31)200407275 質厚度。意指其可連續使用而不釋出粉塵，直至其上層形 成氮化物厚膜。此外，其於操作期間釋出之粒子極少。 相反地，不符合表面坑洞數目及細長凹陷總長度之要 求的試樣編號1 1及1 2具有下列缺點。 未進行化學表面蝕刻（熱氧化）之試樣編號1 1導致 氮化物薄膜在開始操作之後迅速裂開。氮化物薄膜之裂開 使得必需早期置換及淸洗該內管，亦於操作期間釋出大量 粒子。 於低溫下進行熱氧化之試樣編號1 2具有較少數之坑 洞及較短之細長凹陷總長度。因此，導致氮化物薄膜於開 始操作之後迅速裂開。氮化物薄膜之裂開使得必需早期置 換及淸洗該內管，亦於操作期間釋出大量粒子。 實施例3 實驗編號1 玻璃樣碳管係如下自購自 Gunei Kagaku Kogyo Co.， Ltd·之市售酚醛樹脂「PL4 8 04」（其已預先脫水）製備。 酉分醛樹脂係使用裝置有模具1 0之離心模製機製成管。置 入預定量之酚醛樹脂，模具1 0於600轉每分鐘下轉動24 小時’表面溫度保持於1 00。(：。該模具冷卻至室溫以進行 脫模。因而得到尺寸爲2 · 5毫米厚、3 3 0毫米外徑、及 12〇〇毫米長之酚醛樹脂管。 隨後，如圖7所示其中插有內芯23之酚醛樹脂管2】 依下列方式於120 (TC下碳化。（此內芯覆有碳纖維賣毛） -34- (32) (32)200407275 。酚醛樹脂管2 1與內芯2 3 —起於充塡氮氣之電爐中加熱 ，於2 t /小時速率下將其中溫度升高至1 2 0 0 °C。該酚醛 樹脂管2 1保持於1 20 0 °C歷經1小時以進行碳化。取出內 芯23。因此得到厚1 .9毫米、外徑（假設爲圓管）249毫 米且長900毫米之玻璃樣碳管22。而該內芯23係爲厚15 晕:米、外徑240毫米、且長約1200毫米之石墨管23a。 其具有一層環繞其外表面之碳纖維氈（3毫米厚）2 3 b， 如圖7所示。 圖8出示本發明所使用之圓度修正夾的一實例。圖8 (a )係爲平面圖，而圖8 ( b )係爲沿A-A線取得之剖面 圖。圓度修正夾係由石墨製得。如圖8 ( A )所示，其係 爲300x300毫米且30毫米厚之正方形板。中心具有直徑 爲250毫米之圓孔24a。此孔24a中插入前述玻璃樣碳管 22 ° 如圖9所示，該圓管修正夾24係排列於該玻璃樣碳 管22之一末端的外側，形成之組合體係於氮氣中於電爐 中加熱，以進行高溫處理。該溫度係於2 0 °C /小時速率 下升高至1 2 00 °C，隨之於2°C/小時速率下升高至1500 °C。此溫度保持1小時。在此高溫處理之後’取出圓度修 正夾2 4。 形成之玻璃樣碳管使用#400氧化鋁粉進行噴砂，以 於其內表面及外表面上進行機械表面糙化。之後，藉著於 含氯氣體氛圍中於2200 °C下加熱而進行純化處理。 在純化處理之後’檢測該玻璃樣碳管之圓度。發現在 -35- (33) (33)200407275 配置圓度修正夾之末端所測量之最大外徑與最小外徑間的 差値爲0 · 3毫米。證明該圓度修正夾可用於製造具有高度 圓度之大型玻璃樣碳管。該圓形玻璃樣碳管不需進行硏磨 以修正尺寸；其可作爲CVD裝置之內管。 實驗編號2 依實驗編號1之方式製備厚2.5毫米、3 3 0毫米外徑 、且1 2 00長之酚醛樹脂管。在其中配置內芯23下於充塡 氮氣之電爐中進行熱處理。溫度於2 °C /小時之速率下升 高至1 5 00 °C。此溫度保持1小時。形成之玻璃樣碳管依 實驗編號1之方式進行機械表面糙化及純化處理。 發現所得之玻璃樣碳管的最大外徑與最小外徑之間具 有1 .2毫米之差値。實驗編號1中之試樣的圓度較差，因 此在作爲內管之前需要進行機械加工。 [本發明效果] 如前文所述，本發明提供一種供CVD裝置使用之玻 璃樣碳內管，及其製造方法。該內管表面經糙化，而不增 加導致粒子之金屬雜質。該經糙化之表面改善其對該 CVD沉積物薄膜之黏著性。該表面糙化不釋出粉塵。因 爲此等特性，該內管不需經常淸洗來去除CVD沉積物。 此外，該玻璃樣碳管具有高度圓度，故適用於CVD裝置 (34) (34)200407275 【圖式簡單說明】 圖1係爲說明垂直低壓CVD裝置之示意圖，其係爲 藉CVD方法製造半導體裝置之CVD裝置之一。 圖2係爲說明使用於本發明之離心模製的示意圖。 圖3係爲掃描式電子顯微鏡相片，顯示存在於本發明 供C V D裝置使用之內管的表面中之小坑洞。 圖4係爲掃描式電子顯微鏡相片，顯示存在於本發明 供C V D裝置使用之內管的表面中之細長凹陷。 圖5係爲掃描式電子顯微鏡相片，顯示供CVD裝置 使用之內管表面上的氮化物薄膜表面中所形成的裂紋。 圖6係爲顯示一片已於90(TC下碳化之玻璃樣碳之長 度變化與溫度之間的關係之圖。 圖7係爲出示內芯（具有碳纖維氈）放置於酚醛樹脂 管中之方式的剖面圖。 圖8 ( a )及8 ( b )個別係爲說明本發明所使用之圓 度修正夾的平面圖及沿A - A取得之剖面圖。 圖9係爲出不外側套有圓度修正夾之玻璃樣碳管（在 高溫熱處理之前）的剖面圖。 主要元件對照表 10 模具 11 模具本體 12 底板 13 凸緣擋板 -37- (35)200407275 2 1 酚 醛 樹 脂 管 23a 石 墨 管 23b 碳 纖 維 氈 23 內 心 24a 圓 孔 24 圓 度 修 正 夾 22 玻 璃 樣 碳 管 1 內 管 2 外 管 3 矽 晶 圓 4 經 負 載 晶 圓板 5 歧 管 5 a 氣 體 噴 出 器 5b 氣 體 排 放 管 6 加 熱 器 -38-Sample numbers 1 to 5 that meet the requirements for the number of surface pits and the total length of the slender depressions allowed the nitride film to grow to a substantial thickness of -31-(29) (29) 200407275 degrees before surface cracks occurred. This means that it can be used continuously without releasing dust until its upper layer forms a thick nitride film. In addition, very few particles are released during operation. In contrast, Sample Nos. 6 and 7 which do not meet the requirements of the number of surface pits and the total length of the slender depressions have the following disadvantages. Sample No. 6 without chemical surface etching (electrolytic oxidation) caused the nitride film to crack rapidly after starting the operation. The cracking of the nitride film makes it necessary to replace and rinse the inner tube early, and also releases a large number of particles during operation. Sample No. 7 using a low amount of current for electrolytic oxidation has fewer pits and a smaller overall length of the elongated depression. Therefore, it causes the nitride film to crack rapidly after the operation is started. The cracking of the nitride film necessitates early replacement and rinsing of the inner tube, and also releases a large number of particles during operation. Experiment No. 8 The aforementioned glass-like carbon tube was honed with sandpaper (# 24 0) to perform mechanical surface roughening on its inner surface and outer surface. This treatment resulted in a surface roughness of 2.1 micrometers. Thereafter, the glass-like carbon tube was thermally oxidized in the air at different temperatures as shown in Fig. 3 for 1 hour. This method does not change the surface roughness (2.1 micron). The glass-like carbon tube that has been thermally oxidized is purified and then washed and dried (in the manner of experiment numbers 1 to 7). The inner tube formed for CVD was tested for surface metal concentration in the same manner as in Example 1. As a result, all the samples were lower than 5xl01 () atoms / cm2. -32- (30) 200407275 Experiment Nos. 9 to 1 2 Samples of glass-like carbon tubes treated with honing were prepared according to Experiment No. 8. It was found to have a surface roughness of 2.1 microns. It performs the thermal oxidation and purification procedure according to the method of Experiment No. 8 '. The temperature in different places is as shown in Table 3. The inner tube formed for use in the CVD apparatus was found to have a surface roughness of 2.1 m. Shows chemical surface etching (thermal oxidation) does not change surface roughness. The surface metal concentration was also tested in the same manner as in Example 1. As a result, all the samples were lower than 5 X 1 0 1G atoms / cm 2. The obtained inner tube for a CVD apparatus was tested for items in Experiment Nos. 1 to 7. The results are shown in Table 3. Table 3 Number of surface cracks generated by long depressions on the surface of the experimental thermal oxidation temperature (° C) Number of pits Total length (microns) Thickness (microns) (per wafer) 8 650 6 58 8 92 9 675 21 114 16 87 10 700 29 — * 26 89 11 • Climbing 0 0 0.6 325 12 600 5 42 1.5 126 Note: It is impossible to measure the number of surface pits and the total length of slender depressions due to excessive etching. Sample No. 8 To 10, the nitride film is grown to a solid thickness of -33- (31) (31) 200407275 before a surface crack occurs. This means that it can be used continuously without releasing dust until its upper layer forms a thick nitride film. In addition, very few particles are released during operation. In contrast, sample numbers 1 1 and 12 that do not meet the requirements of the number of surface pits and the total length of the slender depressions have the following disadvantages. Sample No. 1 without chemical surface etching (thermal oxidation) caused the nitride film to crack rapidly after starting the operation. The cracking of the nitride film makes it necessary to replace and rinse the inner tube early, and also releases a large number of particles during operation. Sample No. 12, which was thermally oxidized at a low temperature, had a smaller number of pits and a shorter total length of the elongated depressions. As a result, the nitride film is caused to crack rapidly after starting the operation. The cracking of the nitride film necessitates early replacement and cleaning of the inner tube, and also releases a large number of particles during operation. Example 3 Experiment No. 1 A glass-like carbon tube was prepared from a commercially available phenolic resin "PL4 8 04" (which had been previously dehydrated) purchased from Gunei Kagaku Kogyo Co., Ltd. as follows. Centrifugal aldehyde resin is made into tubes using a centrifugal molding machine equipped with a mold 10. By inserting a predetermined amount of phenolic resin, the mold is rotated at 600 revolutions per minute for 24 hours, and the surface temperature is maintained at 100. (: The mold was cooled to room temperature for demolding. Thus, a phenol resin tube having a size of 2.5 mm thick, an outer diameter of 330 mm, and a length of 12,000 mm was obtained. Subsequently, as shown in FIG. 7 Phenolic resin tube 2 with inner core 23] Carbonized at 120 (TC.) (The inner core is covered with carbon fiber wool) -34- (32) (32) 200407275. Phenolic resin tube 2 1 and inner core 2 3 —Heating in an electric furnace filled with nitrogen and increasing the temperature to 1 2 0 ° C at a rate of 2 t / hour. The phenol resin tube 21 was maintained at 1 200 0 ° C for 1 hour to Carburizing. Take out the inner core 23. Therefore, a glass-like carbon tube 22 with a thickness of 1.9 mm, an outer diameter (assuming a round tube) of 249 mm, and a length of 900 mm is obtained. The core 23 is 15 thick halo: meters, A graphite tube 23a with an outer diameter of 240 mm and a length of about 1200 mm. It has a layer of carbon fiber felt (3 mm thick) 2 3 b surrounding its outer surface, as shown in Figure 7. Figure 8 shows the roundness used in the present invention An example of a correction clip. Figure 8 (a) is a plan view, and Figure 8 (b) is a cross-sectional view taken along line AA. The roundness correction clip is made of graphite As shown in Fig. 8 (A), it is a 300x300 mm and 30 mm thick square plate. The center has a round hole 24a with a diameter of 250 mm. The aforementioned glass-like carbon tube 22 is inserted into this hole 24a as shown in Fig. 9 The round tube correction clip 24 is arranged outside the one end of the glass-like carbon tube 22, and the combined system formed is heated in an electric furnace in nitrogen for high-temperature treatment. The temperature is at a rate of 20 ° C / hour The temperature rises to 1 200 ° C, and then rises to 1500 ° C at a rate of 2 ° C / hour. This temperature is maintained for 1 hour. After this high temperature treatment, the 'roundness correction clip 24' is removed. The glass formed The sample carbon tube was sandblasted with # 400 alumina powder to mechanically roughen its inner and outer surfaces. After that, it was purified by heating at 2200 ° C in a chlorine-containing gas atmosphere. Purification After processing, 'roundness of the glass-like carbon tube was detected. It was found that the difference between the maximum outer diameter and the minimum outer diameter measured at the end of the -35- (33) (33) 200407275 equipped with a roundness correction clip was 0 · 3 Mm. Prove that the roundness correction clip can be used to make Type glass-like carbon tube. This round glass-like carbon tube does not need to be honed to modify the size; it can be used as the inner tube of a CVD device. Experiment No. 2 According to the method of Experiment No. 1, a thickness of 2.5 mm and an outer diameter of 330 mm Phenol resin tube with a diameter of 1 200. Heat treatment is performed in an electric furnace filled with nitrogen under the inner core 23. The temperature is increased to 15 00 ° C at a rate of 2 ° C / hour. This temperature Hold for 1 hour. The formed glass-like carbon tube was subjected to mechanical surface roughening and purification treatment according to the method of Experiment No. 1. It was found that there was a difference of 1.2 mm between the maximum outer diameter and the minimum outer diameter of the obtained glass-like carbon tube. The roundness of the sample in Experiment No. 1 was poor, so it needed to be machined before being used as an inner tube. [Effect of the present invention] As described above, the present invention provides a glass-like carbon inner tube for use in a CVD apparatus, and a method for manufacturing the same. The inner tube surface is roughened without adding metallic impurities that cause particles. The roughened surface improves its adhesion to the CVD deposited film. This surface roughening does not release dust. Because of these characteristics, the inner tube does not require frequent rinsing to remove CVD deposits. In addition, the glass-like carbon tube has a high degree of roundness, so it is suitable for a CVD device (34) (34) 200 407 275 One of the CVD devices. FIG. 2 is a schematic diagram illustrating centrifugal molding used in the present invention. Fig. 3 is a photograph of a scanning electron microscope showing small pits existing in the surface of the inner tube for a CVD device according to the present invention. Fig. 4 is a photograph of a scanning electron microscope showing an elongated depression in the surface of the inner tube for a CVD device of the present invention. Fig. 5 is a scanning electron microscope photograph showing cracks formed in the surface of the nitride film on the surface of the inner tube used by the CVD apparatus. Figure 6 is a graph showing the relationship between the length change of a piece of glass-like carbon that has been carbonized at 90 ° C and temperature. Figure 7 is a diagram showing the manner in which an inner core (with carbon fiber felt) is placed in a phenolic resin tube Sectional views. Figures 8 (a) and 8 (b) are plan views of the roundness correction clips used in the present invention and cross-sectional views taken along A-A. Figure 9 shows the roundness correction of the outer sleeve. Sectional view of a glass-like carbon tube (before high-temperature heat treatment). Main component comparison table 10 Mold 11 Mold body 12 Bottom plate 13 Flange baffle-37- (35) 200407275 2 1 Phenolic resin tube 23a Graphite tube 23b Carbon fiber felt 23 Inner core 24a Round hole 24 Roundness correction clip 22 Glass-like carbon tube 1 Inner tube 2 Outer tube 3 Silicon wafer 4 Loaded wafer plate 5 Manifold 5 a Gas ejector 5b Gas exhaust tube 6 Heater -38-