1326109 九、發明說明： 【發明所屬之技術領域】 本發明係關於用以將半導體晶圓或玻璃基板等加以熱處 理所需之熱處理裝置及基板之製造方法。 【先前技術】 在此種熱處理裝置中，將基板加以熱處理時，通常則以 將基板支撐在晶舟 '保持器或承受器等（下稱爲「支撐器 」）之狀態下進行。基板之熱處理，由於其係例如在〗，〇〇〇 °c以上之高溫下進行，因此支撐器則需要使用矽、碳化矽 鲁 (SiC)等之耐熱材料。該等材料之硬度也高（高於基板之 硬度），以致一接觸到支撐器即將容易造成基板產生滑動 之難題。 爲防止該滑動之產生，以往即有一種以矽爲基材，並在 該基材表面設置矽氧化膜（Si02 )，以隔著該矽氧化膜來 支撐基板之方法已爲眾所皆知（發明專利文獻1 )。 另外，其他之先前實例，則有一種支撐器之構成材料係 由表層與內部層之至少兩層所構成，且表層爲具有硬度低 · 於該基板之硬度者巳爲眾所皆知（發明專利文獻2 )。其 表層係由Si02、CaF2、Ce02、乙11〇2或MgO所構成。 並且，另一其他之先前實例，則有一種將支撐器在氬氣 、氫氣，或氬氣與氫氣的混合氣體中，在U〇〇〇°C以上之高 溫下使其滞留10分鐘以上，以除去支撐器表面之自然氧化 膜，爾後在含氧氣氣氛下加以熱處理，以使由氧化膜所構 成之保護膜生成於支撐器表面上巳爲眾所皆知（發明專利 1326109 文獻3 )。 發明專利文獻1:日本國專利特開第2002-231726號公 報 發明專利文獻2 :日本國專利特開平第6-5530號公報 發明專利文獻3:世界發明專利第WO 0 1/59826號小冊 子 【發明內容】 〔發明所欲解決之問題〕 然而，支撐器之基材若使用例如SiC時，則因SiC本身 之硬度高，不易施加表面加工，以致大小爲約數微米之「 硬突起」將殘留於與基板之接觸部份，導致基板因該「硬 突起」而形成傷痕，並以該傷痕爲起始點，在熱處理中將 產生滑動。在此情形下，本發明人等發現如先前方式僅採 取在基材表面上單純地設置3102膜之措施，仍然不能充分 防止以如上所述者爲起因的基板之傷痕產生或滑動之產生 因此，本發明之目的係提供一種可減少在熱處理中所產 生之基板的傷痕及滑動的產生，以製造高品質的半導體裝 置或基板之熱處理裝置及基板之製造方法。 〔解決問題之方法〕 爲解決上述問題，本發明之第一特徵是一種熱處理裝置 ，其係具有用以將基板加以熱處理之反應爐，與用以在該 反應爐內支撐基板之支撐器，且在該支撐器至少在會與基 板接觸之部份形成含有OH (羥）基之矽氧化膜。該矽氧化 1326109 膜中OH基含量較佳爲20 ppm以上，進一步更佳爲20 ppm 〜數萬ppm。另外’在該熱處理裝置中，其熱處理較佳爲 在1，200°C以上之溫度下實施，或在1，3 5 0°C以上之溫度下 實施。 本發明之第二特徵是一種熱處理裝置，其係具有用以將 基板加以熱處理之反應爐，與用以在該反應爐內支撐基板 之支撐器，且在該支撐器至少在會與基板接觸之部份形成 經在含有氫原子與氧原子之氣氛下施加氧化處理所形成之 矽氧化膜。該矽氧化膜係也可在含有氫氣（H2)與氧氣（ 〇2)之氣氛下形成，或在含有水（h2o)之氣氛下形成。 或是也可在含有水（h2o )與惰性氣體之氣氛下形成。進一 步也可在含有以外部燃燒裝置燃燒氫氣（H2)與氧氣（02 )所生成之水蒸氣之氣氛下在高溫氧化所形成，也可在含 有以惰性氣體使純水發泡所生成之水份的氣氛下形成。 本發明之第三特徵是一種熱處理裝置，其係具有用以將 基板加以熱處理之反應爐，與用以在該反應爐內支撐基板 之支撐器，且在該支撐器至少在會與基板接觸之部份形成 黏性率爲未含有OH基的矽氧化膜之黏性率之1/100以下之 矽氧化膜。 本發明之第四特徵是一種熱處理裝置，其係具有用以將 基板加以熱處理之反應爐，與用以在該反應爐內支撐基板 之支撐器，且在該支撐器至少在會與基板接觸之部份形成 含有OH基之矽氧化膜，該矽氧化膜係在未含有OH基之氣 氛中施加徐冷處理。該未含有OH基之氣氛爲含有例如選 1326109 自由氧氣、氮氣 '氬氣、或氦氣等之惰性氣體所構成之族 群中至少一種氣體或數種之混合氣體之氣氛。 本發明之第五特徵是如具有用以將基板加以熱處理之反 應爐’與用以在該反應爐內支撐基板之支撐器，且在該支 撐器至少在會與基板接觸之部份形成含有OH基之矽氧化 膜之熱處理裝置中，該矽氧化膜表面之OH基含量係比其 他部份較少。 本發明之第六特徵是如在具有用以將基板加以熱處理之 反應爐，與用以在該反應爐內支撐基板之支撐器，且在該 鲁 支撐器至少在會與基板接觸之部份形成含有〇H基之矽氧 化膜的熱處理裝置中，該矽氧化膜表面之黏性率係比其他 部份較高。 本發明之第七特徵是如在具有用以將基板加以熱處理之 反應爐，與用以在該反應爐內支撐基板之支撐器，且在該 支撐器至少在會與基板接觸之部份形成含有OH基之矽氧 化膜的熱處理裝置中，在該矽氧化膜表面形成比該矽氧化 膜膜厚較薄、且OH基含量較少之膜。 Φ 本發明之第八特徵是如在具有用以將基板加以熱處理之 反應爐’與用以在該反應爐內支撐基板之支撐器，且在該 支撐器至少在會與基板接觸之部份形成含有OH基之矽氧 化膜的熱處理裝置中，在該矽氧化膜表面形成比該矽氧化 膜膜厚較薄且黏性率較高之膜。 本發明之第九特徵是如在具有用以將基板加以熱處理之 反應爐’與用以在該反應爐內支撐基板之支撐器，且在該 1326109 支撐器至少在會與基板接觸之部份形成含有OHS之矽氧 化膜的熱處理裝置中，該支撐器係由碳化矽（Sic)、矽（1326109. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a heat treatment apparatus and a method of manufacturing a substrate for heat treatment of a semiconductor wafer or a glass substrate. [Prior Art] In the heat treatment apparatus, when the substrate is subjected to heat treatment, it is usually carried out in a state where the substrate is supported by a wafer boat holder or a susceptor (hereinafter referred to as a "supporter"). The heat treatment of the substrate is carried out at a high temperature of, for example, 〇〇〇 ° C or higher, so that the support member needs to use a heat-resistant material such as tantalum or carbonized ruthenium (SiC). The hardness of these materials is also high (higher than the hardness of the substrate), so that the contact with the support will easily cause the substrate to slip. In order to prevent the occurrence of the sliding, a method in which a tantalum oxide film (SiO 2 ) is provided on the surface of the substrate and a substrate is supported by the tantalum oxide film is known in the prior art ( Invention Patent Document 1). In addition, in other prior examples, there is a support material which is composed of at least two layers of a surface layer and an inner layer, and the surface layer is known to have a low hardness and hardness of the substrate (invention patent) Literature 2). The surface layer is composed of SiO 2 , CaF 2 , Ce02, B 11 〇 2 or MgO. And, in another other prior example, there is a method in which the support is retained in a mixed gas of argon gas, hydrogen gas, or argon gas and hydrogen gas at a temperature higher than U 〇〇〇 ° C for more than 10 minutes. The natural oxide film on the surface of the support is removed, and then heat-treated under an oxygen-containing atmosphere to form a protective film composed of an oxide film on the surface of the support (Japanese Patent No. 1326109, Document 3). Patent Document 1: Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Contents] [Problems to be Solved by the Invention] However, when SiC is used as the substrate of the support, the hardness of SiC itself is high, and surface processing is not easy to be applied, so that "hard protrusions" having a size of about several micrometers remain in the The contact portion of the substrate causes the substrate to form a flaw due to the "hard protrusion", and the scratch is used as a starting point to cause sliding during the heat treatment. In this case, the present inventors have found that, as in the prior art, only the measure of simply providing the 3102 film on the surface of the substrate is employed, and the occurrence of scratches or slippage of the substrate caused by the above is still not sufficiently prevented. An object of the present invention is to provide a heat treatment apparatus and a method of manufacturing a substrate which can reduce the occurrence of scratches and slippage of a substrate which is generated during heat treatment to produce a high-quality semiconductor device or substrate. [Means for Solving the Problems] In order to solve the above problems, a first feature of the present invention is a heat treatment apparatus having a reaction furnace for heat-treating a substrate, and a support for supporting the substrate in the reaction furnace, and An oxide film containing an OH (hydroxyl) group is formed on the support at least in a portion in contact with the substrate. The content of OH groups in the ruthenium oxide 1326109 film is preferably 20 ppm or more, and more preferably 20 ppm to tens of thousands ppm. Further, in the heat treatment apparatus, the heat treatment is preferably carried out at a temperature of 1,200 ° C or higher, or at a temperature of 1,350 ° C or higher. A second feature of the present invention is a heat treatment apparatus having a reaction furnace for heat-treating a substrate, and a support for supporting the substrate in the reaction furnace, and at least the substrate is in contact with the substrate. Part of the formation is a tantalum oxide film formed by applying an oxidation treatment in an atmosphere containing a hydrogen atom and an oxygen atom. The ruthenium oxide film may be formed in an atmosphere containing hydrogen (H2) and oxygen (?2) or in an atmosphere containing water (h2o). Or it can be formed in an atmosphere containing water (h2o) and an inert gas. Further, it may be formed by oxidizing at a high temperature in an atmosphere containing water vapor generated by burning an internal combustion device of hydrogen (H2) and oxygen (02), or may be formed by containing a water which is made by foaming pure water with an inert gas. Formed under the atmosphere. A third feature of the present invention is a heat treatment apparatus having a reaction furnace for heat-treating a substrate, and a support for supporting the substrate in the reaction furnace, and at least the substrate is in contact with the substrate. The partial viscous film is a ruthenium oxide film having a viscosity ratio of 1/100 or less which does not contain an OH group. A fourth feature of the present invention is a heat treatment apparatus having a reaction furnace for heat-treating a substrate, and a support for supporting the substrate in the reaction furnace, and at least the substrate is in contact with the substrate. A portion of the ruthenium oxide film containing an OH group is formed, and the ruthenium oxide film is subjected to a quenching treatment in an atmosphere containing no OH group. The atmosphere containing no OH group is an atmosphere containing at least one gas or a mixture of several gases of an inert gas such as 1326109 free oxygen, nitrogen 'argon gas, or helium gas. A fifth feature of the present invention is that there is a reactor for heat-treating a substrate and a holder for supporting the substrate in the reactor, and the support is formed to contain OH at least in a portion in contact with the substrate. In the heat treatment apparatus of the base oxide film, the surface of the tantalum oxide film has a smaller OH group content than other parts. A sixth feature of the present invention is as in a reactor having a heat treatment for heat-treating a substrate, and a support for supporting the substrate in the reactor, and forming the support at least in a portion in contact with the substrate In the heat treatment apparatus containing the ruthenium oxide film of the ruthenium H group, the viscosity of the surface of the ruthenium oxide film is higher than that of the other portions. A seventh feature of the present invention is to have a reactor for heat-treating a substrate, a support for supporting the substrate in the reactor, and a portion containing the support at least in contact with the substrate In the heat treatment apparatus for the OH-based ruthenium oxide film, a film having a thickness thinner than the ruthenium oxide film and having a small OH group content is formed on the surface of the ruthenium oxide film. Φ The eighth feature of the present invention is as in the case of having a reactor for heat-treating the substrate and a support for supporting the substrate in the reactor, and forming at least the portion of the support which is in contact with the substrate In a heat treatment apparatus containing an OH-based tantalum oxide film, a film having a thinner thickness and a higher viscosity ratio than the tantalum oxide film is formed on the surface of the tantalum oxide film. A ninth feature of the present invention is as in the case of a reactor having a substrate for heat treatment and a support for supporting a substrate in the reactor, and wherein the 1326109 support is formed at least in contact with the substrate In a heat treatment apparatus containing a ruthenium oxide film of OHS, the support is made of tantalum carbide (Sic), niobium (
Si )或經在表面塗佈碳化矽（SiC )之矽（Si )所構成。 本發明之第十特徵是如在具有用以將基板加以熱處理之 反應爐，與用以在該反應爐內支撐基板之支撐器，且在該 支撐器至少在會與基板接觸之部份形成含有〇H基之矽氧 化膜的熱處理裝置中，該支撐器係具有本體部、與基板接 觸之支撐部，且支撐部係由板狀構件所構成。 本發明之第十一特徵是一種基板之製造方法，其係包括 · 將基板搬入反應爐內之步驟，由至少在會與基板接觸之部 份形成含有OH基之矽氧化膜之支撐器來支撐基板之步驟 ，在該反應爐內以由該支撐器支撐基板之狀態下實施熱處 理之步驟，以及由該反應爐搬出熱處理後之基板之步驟。 本發明之第十二特徵是如包括將基板搬入反應爐內之步 驟，由至少在會與基板接觸之部份形成含有OH基之矽氧 化膜之支撐器來支撐基板之步驟，在該反應爐內以由該支 撐器支撐基板之狀態下實施熱處理之步驟，以及由該反應 鲁 爐搬出熱處理後之基板之步驟的基扳之製造方法中，在該 反應爐內搬入基板之前，將空的支撐器搬入反應爐內並在 含有氫原子與氧原子之氣氛下對支撐器施加氧化處理。 本發明之第十三特徵是一種基板之製造方法，其係包括 將基板搬入反應爐內之步驟，由至少在會與基板接觸之部 份形成在未含有OH基之氣氛下所施加徐冷處理的含有OH 基的矽氧化膜之支撐器來支撐基板之步驟，在該反應爐內 -9 - 1326109 以由該支撐器來支撐基板之狀態下實施熱處理之步驟，以 及由該反應爐搬出熱處理後之基板之步驟。 本發明之第十四特徵是如包括將基板搬入反應爐內之步 驟，以至少在與基板接觸之部份形成含有經在未含有OH 基之氣氛下所施加徐冷處理的含有OH基之矽氧化膜之支 撐器來支撐基板之步驟，在該反應爐內以由該支撐器支撐 基板之狀態下實施熱處理之步驟，以及由該反應爐搬出熱 處理後之基板之步驟的基板之製造方法中，在將基板搬入 反應爐內之前，將空的支撐器搬入反應爐內並在未含有ΟΗ φ 基之氣氛中實施徐冷處理。 本發明係經對適合與基板相接觸之材料進行各種硏討結 果，發現以含有〇 Η基之Si02爲最適當而達成本發明。關 於石英，已知其黏性率係視含在石英中之水份（OH基）量 而變化。在此所謂「黏性（viscosity )」，若欲能以各種 外力移動物體時，則必在物體內會產生抗拒其之力，亦即 ，對於變形的抗拒力，黏性就是表示其程度之性質。 黏性率7? 〔 Pa _ s〕（=〔泊（poise)〕）係意指在面積 φ 爲S〔 m2〕之兩片平板之間（距離爲d〔 m〕）挾住流體， 並使一方之板保持平行同時以一定速度（v〔m/s〕）移動 時，關於板由液體所受到之力（F〔 N〕）之量： F/S = η v/d η = 〔N〕 〔m〕/〔m2〕[ m/s ] = [ N ] 〔s〕/〔m2 〕=〔Pa〕〔 s〕。 在第1圖展示因〇H基含量所造成黏性率之溫度相依性 -10 - 1326109 (出 自 於 http : //www.asahi-net.or.jp/%7Eup5s- andu/index.htm )。石英中OH基含量愈多，則黏性率7?愈 低。黏性率77之基準爲在第1圖之軟化點以下爲可供施加 玻璃工藝之上限，在應變點以上爲被視爲長時間（以年爲 單位）不致於變形之領域。在其間之徐冷點以上，則以月 爲單位之使用即將變形之領域，其以下則以日爲單位之使 用即將變形之領域。 本發明係至少將會與基板相接觸之部份做成爲含有OH 基之矽氧化膜，以使其具有適當的黏性率。黏性率係在 l,〇〇〇°C則以10泊以下爲佳，在1,200°C則以13泊以下爲 佳，在1，3 50 °C則以15泊以下爲佳。爲使其具有如此之黏 性率，則必須使矽氧化膜中OH基含量設定爲20 ppm以上 。在此情形下，含OH基的矽氧化膜之黏性率，如與未含 有OH基的矽氧化膜之黏性率相比較，在1,000 °C則爲 1/100以下，在1，200°C則爲1/100以下，在1，3 50°C則爲 1Π00以下。進一步較佳爲矽氧化膜中OH基含量宜設定爲 2 0 ppm〜數萬PPm。此情形下，含OH基的矽氧化膜之黏 性率’如與未含有OH基的矽氧化膜之黏性率相比較，在 l，〇〇〇°C 則爲 1/100 ~ 1/1012，在 1，200°C 則爲 1/100 〜1/1010 ，在l，35〇°C則爲1/100〜1/108。進一步較佳爲矽氧化膜中 OH基含量較佳爲設定在20 ppm〜1萬ppm。此情形下， 含OH基的矽氧化膜之黏性率，如與未含有〇H基的矽氧化 膜之黏性率相比較，在1，0 0 0 t則爲1 /1 0 0〜1 /1 0 1 °，在 l，2〇〇°C 則爲 1/100 ~ 1/1〇8，在 1，3 5 0°C 則爲 1/100 〜1/106 1326109 。另外’也可使矽氧化膜中OH基含量設定爲1萬ppm〜 數萬ppm。此情形下，含〇H基的矽氧化膜之黏性率，如 與未含有OH基的矽氧化膜之黏性率相比較，在1，〇〇〇。(：則 爲 1/101。〜1/1012，在 1，20(TC 則爲 1/108 〜1/101。，在 1，3 50°C則爲1/106〜1/108。另外，在此所謂「ppm」係意 謂 Parts Per Million (百萬分之 1)。 另外，已知隨著溫度升高，石英中OH基將起熱解離， 以釋放出活性氫氣。在第2圖展示〇 Η基熱解離量之溫度 相依性（出自於 http : //www.asahi-net.or_jp/%7Eup5s-andu/index.htm )。在 1,000°C 〜1，4 0 0 °C 之溫度域，貝IJ 可 槪算爲溫度每上升約100 °C，即有10倍之OH基將起熱解 離。然而，如第2圖所示，在1，400°C，熱解離度也爲約 1 E-3 (莫耳％ )，因此，在實際使用上可不必考慮起因於 熱解離的OH基含量之減少。在目的之熱處理中，通常實 施藉由氧氣之氧化（OH基含量大致爲數PPm )，或使用惰 性氣體之徐冷。由於熱解離所釋放出來之活性氫係具有非 常強的還原力，因此，將與矽氧化膜中Si _0_ Si鍵結之 · 氧原子起反應。其反應係如次式所示。 ξ Si - 0 - Si ξ +H (氣體）—Si - Ο - H + Si 另外，活性氫係其原子半徑爲非常小，因此該反應係有 可能在經由目的之熱處理中所形成的矽氧化膜之膜中深部 也會產生。在目的之熱處理中，經取入於矽氧化膜之Η係 屬雜質，有可能將構成降低基板膜質之.原因，因此宜避免 使其殘留於經熱處理後的矽氧化膜中（尤其是在矽氧化膜/ -12 - 1326109 矽板界面附近）。爲避免此情形之發生而使多量的OH基 含在支撐器表面之氧化處理，較佳爲將基板放在反應爐之 前實施。 若使用含有OH基之矽氧化膜時，則即使在表面有某一 程度之粗糙面之支撐器上形成矽氧化膜時，也有能抑制基 板滑動之產生的優點。亦即，供形成矽氧化膜的支撐器之 表面狀態並不必要過於太拘執。其係經由OH基的混入， 矽氧化膜本身即將變軟，使得流動性變高而成爲緩衝材， 變得易於釋放應力的狀態之緣故。另外，也有在處理基板 φ 時之製程窗（在製程上之允許範圍）將變得寬闊之優點。 例如，即使將進行基板處理時之升溫率予以增快某一程度 ，也能抑制基板滑動之產生。 與此相對，若使用未含有OH基的矽氧化膜時，則除非 支撐器表面爲受到限制的表面狀態、面粗糙度之範圍內， 否則基板即有可能會產生滑動。在此種情形下，則需要對 支撐器之表面狀態（表面粗糙度等）加以注意，並必須調 節支撐器表面以徹底消除產生滑動之原因，結果將導致成 · 本上升。而且也有會造成在處理基板時之製程窗將變得狹 窄之缺點。例如升溫速率將受限於一定速率以下等，對基 板處理條件將帶來各種限制。 如欲降低矽氧化膜之黏性率，則將其他之雜質混合於矽 氧化膜即可達成。但是Ο Η基，就其可在不致於對基板構 成污染源下可降低矽氧化膜之黏性的特性而言，則比較其 他雜質爲優異。 -13 - 1326109 含有OH基的矽氧化膜之膜厚，較佳爲Ι,ΟΟΟΑ〜數微米 (例如3~5微米）。更佳爲設定爲數千Α〜數微米。若 * 矽氧化膜之膜厚設定爲比l，〇〇〇A較薄時，則在支撐器表面 的約數微米之突起即有可能會剌破矽氧化膜，使得作爲緩 衝層的矽氧化膜之作用大打折扣。相反地，將矽氧化膜之 膜厚作成爲比數微米較厚時，則有可能造成矽氧化膜剝離 之情形，因此需要一些抗剝離對策。 然而，對剛形成含有OH基的矽氧化膜之後緊接著施加 熱處理之基板進行滑動評估結果，已確認到有一些滑動。 φ 將基板表面之顯微鏡照片展示於第1 2圖。由圖即可知在縱 橫方向已形成少許的數條滑動（條紋花樣）。其原因爲如 下。 亦即，如第10 ( a)圖所示，在SiC製之支撐器30的表 面被形成硬突起1〇〇、100，且含有OH基的矽氧化膜74係 被形成在其上，因此如第10(b)圖所示，在該支撐器30 上載置基板72且實施熱處理時，則含有黏性率爲低的OH 基之矽氧化膜74將被壓破，使含有〇H基的矽氧化膜74 φ 黏附在基板72之數處。因此，如第l〇(c)圖所示，在熱 處理中的升降溫時，基板72雖然將要起變形，但是由於在 黏附之處基板72與含有OH基的矽氧化膜74係受到固定 ，因此應力將在黏附處之間集中於基板7 2。此時，當基板 72將要起變形之力超過黏附力時，則將一口氣釋放出黏附 處之間之應力，使基板72因其衝擊而產生滑動。 然後在本發明中，則經藉由將含有OH基的矽氧化膜在 -14 - 1326109 未含有OH基之氣氛中實施徐冷處理，使存在於含有低黏 性率的OH基之矽氧化膜最表面之〇H基（導致黏性率減少 之主要原因）脫除少許，使其表面之黏性率變得高一些》 換言之，如第11 (a)圖所示，經在未含有OH基之氣氛 下實施徐冷處理，藉此在含有低黏性率的OH基之矽氧化 膜74最表面，使OH基 除而形成黏性率較高少許（較硬 的）之膜102，使含有OH基之矽氧化膜74以該膜102加 以覆蓋。因此，如第11(b)圖所示，當在支撐器30上載 置基板72而實施熱處理，基板72即接觸於黏性率較高少 φ 許之膜1 02，以使基板72與含有OH基之矽氧化膜74不易 相黏附。因此，如第U ( c )圖所示，在熱處理之升降溫 時，即使基板72起變形，由於與含有〇H基的矽氧化膜74 之黏附部份較少，可使基板72與膜1 02之間產生滑動，以 使基板72緩慢地起變形，所以當可防止應力集中，以防止 基板72之產生滑動。 並且，由於膜1 〇 2係非常薄（例如爲1 〇 〇奈米以下）， 當不致於阻礙到後述第一實施形態（上述第一特徵等）之 鲁 發明效果。該第一實施形態就是用以形成含有OH基的矽 氧化膜74者。並且’含有OH基的矽氧化膜在未含有〇H 基的氣氛下之徐冷，係在剛形成含有OH基的砂氧化膜74 後緊接著的一批以上之熱處理中，即可不必將基板放入反 應爐內，而以僅放入支撐器的空批方式來實施。 〔發明之效果〕 在本發明中，由於構成爲在支撐器中至少在會與基板接 -15 - 1326109 觸之部份設置低黏性率（較軟的）之材料’以由該低黏性 率之部份來支撐基板，因此’即使以例如SiC等般之非平 坦且較硬的材料作爲支撐器母材’也可防止在基板形成傷 痕，防止在基板產生滑動。 而且，由於在低黏性率之材料最表面將黏性率較高的層 形成較薄，因此也可防止與基板之間所產生之黏附，以防 止起因於黏附之滑動產生。 【實施方式】 〔實施發明之最佳形態〕 Φ 接著，根據圖式說明本發明之實施形態如下。 第3圖係展示本發明實施形態之熱處理裝置1 0。該熱處 理裝置1 〇係例如外形爲縱型，且具有供配置主要部份之機 箱1 2。密閉莢式容器台1 4係連接於該機箱1 2，密閉莢式 容器16係搬送在該密閉莢式容器台14。密閉莢式容器16 供收納例如25片之基板，並以由未圖示的蓋所蓋住之狀態 下擺放在密閉莢式容器台14。 在機箱12內，在相對於密閉莢式容器台Μ之位置，則 鲁 配置一密閉莢式容器搬送裝置18。另外，在該密閉莢式容 器搬送裝置1 8之附近，則配置密閉莢式容器棚2 0、密閉 莢式容器開蓋器22及基板片數檢測器24。密閉莢式容器 搬送裝置18，係用以在密閉莢式容器台14與密閉莢式容 器擱架20與密閉莢式容器開蓋器22之間搬送密閉莢式容 器1 6。密閉莢式容器開蓋器22係用以打開密閉莢式容器 1 6之蓋者，經被打開該蓋的密閉莢式容器丨6內之基板片 -16 - 1326109 數係由基板片數檢測器24來加以檢測。 另一方面，在機箱1 2內則配置基板移載機26、凹槽調 準器28及支撐器30 (晶舟）。基板移載機26係例如具有 一次可取出5片基板之臂32，且藉由操作該臂32，即可在 擺放在密閉莢式容器開蓋器22之位置的密閉莢式容器、凹 槽調準器28及支撐器30之間搬送基板。凹槽調準器28係 用作爲檢測經預先形成在基板上之凹槽或定向平面以供將 基板之凹槽或定向平面排齊成一定位置者。支撐器30係由 圓板上之上板34及下板36，以及用以連接該上板34與下 · 板36之3支至4支之支柱38所構成" 反應爐40係展示在第4圖中。該反應爐40係具有反應 管42，支撐器30係插放在該反應管42內。反應管42之 下方係開放以供插放支撐器3 0，且該開放部份係構成爲可 供以密封蓋44加以密閉》反應管42周圍係由均勻加熱管 46所覆蓋，並且在均勻加熱管46之周圍配置加熱器48。 熱電偶50係配置於反應管42與均勻加熱管46之間，且構 成爲可監控反應爐40內之溫度。此外用以引進製程氣體之 隹 導入管52，與用以排放製程氣體之排氣管54係連接於反 應管42。 氣體供應系56係連接於氣體導入管52。氣體供應系56 係具有後述H20產生裝置58、N2氣體源60及〇2氣體源 62，並在該等H20產生裝置58、N2氣體源60及〇2氣體源 62，連接H20供應線64a、N2供應線64b及02供應線64c 。該等供應線60、6朴、64c係各自設置開閉閥66a、66b -17 - 1326109 、66c及質流控制器（MFC ) 68a、68b、68c，以經由該 MFC 68a、68b、68c調節氣體流量後，供應至反應爐40。 接著，就如上述所構成之熱處理裝置10說明其作用如下 〇 首先，當將收容數片基板之密閉莢式容器16放置在密閉 莢式容器台14時，即由密閉莢式容器搬送裝置18將密閉 莢式容器16自密閉莢式容器台14搬送至密閉莢式容器擱 架20 ’並儲存於該密閉莢式容器擱架20。然後，以密閉莢 式容器搬送裝置18，將儲存在該密閉莢式容器擱架20之 密閉莢式容器16搬送至密閉莢式容器開蓋器22並予以架 設固定，然後以該密閉莢式容器開蓋器22打開密閉莢式容 器1 6之蓋，供由基板片數檢測器24檢測收容在密閉莢式 容器16中之基板片數。 接著，由基板移載機26由位於密閉莢式容器開蓋器22 之位置的密閉莢式容器16取出基板，並移載至凹槽調準器 2 8。該凹槽調準器2 8即將使基板回轉同時檢測凹槽，並根 據經檢測到之資訊來使數片基板之凹槽排齊成同一位置。 然後以基板移載機26由凹槽調準器28取出基板並移載至 支撐器30。 當以如上述方式將一批量份基板移載至支撐器3 0時，則 將經裝上數片基板的支撐器30裝入經將溫度設定成例如爲 約600°C之反應爐40內，然後，以密封蓋44將反應管42 內加以密閉。其次，則將爐內溫度升溫至熱處理溫度，然 後由導入管52導入作爲製程氣體之氮氣及氧氣。導入製程 -18 - 1326109 氣體係經由打開開閉閥66b、66c ’以MFC 68b、68c調節 氣體流量，並自N2氣體源60及02氣體源62經過供應線 6 4b ' 64c來實施》將基板加以熱處理時，基板係受到例如 爲l，000°c以上，甚至爲1，350°C以上之溫度的加熱。在該 期間中，當然經由熱電偶50來監控反應管42內之溫度同 時依照預先設定之升溫、熱處理程式來進行基板之熱處理 〇 基板之熱處理一結束，則例如將爐內溫度降溫成約6 0 0 它之溫度後，即將支撐器30由反應爐40卸載，並使支撐 器30在特定位置待命，直至所有被支撐在支撐器30內之 基板受到冷卻爲止。另外，使爐內溫度降溫時’也以熱電 偶5 0來監控反應管4 2內之溫度同時依照預先所設定之降 溫程式來進行降溫。接著，俟待命的支撐器3 0之基板冷卻 至特定溫度時，即由基板移載機26由支撐器30取出基板 ，搬送至放置在密閉莢式容器開蓋器22之空密閉莢式容器 16並予以收容。然後’以密閉莢式容器搬送裝置18將收 容基板的密閉莢式容器16搬送至密閉莢式容器擱架20’ 並且再搬送至密閉莢式容器台14以結束。 其次就上述支撐器30詳加說明如下。 在第5(a)圖中’在支撐器30之各支柱38則將許多支 撐片7〇向支撐器30之內側突出形成。在該支撐片7〇則以 略水平姿勢載置矽晶圓等之基板72 ’在支撐器30則以略 平行狀態且在隔著間隙下支撐許多基板7 2。 如第5 ( b )圖所示，包括支撐片70在內的支柱3 8，係 1326109 例如由矽（Si )或碳化矽（SiC)所形成，且在包括支撐片 7〇在內的支柱38之全面形成矽氧化膜（Si 02膜）74。在 該矽氧化膜74中，含有OH基，且矽氧化膜74中之OH基 含量爲20 ppm〜數萬ppm (例如2 ~ 3萬ppm)。另外， 矽氧化膜74之膜厚爲1，〇〇〇Α ~數微米（例如3〜5微米 )。如第5(c)圖所示，也可將包括支撐片70在內的支 柱38之構成材料使用矽（Si)，且在該矽製支柱38(包含 支撐片7 0 )全面形成例如由碳化矽（s i C )所構成之塗佈 層76，且在該塗佈層76形成上述矽氧化膜74。 · 另外，塗佈層76係由電漿CVD (化學氣相沉積）法或 熱CVD法所形成。該塗佈層76之厚度較佳爲形成爲介於 0.1微米〜50微米範圍。該碳化矽製之塗佈層76若形成 較厚時’則將因矽與碳化矽的熱膨脹率之差，使矽製之支 撐片70爲碳化矽製之塗佈層76所牽引而導致支撐片全體 之變形量變爲大，以造成因該大的變形而使基板72產生滑 動之顧慮。與此相對，若將碳化矽製之塗佈層7 6設定爲如 上所述之厚度時，則可使矽製之支撐片70爲碳化矽製之塗 · 佈層76所牽引之量變得少，使得支撐片全體之變形量亦將 變較少。換言之，使碳化矽製之塗佈層76設定爲薄時，即 可減少因支撐片70與塗佈層76的熱膨脹率之差所引起之 應力，使得支撐片全體之變形量變少，支撐片全體之熱膨 脹率也將接近於矽本來之熱膨脹率（基板72若爲矽製時， 則爲略同等之熱膨脹率），因此可防止滑動之產生。 碳化矽製塗佈層7 6之厚度若設定爲小於0.1微米時’則 -20 - 1326109 將因碳化矽塗佈層76太薄而消耗，造成矽製之支撐片70 必須再行塗佈碳化矽，以致能反復使用同一支撐器3 0。若 將該塗佈層76之厚度設定爲0.1微米以上時，則可不必將 碳化矽之塗佈層76頻繁地再塗佈於矽製之支撐片7〇，使 得同一支撐器30得以反復使用。另外，若將碳化矽製之塗 佈層76之厚度設定爲1微米以上時，則因膜將更不易消耗 而可更加增多可反復使用同一支撐器30之次數。 碳化矽製塗佈層76之厚度若設定爲大於50微米時，則 將導致碳化矽製塗佈層76本身易於破裂，且以因該破裂爲 原因此在基板72也容易產生滑動。該塗佈層76之厚度若 設定爲5 0微米以下時，則塗佈層7 6之破裂即不易發生， 且如上所述由於也可減少矽製之支撐片70與碳化矽製之塗 佈層76之因熱膨脹率差所引起之應力，因此支撐片全體之 變形將變少’故可防止基板72之滑動產生。碳化矽製塗佈 層76之厚度若設定爲1 5微米以下時，則基板之滑動將幾 乎不致於產生。更進一步若使碳化矽製塗佈層76之厚度設 定爲0.1微米〜3微米時，則基板72之滑動就不會產生。 因此，碳化矽製塗佈層76之厚度係以0.1微米〜50微米 爲佳，更佳爲0.1微米〜15微米，進一步更佳爲0.1微米 ~ 3微米。矽製支撐片70與碳化矽製塗佈層76之厚度若以 兩者之比率表示，則以使碳化矽製塗佈層76之厚度設定爲 矽製支撐片70之厚度的0.0025 %〜1.25 %爲佳，更佳爲 0.0025 % 〜0.38 %，進一步更佳爲 0.0025 % 〜0.25 %。 塗佈層76係除碳化矽以外，也可使氮化矽（SiN )同樣 1326109 地以電漿CVD法或熱CVD法來塗佈形成。採取氮化矽製 時’該塗佈層76之厚度，較佳爲設定爲〇1微米~3〇微 米，更佳爲設定爲0.1微米〜5微米。該塗佈層76係用作 爲防止支撐片70與基板72之黏合而作爲接著防止層所設 置。 含有OH基之砂氧化膜74係可不必形成在支柱38之全 面’至少形成在會與基板7 2接觸之部份即用，例如如第 5圖（d)所示’也可形成在矽（Si)或碳化矽（sic)製之 支柱38的支撐片70之上面一部份，並使基板72接觸於形 · 成在該支撐片70之砂氧化膜74。也可進一步如第5(e) 圖所示’在矽（Si)製支柱38的支撐片70之上面形成例 如由碳化矽（SiC)所構成之塗佈層76，然後在該塗佈層 76上形成含有OH基之矽氧化膜74。 此外，支撐器30也可採取如第6圖所示，以本體部的支 柱3 8之支撐片7 0來支撐板狀構件的保持器8 〇，然後經由 該保持器80來支撐基板72之形式者《 保持器8 0之直徑係比基板7 2之直徑爲小，亦即，保持 · 器80之上面係具有比基板72之下面的平坦面之面積較小 之面積’基板72係以除該基板72之周緣以外之部份爲保 持器80所支撐（保持器80係以未與基板72之外周緣接觸 之狀態下支撐基板72 )。基板72係例如直徑爲3 00毫米 ，因此保持器80之直徑爲小於300毫米，即以約100毫米 〜250毫米（基板外徑之約1/3〜5/6 )爲佳。 而且，該保持器80之厚度係形成爲比基板72之厚度較 -22 - 1326109 厚。基板72之厚度爲例如700微米，因此，支撐部72之 厚度係大於7 00微米，甚至於可達到10毫米，較佳爲基板 72之厚度之至少2倍以上，例如以3毫米〜1 0毫米爲佳 ，更佳爲3毫米〜6毫米，進一步更佳爲4毫米〜5毫米 。另外，該保持器80之厚度係比支撐片70之厚度較厚。 將保持器80之厚度設定爲如此之厚度之理由，係爲使保持 器8 0本身之剛性增加，以抑制保持器80在熱處理時之變 形。當然只要爲能抑制在熱處理時之變形者，則不一定是 必須使矽氧化製保持器80之厚度形成爲比基板72之厚度 較厚。另外，保持器80之直徑（面積）係也可形成爲比基 板72之直徑（面積）爲大。此種情形下，保持器8〇之厚 度則應再形成較厚一些。 在上述形式之支撐器30，如第6圖（b)所示，其保持 器80係例如由矽（Si )或碳化矽（SiC )所形成，且在該 保持器80之全面形成上述含有〇H基之矽氧化膜74。如第 6圖（c)所示’也可使保持器80之構成材料爲矽（Si)， 且在該矽氧化製保持器80之全面形成例如第5圖（c)所 示之由碳化矽（SiC)所構成之塗佈層76，然後，在該塗 佈層76形成上述之矽氧化膜74。含有OH基之矽氧化膜 74，係不必形成在保持器80之全面，而至少形成在基板 72會接觸之部份即足夠，例如第6圖（d)所示，也可僅 在矽（Si)或碳化矽（SiC)製保持器80之上面形成，以 供基板72接觸於形成在該保持器80上面之矽氧化膜74。 並且’如第6圖（e)所示，也可在矽（Si)製保持器80 1326109 之上面形成例如由碳化矽（S i C )所構成之塗佈層7 6 ’並 在該塗佈層76形成含有OH基之矽氧化膜74。 接著，就有關在支撐器（包含晶舟或保持器）形成含有 Ο Η基的矽氧化膜之方法之第一實施形態說明如下。 如欲形成含有ΟΗ基之矽氧化膜，則可使用與用以熱處 理基板的反應爐同一反應爐。如第4圖所示’在氣體供應 系56設置Η20產生裝置58，並由該Η20產生裝置58供應 水份於收容支撐器30的反應爐40，藉此，即可使含有ΟΗ 基之矽氧化膜形成在支撐器30。如此之可執行對支撐器30 · 之處理與基板的處理雙方之反應爐40,係只要對用以對基 板施加熱處理之反應爐，追加一用以供應水份（Η20 )的 Η20供應線64a，即可簡單地構成。 另外，對支撐器30的含有OH基的矽氧化膜之形成，與 對基板的熱處理，係可採取分開在個別之反應爐中實施之 方式。 使用經由上述H20產生裝置58所產生H20來氧化支撐 器表面之方法’其第1例則有一種使用高溫氧化之方法。 修 其係在第7 ( a)圖中’ H20產生裝置58係具有H2氣體源 82、02氣體源84及外部燃燒裝置86。H2氣體源82與02 氣體源8 4係分別經由開閉閥8 8 a、8 8b及質流控制器（ MFC) 90a、90b并排連接於外部燃燒裝置86，並以外部燃 燒裝置86燃燒供自H2氣體源82與〇2氣體源84之氫氣（ H2 )與氧氣（02 )以產生水蒸氣（h2〇 )，且將經產生之 水蒸氣（H20)與氧氣（〇2)供應於收容支撐器3〇的反應 -24 - 1326109 爐40內，並在約1，000 ~ 1,200°C之溫度、在大氣壓下進行 支撐器30表面之氧化。藉此’即可使含有OH基之矽氧化 膜形成在支撐器30表面。 另外，矽氧化膜中〇H基含量之控制，係藉由將H2、02 或H20之供給流量、氧化處理溫度、氧化處理時間等加以 控制來實施。 使用經由上述H20產生裝置58所產生H20來氧化支撐 器表面之方法，其第二例則有一種使用經以惰性氣體使純 水發泡所生成的H20來氧化之方法。其係在第7(b)圖中 ，H20產生裝置5 8係具有儲存屬惰性氣體的例如N2氣體 之N2氣體源92，與儲存純水之純水容器94。N2氣體源92 係被連接成可經由開閉閥96及質流控制器（MFC ) 98而 開口於盛在純水容器94中的純水下部。因此，以例如來自 N2氣體源之氮氣（N2 )使純水容器94中純水（H20)起發 泡以使其產生水份，並將所產生之水蒸氣（H20 )與氧氣（ 〇2)供應於收容支撐器30之反應爐40內，並在約1,〇〇〇〜 1，200 °C之溫度在大氣壓下進行支撐器30表面之氧化。藉 此，即可使含有OH基之矽氧化膜形成在支撐器30表面。 另外，矽氧化膜中OH基含量之控制，係藉由將N2、H20 或〇2之供給流量、氧化處理溫度、氧化處理時間等加以控 制來實施。 使用經由上述H20產生裝置58所產生H20來氧化支撐 器表面之方法，其第三例則有一種僅使用水份（H20 )與載 氣來氧化之方法。其係與第二例同樣地使用第7 ( b )圖所 -25 - 1326109 示之H20產生裝置58，以例如來自N2氣體源之氮氣（N2 )使純水容器94中純水（H20 )起發泡以使其產生水份， 並將所產生之水蒸氣（H20)與載氣供應於收容支撐器30 之反應爐40內，並在約1，000〜1，2 00 °C之溫度在大氣壓下 進行支撐器30表面之氧化。藉此，即可使含有OH基之矽 氧化膜形成在支撐器30表面。另外，矽氧化膜中〇H基含 量之控制，係藉由將N2、H20或載氣之供給流量、氧化處 理溫度、氧化處理時間等加以控制來實施。載氣則有惰性 氣體，例如氮氣（N2) '氦氣（He)、氬氣（Ar)等。如 春 此，也可在不必使用氧（〇2 )氣體下，僅使用水份（H20 )與載氣來形成含有OH基之矽氧化膜。 使用經由上述H20產生裝置58所產生H20來氧化支撐 器表面之方法，其第四例則有一種組合乾式氧化與濕式氧 化之方法。亦即，其係將氧氣（02 )與氮氣（N2 )供應於 收容支撐器30之反應爐40內，並在約1，〇〇〇〜1，200°C之 溫度’在大氣壓下進行支撐器30表面之氧化處理（乾式氧 化）。經由該處理即可在支撐器30表面形成未含有OHS # 之矽氧化膜。其後則實施使用水份（H20 )之氧化處理（濕 式氧化）。濕式氧化則有例如上述之高溫氧化。藉此，即 可使含有OH基之矽氧化膜形成在支撐器30表面。另外， 矽氧化膜中〇H基含量之控制，係藉由將經乾式氧化後所 實施之濕式氧化中的H2、N2或H20之供給流量、氧化處理 溫度、氧化處理時間等加以控制來實施。如此藉由經在乾 式氧化後施加濕式氧化，也可形成含有OH基之矽氧化膜 -26 - 1326109 綜合上述在反應爐之處理，結果如第8圖所示。 首先，在步驟S10，將空的支撐器30(未裝放基板之支 撐器3〇)搬入反應爐40內。在其次之步驟S12，則在已搬 入空的支撐器3 0之反應爐40內供應經以上述方法所製得 之含有水份之氣體，以在支撐器30形成含有OH基之矽氧 化膜。在其次之步驟s 1 4，則將經形成含有OH基之矽氧化 膜的支撐器30由反應爐40搬出。在其次之步驟S16，則 將基板72支撐於經形成含有〇H基之矽氧化膜的支撐器30 φ 上。在其次之步驟s 1 8，則將在已支撐基板72的狀態之支 撐器30搬入反應爐40內。在其次之步驟S20，則以上述 方法對基板72施加熱處理。在其次之步驟S22，則將已結 束對基板72的熱處理之支撐器30由反應爐40搬出。在其 次之步驟S24 ’則加以判定對基板72施加熱處理之次數（ 連續處理之次數）是否已達到特定次數。在該步驟S24中 ，若判定爲對基板72施加熱處理次數已達到特定次數時， 則返回起初之步驟S10，以執行支撐器30表面之再氧化處 鲁 理。藉此’即可使因連續處理所減少的支撐器表面之矽氧 化膜中OH基復原。在步驟S24中，若判定爲對基板72施 加熱處理次數並未達到特定次數時，則返回步驟S 1 6，以 對基板72實施熱處理直至能達到特定次數爲止。 此外’在步驟S24中所謂特定次數，亦即必須執行補充 基板因連續處理所減少的支撐器表面之矽氧化膜中OH基 的再氧化處理之頻度’係依照下述方式來設定。即在實施 -27 - 1326109 基板的連續處理之前，先取得相對於基板處理次數（分批 次數）的支撐器表面之矽氧化膜中〇H基含量（或減少量 )之數據，並查出OH基含量會減少至特定 所需之處理 次數。然後將該處理次數設定爲自開始對支撐器施加氧化 處理起至施加再氧化處理爲止之處理次數（在步驟S 24之 特定次數）。另外，矽氧化膜中之〇H基含量，係例如藉 由以傅立葉轉換紅外線光譜分析儀（FTIR : Fourier Transform Infrared Spectrometer)測定砂氧化膜之光譜來 算出。此時，被檢物係雙面皆需爲光學面（硏磨）。因此 ，在測定前即實施支撐器表面的矽氧化膜之硏磨，以形成 光學面。在經由測定所得光譜之波長2.73微米處將出現起 因於「Si — OH」鍵結之吸收，因此由其尖峰 ，即可算出 OH基含量。在進行基板之連續處理時，則應設定爲能按照 事前所調查出之能使支撐器表面之矽氧化膜中OH基符合 特定 的處理次數來對支撐器表面施加使用水份之再氧化 處理。經由該再氧化處理即可補充因連續處理所減少的支 撐器表面之矽氧化膜中OH基，以使矽氧化膜中之OH含量 復原成爲連續處理前之適當的。另外，〇H基之含量特定 ，較佳爲設定爲矽氧化膜之黏性率即將變爲會導致基板 產生滑動的程度之黏性率 之20 ppm以上，例如設定爲 20 ppm。也可爲保持某一程度之富餘而設定爲例如爲1〇〇 ppm以上之 或l,000ppm以上之 。 其次，說明由本發明人等所實施之實驗結果如下。 本發明人等已在由表面形成矽氧化膜之支撐器來支撐基 -28 - 1326109 板狀態下，實施在1,3 5 0°C之處理溫度、且在含有〇2及N2 之氣氛下將基板加以熱處理數小時之實驗。實驗係將矽氧 化膜中OH基含量以〇 ~ 10,000 ppm之範圍內予以變化而 進行。其結果，使OH基含量設定爲0 ppm、1 ppm時，即 在基板產生滑動，但是設定爲20 ppm、1 0,000 ppm時，則 在基板並未產生滑動。因此得知，OH含量愈多，滑動即不 容易產生，且只要至少設定爲20 ppm以上時，滑動就幾乎 不再會產生。其係因OH基含量愈多，矽氧化膜之黏性率 即愈下降，且OH基含氧量至少有20 ppm以上，則矽氧化 φ 膜之黏性率將變得不致於使基板產生滑動的程度之黏性率 之緣故。而且，已確認到OH基將在矽氧化膜中至少會進 入約數萬ppm (例如20,000 ppm〜30,000 ppm )。因此， 矽氧化膜中OH含量，較佳爲設定爲20 ppm以上，在實用 上則以設定成爲自20 ppm至數萬ppm爲佳。並且，OH基 含量也可設定爲經以實驗所確認到範圍之20 ppm ~ 10,000 ppm，也可設定爲比其會使黏性率更加下降的範圍之 1 0,000 ppm 以上。 鲁 再者，在上述實驗中，係將經以氮氣（N 2 )使純水（ H20 )發泡所生成之水份（H20 ) 1 %與氧氣（〇2 )，供應 於已收容支撐器之反應爐內，並在1，200°c之溫度、在大氣 壓下施加爲時1 ~ 2小時的支撐器表面之氧化處理（濕式 氧化）。藉此即將含有1 ppm、20 ppm、10,000 ppm的〇H 基之矽氧化膜形成在支撐器表面。相對地未含有〇H基（ OH基含量爲0 ppm)之矽氧化膜，則將氧氣（〇2)與氮氣 -29 - 1326109 (N2)供應於已收容支撐器之反應爐內，並以溫度1,200°C 、在大氣壓下施加爲時1〜2小時的支撐器表面之氧化處 理，以形成（乾式氧化）。 其次，就有關在支撐器（包含晶舟或保持器）形成含有 OH基之矽氧化膜之方法的第二實施形態說明如下。第二實 施形態係對第十實施形態加上徐冷處理者。亦即，含有OH 基之矽氧化膜的形成一結束，則予以關閉開閉閥66a、66c ，並打開開閉閥66b，以N2淸除含有水份氣體之反應管42 內，其後則對經形成在支撐器表面之含有OH基之矽氧化 0 膜施加徐冷處理。徐冷處理係在打開開閉閥66b或66c， 使N2氣體和/或02氣體導入於反應管42內，以在未含有 OH基之氣氛下進行。徐冷處理較佳爲在處理溫度爲1，2 00 °C 〜1，4〇〇°C之範圍內，並以處理時間爲0.5小時〜10小 時之範圍內實施。 另外，徐冷處理係除氣體或02氣體之外，也可在Ar 、He等之惰性氣體或在該等之混合氣體的氣氛下實施。 綜合上述在反應爐之處理，結果如第9圖所示。 鲁 首先’在步驟S10,將空的支撐器30(未裝放基板之支 撐器30)搬入反應爐40內。在其次之步驟S12，則在已搬 入空的支撐器30之反應爐40內，以上述方法供應含有水 份之氣體’以使含有OH基之矽氧化膜形成在支撐器30。 在其次之步驟S26，則對以上述方法在步驟S 12所形成之 含有OH基之矽氧化膜實施徐冷處理。在其次之步驟S14， 則將已形成含有OH基之矽氧化膜之支撐器30由反應爐40 -30 - 1326109 搬出。在其次之步驟S16,則將基板72支撐於已形成含有 OH基的矽氧化膜之支撐器30。在其次之步驟S18，則將已 支撐基板72的狀態之支撐器30搬入反應爐40內。在其次 之步驟S20，則以上述方法對基板72實施熱處理。在其次 之步驟S22 ’則將支撐已結束對基板72的熱處理的支撐器 3 〇由反應爐40搬出。結束熱處理後之基板72係經冷卻至 特定溫度後，予以回收。在其次之步驟S 2 4，則加以判定 對基板72的熱處理次數（連續處理之次數）是否已達到特 定次數’亦即，加以判定支撐器表面之矽氧化膜中OH基 φ 是否巳減少至特定 （需要補充的程度之）。在該步驟 S24，若判定爲對基板72之熱處理次數已達到特定次數， 亦即’矽氧化膜中OH基已減少至需要補充的程度時，則 返回最初之步驟S10,以實施對支撐器30表面之再氧化處 理。藉此’即可使因連續處理所減少的矽氧化膜中OH基 復原。在步驟S24，若判定爲對基板72之熱處理次數未達 到特定次數’亦即，矽氧化膜中OH基並未減少至需要補 充的程度時，則返回步驟S16，對新的基板實施處理，以 鲁 供對基板72之熱處理能繼續實施直至熱處理次數達到特定 次數爲止。 其次’說明本發明人等所實施之實驗結果如下。 本發明者人等已在以在表面形成含有OH基的矽氧化膜 之支撐器來支撐基板之狀態下，進行在1,350 r之處理溫度 、且在含有〇2及N2之氣氛下將基板加以熱處理數小時之 實驗。實驗係以0〜1 0,000 ppm之範圍內改變矽氧化膜中 -31 - 1326109 OH基含量而進行。 另外，含有OH基之矽氧化膜，係藉由將以氮氣（N2 ) 使純水（H20 )發泡所生成之水份（H20 ) 1 %與氧氣（〇2 )供應於收容支撐器之反應爐內，並在1，200°C溫度、大氣 壓下，實施1 ~ 2小時之支撐器表面氧化處理（濕式氧化 )所形成。 其結果、在支撐器表面形成含有約10,000 ppm的OH基 之矽氧化膜後，立即施加基板之熱處理時，亦即，經在支 撐器表面形成含有OH基之矽氧化膜後、施加第一次之基 φ 板熱處理時，經以顯微鏡觀察熱處理後之基板表面結果也 有如第〗2圖所示，朝縱橫方向形成數條之滑動（條紋花樣 )者。其係起因於基板與含有OH基的矽氧化膜黏附所造 成之滑動。在該等並不存在如同傷痕般等的滑動之產生起 始點。 與此相對，以上述方法在支撐器表面形成含有OH基的 矽氧化膜後，對其含有OH基的矽氧化膜施加徐冷處理後 ’施加基板熱處理時，經以顯微鏡觀察熱處理後之基板表 鲁 面結果如圖1 3所示，並未看到有滑動之情事。 另外，對含有OH基的矽氧化膜之徐冷處理，係在未含 有OH基之氣氛中，使處理溫度設定爲1，350 °C、且使處理 時間設定爲1 0小時所實施者。 另外’在上述實施形態中，對形成在支撐器表面的矽氧 化膜補充（支撐器之再氧化處理）OH基，係針對於按每一 次特定的處理次數在基板之熱處理步驟前，在可不必將基 -32 - 1326109 板插放在反應爐內而以插放空的支撐器之狀態下所進行時 之情形加以說明，但是對矽氧化膜的OH基之補充，也可 在除此以外之時序時進行》 例如，即使在反應爐內插放已支撐基板的支撐器之狀態 ，亦即，即使在對基板施加熱處理步驟之途中，只要其爲 在熱處理步驟上係屬無難題之步驟，即可實施對矽氧化膜 之OH基補充。在熱處理步驟上係屬無難題之步驟，係包 括在最高處理溫度下的熱處理以外之步驟，亦即，在最高 處理溫度之熱處理前（基板升溫步驟）、在最高處理溫度 鲁 之熱處理後（基板降溫步驟）等。在該等步驟中，使H2〇 等之水份流通於反應爐內，即可在不致於影響到熱處理步 驟下，對形成在支撐器之矽氧化膜補充OH基》並且經補 充OH基後，停止H20等之水份供應，而供應n2或〇2等 之氣體時，即可在未含有OH基之氣氛下施加徐冷處理。 另外，在最高處理溫度之熱處理步驟中，使少量在熱處 理步驟上不致於造成影響的程度之h2o流通，藉此也可在 對熱處理步驟不致於造成影響下對形成在支撐器的矽氧化 鲁 膜補充OH基。在此種情形下，也可在最高處理溫度下之 熱處理步驟以外之步驟，或在含有例如在最高處理溫度的 熱處理前（基板升溫步驟），或在最高處理溫度下之熱處 理後（基板降溫步驟）中’使少量之h2o流通。另外，也 可在反應爐自搬入基板後直至搬出之期間，經常使少量的 Η 2 Ο流通。另外’在此種情形下’也可停止Η 2 Ο等之水份 供應而供應Ν2或02等之氣體時’也可在未含有ΟΗ基之 -33 - 1326109 氣胡I下施加徐冷。 如此，若在反應爐內插入已支撐基板的支撐器之狀態， 亦即，對基板施加熱處理步驟之途中，對形成在支撐器的 矽氧化膜施加OH基之補充時，則可在不必另外設置支撐 器再處理步驟下，即可提高產率。 另外，對形成在支撐器的矽氧化膜施加OH基之補充時 ，則即使取代H20而使用H2 (氫氣）等之含氫氣體，也可 獲得相同效果。 本發明之熱處理裝置也可適用於基板之製造步驟。 · 茲就在屬SOI (絕緣層上有砂；Silicon On Insulator)晶 圓之一種的 SIMOX (氧植入隔離；Separation by Implanted Oxygen )晶圓之製造步驟之一步驟適用本發明熱處理裝置 之實例說明如下。 首先，以離子注入裝置等對單結晶矽晶圓內植入氧離子 。其後，則使用上述實施形態之熱處理裝置，將經植入氧 離子之晶圓，例如在 Ar ' 〇2氣氛之下，在1，300 °C 〜 l，4〇〇°C，例如在1,3 5 0 °C以上之高溫下施加徐冷處理。經 修 由該等處理，即可製得在晶圓內部形成Si02層（埋入Si02 層）之SIMOX晶圓。 此外，除SIMOX之外，在氫徐冷晶圓製造步驟之一步驟 也可適用本發明之熱處理裝置。此種情形下，則將晶圓使 用本發明之熱處理裝置並在氫氣氛中在1，200°C以上之高溫 下加以徐冷處理。藉此，即可減少用作爲製造1C (積體電 路）的晶圓表面層之結晶缺陷，以提高結晶之完整性。另 -34 - 1326109 外，其他也可在磊晶晶圓製造步驟之一步驟適用本發明之 熱處理裝置。 即使爲作爲如上所述基板製造步驟之一步驟所實施的高 溫徐冷處理之情形，只要經使用本發明之熱處理裝置，即 可防止基板滑動之產生。 本發明之熱處理裝置也可適用於半導體裝置之製造步驟 。尤其是以適用於在較高的溫度下所進行之熱處理步驟， 例如濕式氧化、乾式氧化、氫氣燃燒式氧化（高溫氧化） 、：HC1 (鹽酸）氧化等之熱氧化，或將硼（B)、磷（P) · 、砷（As ) '銻（Sb )等之雜質（摻雜物）擴散於半導體 薄膜之熱擴散步驟等爲佳。 即使爲作爲如上所述半導體裝置製造步驟之一步驟所實 施的熱處理步驟之情形，只要經使用本發明之熱處理裝置 ，即可防止滑動之產生。 如上所述，本發明係雖然以申請專利範圍所記載之事項 爲其特徵，但是也包含下述實施形態。 (1) 在如申請專利範圍第1項之熱處理裝置中，熱處理 鲁 係在1，000°C以上之溫度下進行。 (2) 在如申請專利範圍第1項之熱處理裝置中，該矽氧 化膜中OH基含量爲20 ppm〜10,000 ppm。 (3 ) 在如申請專利範圍第1項之熱處理裝置中，該矽氧 化膜中OH基含量爲1〇, 〇〇〇 ppm〜數萬ppm。 (4 ) 在如申請專利範圍第2項之熱處理裝置中，該矽氧 化膜係由經在含有氧氣（〇2 )且未含有水（H20 ) -35 - 1326109 之氣氛下氧化（乾式氧化）後，在含有水（H2 0)之 氣氛下氧化（濕式氧化）所形成。 (5) 在如申請專利範圍第1項之熱處理裝置中，該支撐器 係構成爲以略水平狀態且隔著間隙使數片基片支撐 成數段。 (6) —種支撐器，其特徵爲用以支撐基板者，且至少在 與基板接觸之部份形成含有ΟΗ基之矽氧化膜。 〔產業上之利用性〕 本發明係在以將基板支撐於支撐器之狀態下實施熱處理 之熱處理裝置中，可利用於需要防止以基板與支撐器之接 觸爲起因的基板之傷痕或滑動者。 【圖式簡單說明】 第1圖係展示石英之因ΟΗ基含量所導致之黏性率之溫 度相依性特性圖。 第2圖係展示石英之ΟΗ熱解離量之溫度相依性特性圖 〇 第3圖係展示本發明實施形態之熱處理裝置立體圖。 第4圖係展示本發明實施形態之使用於熱處理裝置之反 應爐剖面圖。 第5圖係展示本發明實施形態之使用於熱處理裝置之支 撐器’且爲在支撐器直接支撐基板之實例，其中（3)爲側 視圖、（b )爲第1例之放大剖面圖、（c )爲第二例之放 大剖面圖、（d )爲第三例之放大剖面圖、（e )爲第四例 之放大剖面圖。 -36 - 1326109 第6圖係展示本發明實施形態之使用於熱處理裝置之支 撐器’係將基板經由保持器支撐在支撐器之實例，其中（a )爲側視圖、（b )爲第1例之放大剖面圖' (c )爲第二 例之放大剖面圖、（d )爲第三例之放大剖面圖、（e )爲 第四例之放大剖面圖。 第7圖係展示本發明實施形態之使用於熱處理裝置之 H20產生裝置，其中（〇係屬燃燒氧氣（〇2)與氫氣（H2 )來生成H20者、（b)係屬使純水發泡以生成H20者。 第8圖係展示本發明第一實施形態之熱處理裝置之控制 流量流程圖。 第9圖係展示本發明第二實施形態之熱處理裝置之控制 流量流程圖。 第1 〇圖係用以說明起因於黏附所導致基板滑動之產生機 制圖。 第1 1圖係用以說明本發明之基板滑動之減少典型圖。 第12圖係展示未實施徐冷處理時之基板表面狀態之顯微 鏡照片。 第1 3圖係展示經實施徐冷處理時之基板表面狀態之顯微 鏡照片。 【主要元件符號說明】 10 熱處理裝置 12 機箱 14 密閉莢式容器台 16 密閉莢式容器 1326109 18 20 22 24 密閉莢式容器搬送裝置 密閉莢式容器擱架 密閉莢式容器開蓋器 基板片數檢測器 26 基板移載機 28 30 32 凹槽調準器 支撐器 臂 34 上板 36 下板 38 支柱 40 反應爐 42 44 46 48 反應管 密封蓋 均勻加熱管 加熱器 50 52 54 56 58 60 、 64b 、 92 62、84 64a 熱電偶 導入管 排氣管 氣體供應系 H20產生裝置 N2氣體源 〇2氣體源 H2o供應線 1326109 64a 、 64b 、 64c 供應線 66a、66b、66c、88a、88b ' 96 開閉閥 68a 、 68b 、 68c 、 90a 、 90b 、 98 質流控制器 70 支撐片 72 基板 74 矽氧化膜 76 塗佈層 80 保持器 82 h2氣體源 86 外部燃燒裝置 94 純水容器 100 、 100 突起 102 膜 102Si) is composed of ruthenium (Si) coated with tantalum carbide (SiC) on the surface. According to a tenth aspect of the present invention, there is provided a reactor for heat-treating a substrate, and a support for supporting the substrate in the reactor, and the support is formed at least in a portion in contact with the substrate. In the heat treatment apparatus of the 〇H-based bismuth oxide film, the support has a body portion and a support portion in contact with the substrate, and the support portion is composed of a plate member. An eleventh feature of the present invention is a method of manufacturing a substrate, comprising the steps of: loading a substrate into a reaction furnace, and supporting the supporter having an OH-based oxide film formed at least in a portion in contact with the substrate; a step of performing a heat treatment in a state in which the substrate is supported by the support in the reactor, and a step of carrying out the heat-treated substrate from the reactor. A twelfth feature of the present invention is the step of supporting a substrate by supporting a substrate containing at least a ruthenium oxide film containing an OH group at least in a step of bringing the substrate into contact with the substrate, in the step of carrying the substrate into the reaction furnace. In the manufacturing method of the step of performing heat treatment in a state where the substrate is supported by the support, and the step of carrying out the heat-treated substrate by the reaction furnace, an empty support is provided before the substrate is carried in the reaction furnace The device is carried into a reaction furnace and an oxidation treatment is applied to the support under an atmosphere containing hydrogen atoms and oxygen atoms. A thirteenth feature of the present invention is a method of manufacturing a substrate, comprising the step of loading a substrate into a reaction furnace, and forming a substrate in contact with the substrate at least in an atmosphere containing no OH group; a step of supporting a substrate by a support of an OH-based ruthenium oxide film, a step of performing heat treatment in a state where the substrate is supported by the supporter in the reactor -9 - 1326109, and a heat treatment after being carried out by the reactor The steps of the substrate. A fourteenth feature of the present invention is the step of carrying the substrate into the reaction chamber to form an oxime-containing oxidizing agent containing an OH group which is subjected to a quenching treatment in an atmosphere not containing an OH group, at least in a portion in contact with the substrate. a step of supporting a substrate by a support of a film, a step of performing heat treatment in a state in which the substrate is supported by the support in the reaction furnace, and a method of manufacturing a substrate in which the substrate after the heat treatment is carried out by the reaction furnace Before the substrate is carried into the reactor, the empty support is carried into the reactor and subjected to a cold treatment in an atmosphere containing no φ φ group. The present invention has been subjected to various begging results for materials suitable for contact with a substrate, and it has been found that the present invention is most suitably obtained by using SiO 2 containing an anthracene group. Regarding quartz, it is known that the viscosity ratio varies depending on the amount of moisture (OH group) contained in the quartz. In this case, "viscosity", if you want to move an object with various external forces, it will have a resistance to it in the object, that is, the resistance to deformation, the viscosity is the nature of the degree. . Viscosity rate 7? [ Pa _ s] (= [poise]) means that the fluid is trapped between two plates of the area φ S [ m 2 ] (distance d [ m ]), and When the plate of one of the plates is parallel and moves at a certain speed (v[m/s]), the amount of force (F[N]) received by the plate from the liquid: F/S = η v/d η = [N] [m] / [m2] [ m / s ] = [ N ] [s] / [m2] = [Pa] [ s]. In Figure 1, the temperature dependence of the viscosity due to the H-based content is shown in the figure -10 - 1326109 (from http : //www. Asahi-net. Or. Jp/%7Eup5s- andu/index. Htm). The more the OH group content in the quartz, the lower the viscosity rate is 7?. The basis for the viscosity ratio 77 is the upper limit of the glass process that can be applied below the softening point of Fig. 1, and the area above the strain point is considered to be a long time (in years) and is not deformed. In the middle of the cold point, the use of the unit is about to be deformed in units of months, and the following is the area in which the deformation is to be used in units of days. In the present invention, at least the portion which is in contact with the substrate is made into an iridium oxide film containing an OH group so as to have an appropriate viscosity ratio. The viscosity ratio is preferably 10 kPa or less at 〇〇〇 ° C, preferably 13 kPa or less at 1,200 ° C, and preferably 15 kPa or less at 1,3 50 °C. In order to have such a viscosity ratio, it is necessary to set the OH group content in the tantalum oxide film to 20 ppm or more. In this case, the viscosity of the OH-containing ruthenium oxide film is, as compared with the viscous ratio of the ruthenium oxide film containing no OH group, at 1/100 or less at 1,000 ° C, at 1,200 ° C is 1/100 or less, and is 1,100 or less at 1,3 50 °C. Further preferably, the OH group content in the ruthenium oxide film is preferably set to 20 ppm to tens of thousands of PPm. In this case, the viscosity ratio of the OH-containing ruthenium oxide film is compared with that of the ruthenium oxide film containing no OH group, and is 1/100 to 1/1012 at 1, 〇〇〇 °C. It is 1/100 to 1/1010 at 1,200 °C and 1/100 to 1/108 at 1,35 °C. Further preferably, the OH group content in the ruthenium oxide film is preferably set at 20 ppm to 10,000 ppm. In this case, the viscosity of the OH-containing ruthenium oxide film is, as compared with the viscous rate of the ruthenium oxide film containing no ruthenium H group, at 1 / 0 0 0 t is 1 / 1 0 0~1 /1 0 1 °, 1/100 ~ 1/1〇8 at l, 2〇〇 °C, 1/100 ～1/106 1326109 at 1,3 50 °C. Further, the OH group content in the tantalum oxide film can be set to 10,000 ppm to tens of thousands of ppm. In this case, the viscosity of the ruthenium oxide film containing ruthenium H group is 1, in comparison with the viscosity of the ruthenium oxide film containing no OH group. (: is 1/101. ~1/1012, at 1,20 (TC is 1/108 to 1/101. It is 1/106 to 1/108 at 1,3 50 °C. In addition, This so-called "ppm" means Parts Per Million (1 part per million). In addition, it is known that as the temperature increases, the OH group in the quartz will thermally dissociate to release active hydrogen. Figure 2 shows 〇 Temperature dependence of sulfhydryl thermal dissociation (from http : //www. Asahi-net. Or_jp/%7Eup5s-andu/index. Htm). In the temperature range of 1,000 ° C ~ 1,400 ° C, the shell IJ can be calculated as a temperature rise of about 100 ° C, that is, 10 times the OH group will be thermally dissociated. However, as shown in Fig. 2, the thermal dissociation degree is also about 1 E-3 (mole %) at 1,400 ° C, and therefore, it is not necessary to consider the content of OH groups due to thermal dissociation in practical use. cut back. In the heat treatment of the purpose, oxidation by oxygen (the OH group content is approximately several ppm) or the use of an inert gas is usually employed. Since the active hydrogen released by thermal dissociation has a very strong reducing power, it reacts with the oxygen atom bonded to Si _0_Si in the ruthenium oxide film. The reaction is shown in the following formula. ξ Si - 0 - Si ξ + H (gas) - Si - Ο - H + Si In addition, the active hydrogen has a very small atomic radius, so the reaction is likely to be a ruthenium oxide film formed by heat treatment through the purpose. The deep part of the film will also be produced. In the heat treatment of the purpose, the ruthenium impurities taken into the ruthenium oxide film may constitute a reduction in the film quality of the substrate. For this reason, it is preferable to avoid leaving it in the heat-treated tantalum oxide film (especially in the vicinity of the tantalum oxide film / -12 - 1326109 矽 plate interface). In order to avoid this, a large amount of OH groups are contained in the oxidation treatment on the surface of the support, and it is preferred to carry out the substrate before the reaction furnace. When a tantalum oxide film containing an OH group is used, there is an advantage that the occurrence of slippage of the substrate can be suppressed even when a tantalum oxide film is formed on a support having a rough surface to some extent. That is, the surface state of the support for forming the tantalum oxide film is not necessarily too restrictive. In the meantime, the ruthenium oxide film itself is softened by the incorporation of the OH group, and the fluidity is increased to become a buffer material, and the stress is easily released. In addition, there is also an advantage that the process window (the allowable range in the process) when the substrate φ is processed becomes wide. For example, even if the temperature increase rate at the time of substrate processing is increased to some extent, the occurrence of substrate sliding can be suppressed. On the other hand, when a tantalum oxide film containing no OH group is used, the substrate may slip if the surface of the support is in a limited surface state or surface roughness. In this case, it is necessary to pay attention to the surface state (surface roughness, etc.) of the support, and the support surface must be adjusted to completely eliminate the cause of slippage, and as a result, the rise is caused. Moreover, there is a disadvantage that the process window when the substrate is processed becomes narrow. For example, the rate of temperature increase will be limited to a certain rate, etc., which will impose various limitations on the processing conditions of the substrate. If you want to reduce the viscosity of the tantalum oxide film, you can do it by mixing other impurities in the tantalum oxide film. However, the ruthenium base is excellent in comparison with other impurities insofar as it can reduce the viscosity of the ruthenium oxide film without causing contamination of the substrate. -13 - 1326109 The film thickness of the ruthenium oxide film containing an OH group is preferably Ι, ΟΟΟΑ to several micrometers (for example, 3 to 5 μm). More preferably, it is set to several thousand Α to several micrometers. If the film thickness of the ruthenium oxide film is set to be larger than l, and 〇〇〇A is thinner, the protrusion of about several micrometers on the surface of the support may break the ruthenium oxide film, so that the ruthenium oxide film as a buffer layer The effect is greatly reduced. On the other hand, when the film thickness of the tantalum oxide film is made thicker than several micrometers, there is a possibility that the tantalum oxide film is peeled off, and therefore some anti-stripping measures are required. However, it has been confirmed that there is some slippage as a result of sliding evaluation of the substrate on which the heat treatment is applied immediately after the formation of the ruthenium oxide film containing the OH group. φ A photomicrograph of the surface of the substrate is shown in Fig. 12. It can be seen from the figure that a small number of slips (striped patterns) have been formed in the longitudinal and lateral directions. The reason is as follows. That is, as shown in Fig. 10(a), hard protrusions 1 and 100 are formed on the surface of the support 30 made of SiC, and an oxide film 74 containing an OH group is formed thereon, and thus As shown in Fig. 10(b), when the substrate 72 is placed on the holder 30 and heat treatment is performed, the tantalum oxide film 74 containing an OH group having a low viscosity is crushed to cause a ruthenium containing a ruthenium H group. The oxide film 74 φ is adhered to the number of the substrate 72. Therefore, as shown in the first graph (c), the substrate 72 is to be deformed during the temperature rise and fall during the heat treatment, but since the substrate 72 and the ruthenium oxide film 74 containing the OH group are fixed at the time of adhesion, The stress will concentrate on the substrate 71 between the bonds. At this time, when the force at which the substrate 72 is to be deformed exceeds the adhesion force, a stress is released from the adhesive portion, causing the substrate 72 to slip due to the impact. Then, in the present invention, the ruthenium oxide film containing the OH group is subjected to a cold treatment in an atmosphere containing no OH group in the range of -14,326,109, so that the ruthenium oxide film existing in the OH group having a low viscosity ratio is the most On the surface, the H-based group (the main cause of the decrease in the viscosity ratio) is removed a little, and the viscosity of the surface becomes higher. In other words, as shown in Fig. 11 (a), the OH group is not contained. The cold treatment is carried out in an atmosphere, whereby the OH group is removed on the outermost surface of the ruthenium oxide film 74 having a low viscosity OH group to form a film 102 having a higher viscosity (harder), so that the OH group is contained. The oxide film 74 is covered with the film 102. Therefore, as shown in Fig. 11(b), when the substrate 72 is placed on the holder 30 to perform heat treatment, the substrate 72 is brought into contact with the film 102 having a higher viscosity ratio, so that the substrate 72 and the OH are contained. The base oxide film 74 is not easily adhered. Therefore, as shown in the figure (c), at the temperature rise and fall of the heat treatment, even if the substrate 72 is deformed, since the adhesion portion to the tantalum oxide film 74 containing the 〇H group is small, the substrate 72 and the film 1 can be made. Sliding occurs between 02 to cause the substrate 72 to slowly deform, so that stress concentration can be prevented to prevent slippage of the substrate 72. In addition, since the film 1 〇 2 is very thin (for example, 1 〇 〇 nanometer or less), the effect of the invention of the first embodiment (the first feature or the like described later) is not hindered. This first embodiment is for forming an yttrium oxide film 74 containing an OH group. Further, the ruthenium oxide film containing an OH group is rapidly cooled in an atmosphere containing no ruthenium H group, and is formed in a batch of heat treatment immediately after the formation of the OH group-containing sand oxide film 74. It is placed in a reaction furnace and is carried out in an empty batch manner in which only the support is placed. [Effects of the Invention] In the present invention, since the material having a low viscosity (softer) is disposed at least in a portion of the support which is in contact with the substrate -15 - 1326109, the low viscosity is formed. The portion of the rate supports the substrate, so that even if a non-flat and hard material such as SiC is used as the support base material, it is possible to prevent the substrate from being scratched and to prevent slippage on the substrate. Further, since the layer having a higher viscosity is formed on the outermost surface of the material having a low viscosity, the adhesion to the substrate can be prevented to prevent the sliding due to adhesion. [Embodiment] [Best Mode for Carrying Out the Invention] Φ Next, an embodiment of the present invention will be described below based on the drawings. Fig. 3 is a view showing a heat treatment apparatus 10 according to an embodiment of the present invention. The heat treatment device 1 has, for example, a vertical shape and has a casing 12 for arranging a main portion. The closed pod container 14 is connected to the casing 12, and the sealed pod container 16 is conveyed to the closed pod container 14. The sealed pod container 16 accommodates, for example, 25 substrates, and is placed in a closed pod container stage 14 in a state of being covered by a cover (not shown). In the casing 12, a closed pod container transporting device 18 is disposed at a position relative to the closed pod container. Further, in the vicinity of the sealed pod container transporting device 18, a closed pod container 20, a closed pod container opener 22, and a substrate number detector 24 are disposed. The closed pod container transfer device 18 is configured to transport the sealed pod container 16 between the closed pod container holder 14 and the closed pod container holder 20 and the closed pod container opener 22. The closed pod container opener 22 is used to open the lid of the closed pod container 16. The substrate piece 16 - 1326109 in the closed pod container 6 of the lid is opened by the substrate number detector 24 to test. On the other hand, in the casing 12, the substrate transfer machine 26, the groove aligner 28, and the holder 30 (boat) are disposed. The substrate transfer machine 26 is, for example, an arm 32 that can take out five substrates at a time, and by operating the arm 32, it can be placed in a closed pod container or groove at a position where the pod pod opener 22 is closed. The substrate is transferred between the aligner 28 and the supporter 30. The groove aligner 28 is used to detect grooves or orientation planes that are pre-formed on the substrate for aligning the grooves or orientation planes of the substrate to a certain position. The support 30 is composed of an upper plate 34 and a lower plate 36 on the circular plate, and three to four pillars 38 for connecting the upper plate 34 and the lower plate 36. The reaction furnace 40 is shown in the first 4 in the picture. The reactor 40 has a reaction tube 42 in which a support 30 is inserted. The lower portion of the reaction tube 42 is opened for inserting the holder 30, and the open portion is configured to be sealed by the sealing cover 44. The reaction tube 42 is surrounded by a uniform heating tube 46 and is uniformly heated. A heater 48 is disposed around the tube 46. The thermocouple 50 is disposed between the reaction tube 42 and the uniform heating tube 46, and is configured to monitor the temperature in the reaction furnace 40. Further, a 导入 introduction pipe 52 for introducing a process gas is connected to the reaction pipe 42 with an exhaust pipe 54 for discharging a process gas. The gas supply system 56 is connected to the gas introduction pipe 52. The gas supply system 56 includes an H20 generating device 58, an N2 gas source 60, and a helium gas source 62, which will be described later, and the H20 generating device 58, the N2 gas source 60, and the helium gas source 62 are connected to the H20 supply lines 64a, N2. Supply lines 64b and 02 supply lines 64c. The supply lines 60, 6 and 64c are each provided with on-off valves 66a, 66b -17 - 1326109, 66c and mass flow controllers (MFC) 68a, 68b, 68c for regulating gas flow rate via the MFCs 68a, 68b, 68c. Thereafter, it is supplied to the reaction furnace 40. Next, the heat treatment apparatus 10 configured as described above will be described as follows. First, when the sealed pod container 16 accommodating a plurality of substrates is placed on the closed pod container stage 14, the closed pod container conveying device 18 will be used. The closed pod container 16 is transferred from the closed pod container stage 14 to the closed pod container holder 20' and stored in the sealed pod container holder 20. Then, the closed pod container 16 stored in the sealed pod container rack 20 is transported to the closed pod container opener 22 and erected and fixed by the closed pod container transporting device 18, and then the sealed pod container is used. The lid opener 22 opens the lid of the closed pod container 16 for detecting the number of substrates accommodated in the closed pod container 16 by the substrate number detector 24. Next, the substrate transfer machine 26 takes the substrate out of the closed pod container 16 at the position of the closed pod container opener 22 and transfers it to the groove aligner 28. The groove aligner 28 is about to rotate the substrate while detecting the grooves, and aligning the grooves of the plurality of substrates into the same position based on the detected information. The substrate is then removed by the groove aligner 28 by the substrate transfer machine 26 and transferred to the holder 30. When a batch of the substrate is transferred to the holder 30 in the above manner, the holder 30 loaded with the plurality of substrates is loaded into the reaction furnace 40 which is set to have a temperature of, for example, about 600 ° C, Then, the inside of the reaction tube 42 is sealed with a sealing cover 44. Next, the temperature in the furnace is raised to the heat treatment temperature, and then nitrogen and oxygen as process gases are introduced from the introduction pipe 52. The introduction process -18 - 1326109 gas system heats the substrate by opening the on-off valves 66b, 66c' to regulate the gas flow rate with the MFCs 68b, 68c, and from the N2 gas source 60 and the 02 gas source 62 through the supply line 6 4b '64c. At the time, the substrate is heated by, for example, a temperature of 1,000 ° C or more, or even 1,350 ° C or more. During this period, of course, the temperature in the reaction tube 42 is monitored via the thermocouple 50, and the heat treatment of the substrate is performed according to a predetermined temperature rise and heat treatment procedure. When the heat treatment of the substrate is completed, for example, the temperature in the furnace is lowered to about 6,000. After its temperature, the support 30 is unloaded from the reaction furnace 40 and the support 30 is placed in a specific position until all of the substrates supported in the support 30 are cooled. Further, when the temperature in the furnace is lowered, the temperature in the reaction tube 4 2 is also monitored by the thermocouple 50, and the temperature is lowered in accordance with a preset cooling program. Then, when the substrate of the standby support 30 is cooled to a specific temperature, the substrate is taken out by the substrate transfer machine 26 from the holder 30 and transferred to the airtight pod container 16 placed in the closed pod container opener 22. And to be accommodated. Then, the sealed pod container 16 of the receiving substrate is transported to the sealed pod container holder 20' by the closed pod container conveying device 18, and then transferred to the closed pod container holder 14 to be completed. Next, the above-described supporter 30 will be described in detail as follows. In Fig. 5(a), in each of the stays 38 of the holder 30, a plurality of support pieces 7 are formed to protrude toward the inner side of the holder 30. In the support sheet 7, the substrate 72' on which the wafer or the like is placed in a slightly horizontal position is supported in the support 30 in a slightly parallel state and supported by a plurality of substrates 7 2 with a gap therebetween. As shown in Fig. 5(b), the struts 38, including the support sheets 70, are formed, for example, of bismuth (Si) or tantalum carbide (SiC), and are included in the struts 38 including the support sheets 7〇. A tantalum oxide film (Si 02 film) 74 is formed in its entirety. The ruthenium oxide film 74 contains an OH group, and the OH group content in the tantalum oxide film 74 is from 20 ppm to several tens of ppm (e.g., 20,000 to 30,000 ppm). Further, the film thickness of the tantalum oxide film 74 is 1, 〇〇〇Α ~ a few micrometers (for example, 3 to 5 μm). As shown in Fig. 5(c), 构成(Si) may be used as the constituent material of the pillars 38 including the support sheets 70, and the tantalum pillars 38 (including the support sheets 70) may be integrally formed, for example, by carbonization. A coating layer 76 composed of cerium (si C ) is formed, and the above-described tantalum oxide film 74 is formed on the coating layer 76. Further, the coating layer 76 is formed by a plasma CVD (Chemical Vapor Deposition) method or a thermal CVD method. The thickness of the coating layer 76 is preferably formed to be between 0. 1 micron to 50 micron range. When the coating layer 76 made of tantalum carbide is formed thick, the support sheet 70 made of tantalum is pulled by the coating layer 76 made of tantalum carbide due to the difference in thermal expansion coefficient between the tantalum and the niobium carbide. The amount of deformation of the entire body becomes large to cause the substrate 72 to slip due to the large deformation. On the other hand, when the coating layer 76 made of tantalum carbide is set to have the above-described thickness, the amount of the support sheet 70 made of tantalum can be reduced by the coating layer 76 made of tantalum carbide. The amount of deformation of the entire support sheet will also be reduced. In other words, when the coating layer 76 made of tantalum carbide is set to be thin, the stress caused by the difference in thermal expansion coefficient between the support sheet 70 and the coating layer 76 can be reduced, and the amount of deformation of the entire support sheet can be reduced, and the entire support sheet can be reduced. The coefficient of thermal expansion will also be close to the original coefficient of thermal expansion (the substrate 72 is slightly equivalent to the coefficient of thermal expansion if it is tantalum), so that the occurrence of slip can be prevented. The thickness of the carbonized tantalum coating layer 76 is set to be less than 0. At 1 micron, then -20 - 1326109 will be consumed because the tantalum carbide coating layer 76 is too thin, so that the tantalum support sheet 70 must be coated with tantalum carbide so that the same support 30 can be used repeatedly. If the thickness of the coating layer 76 is set to 0. When the thickness is 1 μm or more, it is not necessary to recoat the coating layer 76 of the tantalum carbide to the supporting sheet 7 of the tantalum, so that the same holder 30 can be repeatedly used. Further, when the thickness of the coating layer 76 made of tantalum carbide is set to 1 μm or more, the number of times the same holder 30 can be repeatedly used can be increased because the film is less likely to be consumed. When the thickness of the tantalum carbide coating layer 76 is set to be larger than 50 μm, the tantalum carbide coating layer 76 itself is liable to be broken, and the substrate 72 is likely to slip due to the crack. When the thickness of the coating layer 76 is set to 50 μm or less, the cracking of the coating layer 76 is less likely to occur, and as described above, the support sheet 70 made of tantalum and the coating layer made of tantalum carbide can also be reduced. Since the stress caused by the difference in thermal expansion rate of 76 is small, the deformation of the entire support piece is reduced, so that the sliding of the substrate 72 can be prevented. When the thickness of the tantalum carbide coating layer 76 is set to 15 μm or less, the sliding of the substrate is hardly caused. Further, if the thickness of the tantalum carbide coating layer 76 is set to 0. When 1 micrometer to 3 micrometers, the sliding of the substrate 72 does not occur. Therefore, the thickness of the carbonized tantalum coating layer 76 is 0. 1 micron to 50 micron is preferred, more preferably 0. 1 micron to 15 micron, further preferably 0. 1 micron to 3 micron. The thickness of the tantalum support sheet 70 and the tantalum carbide coating layer 76 is expressed by the ratio of the two, so that the thickness of the tantalum carbide coating layer 76 is set to 0. 0025 %~1. 25 % is better, more preferably 0. 0025 % ~0. 38%, further better is 0. 0025 % ~0. 25 %. The coating layer 76 may be formed by coating a tantalum nitride (SiN) by a plasma CVD method or a thermal CVD method in addition to niobium carbide. When the tantalum nitride is used, the thickness of the coating layer 76 is preferably set to 〇1 μm to 3 μm, more preferably set to 0. 1 micron to 5 micron. The coating layer 76 is used as an adhesion preventing layer to prevent adhesion of the support sheet 70 to the substrate 72. The OH-containing sand oxide film 74 may be formed in the entire portion of the pillars 38, at least in a portion that will be in contact with the substrate 724, for example, as shown in Fig. 5(d), or may be formed in 矽( The upper portion of the support piece 70 of the pillar 38 made of Si) or sic is made of the substrate, and the substrate 72 is brought into contact with the sand oxide film 74 formed on the support sheet 70. Further, as shown in Fig. 5(e), a coating layer 76 composed of, for example, tantalum carbide (SiC) may be formed on the support sheet 70 of the crucible (Si) pillar 38, and then the coating layer 76 may be formed thereon. An antimony oxide film 74 containing an OH group is formed thereon. Further, the holder 30 may also take the form of the holder 8 of the plate-like member supported by the support piece 70 of the support portion of the body portion as shown in Fig. 6, and then support the form of the substrate 72 via the holder 80. The diameter of the holder 80 is smaller than the diameter of the substrate 723, that is, the upper surface of the holder 80 has an area smaller than the area of the flat surface of the lower surface of the substrate 72. A portion other than the periphery of the substrate 72 is supported by the holder 80 (the holder 80 supports the substrate 72 in a state where it is not in contact with the outer periphery of the substrate 72). The substrate 72 is, for example, 300 mm in diameter, so that the diameter of the holder 80 is less than 300 mm, i.e., about 100 mm to 250 mm (about 1/3 to 5/6 of the outer diameter of the substrate). Moreover, the thickness of the holder 80 is formed to be thicker than the thickness of the substrate 72 by -22 - 1326109. The thickness of the substrate 72 is, for example, 700 μm. Therefore, the thickness of the support portion 72 is greater than 700 μm, and even 10 mm, preferably at least 2 times the thickness of the substrate 72, for example, 3 mm to 10 mm. Preferably, it is preferably 3 mm to 6 mm, and further preferably 4 mm to 5 mm. In addition, the thickness of the retainer 80 is thicker than the thickness of the support sheet 70. The reason why the thickness of the holder 80 is set to such a thickness is to increase the rigidity of the holder 80 itself to suppress deformation of the holder 80 at the time of heat treatment. Of course, it is not necessarily necessary to form the thickness of the tantalum oxide holder 80 to be thicker than the thickness of the substrate 72 as long as it can suppress deformation at the time of heat treatment. Further, the diameter (area) of the retainer 80 may be formed to be larger than the diameter (area) of the substrate 72. In this case, the thickness of the retainer 8 should be thicker. In the above-described form of the holder 30, as shown in Fig. 6(b), the holder 80 is formed, for example, of bismuth (Si) or tantalum carbide (SiC), and the above-described inclusion 〇 is formed in the holder 80 in its entirety. The H-based oxide film 74. As shown in Fig. 6(c), the constituent material of the holder 80 can also be made of bismuth (Si), and the tantalum carbide holder 80 can be formed integrally with, for example, the tantalum carbide shown in Fig. 5(c). The coating layer 76 composed of (SiC) is then formed on the coating layer 76 to form the above-described tantalum oxide film 74. The ruthenium oxide film 74 containing an OH group is not necessarily formed in the entirety of the holder 80, and at least a portion which is formed in contact with the substrate 72 is sufficient, for example, as shown in Fig. 6(d), or only in 矽 (Si) Or a top surface of the holder (80) made of tantalum carbide (SiC) is formed so that the substrate 72 is in contact with the tantalum oxide film 74 formed on the holder 80. And, as shown in Fig. 6(e), a coating layer 76' composed of, for example, tantalum carbide (S i C ) may be formed on the top of the crucible (Si) holder 80 1326109 and coated. Layer 76 forms a tantalum oxide film 74 containing an OH group. Next, a first embodiment of a method for forming a tantalum oxide film containing an anthracene group in a support (including a boat or a holder) will be described below. If a tantalum oxide film containing a mercapto group is to be formed, the same reactor as the reactor for heat-treating the substrate can be used. As shown in Fig. 4, 'the gas supply system 56 is provided with a crucible 20 generating means 58, and the crucible 20 generating means 58 supplies water to the reaction furnace 40 for accommodating the holder 30, whereby the niobium containing niobium can be oxidized. The film is formed on the holder 30. The reaction furnace 40 that can perform both the processing of the support 30 and the processing of the substrate is to add a Η20 supply line 64a for supplying moisture (Η20) to the reaction furnace for applying heat treatment to the substrate. It can be constructed simply. Further, the formation of the OH-containing ruthenium oxide film of the support 30 and the heat treatment of the substrate can be carried out separately in individual reactors. The method of oxidizing the surface of the support by the H20 generated by the above-described H20 generating means 58 is used. The first example has a method of using high temperature oxidation. The H20 generating device 58 has an H2 gas source 82, a 02 gas source 84, and an external combustion device 86 in Fig. 7(a). The H2 gas source 82 and the 02 gas source 84 are connected side by side to the external combustion device 86 via the on-off valves 8 8 a, 8 8b and the mass flow controllers (MFC) 90a, 90b, respectively, and are combusted by the external combustion device 86 from H2. The gas source 82 and the hydrogen gas (H2) and the oxygen gas (02) of the gas source 84 of the helium gas 2 generate water vapor (h2〇), and supply the generated water vapor (H20) and oxygen gas (〇2) to the storage support 3 The reaction of ruthenium - 2426109 is carried out in furnace 40 and the surface of support 30 is oxidized at atmospheric pressure at a temperature of about 1,000 to 1,200 °C. Thereby, the ruthenium oxide film containing an OH group can be formed on the surface of the support 30. Further, the control of the 〇H group content in the ruthenium oxide film is carried out by controlling the supply flow rate of H2, 02 or H20, the oxidation treatment temperature, the oxidation treatment time, and the like. The method of oxidizing the surface of the support by the H20 produced by the above-described H20 generating means 58 is used, and the second example is a method of oxidizing using H20 formed by foaming pure water with an inert gas. It is shown in Fig. 7(b), and the H20 generating unit 58 has a N2 gas source 92 storing, for example, N2 gas, which is an inert gas, and a pure water container 94 for storing pure water. The N2 gas source 92 is connected so as to be open to the lower portion of the pure water contained in the pure water container 94 via the opening and closing valve 96 and the mass flow controller (MFC) 98. Therefore, the pure water (H20) in the pure water container 94 is foamed to generate moisture by, for example, nitrogen gas (N2) from a source of N2 gas, and the generated water vapor (H20) and oxygen (?2) are generated. The inside of the reaction furnace 40 for accommodating the holder 30 is supplied, and the surface of the support 30 is oxidized at atmospheric pressure at a temperature of about 1, 〇〇〇 1, 1,200 °C. Thereby, the ruthenium oxide film containing an OH group can be formed on the surface of the support 30. Further, the control of the OH group content in the tantalum oxide film is carried out by controlling the supply flow rate of N2, H20 or 〇2, the oxidation treatment temperature, the oxidation treatment time, and the like. The method of oxidizing the surface of the support by the H20 generated by the above-described H20 generating means 58 is used, and the third example has a method of oxidizing only using moisture (H20) and a carrier gas. In the same manner as the second example, the H20 generating device 58 shown in Fig. 7 (b) is used to make the pure water (H20) in the pure water container 94, for example, nitrogen gas (N2) from the N2 gas source. Foaming to generate moisture, and the generated water vapor (H20) and carrier gas are supplied into the reaction furnace 40 of the storage support 30 at a temperature of about 1,000 to 1,200 ° C. Oxidation of the surface of the support 30 is carried out under atmospheric pressure. Thereby, an iridium oxide film containing an OH group can be formed on the surface of the holder 30. Further, the control of the ruthenium H group content in the ruthenium oxide film is carried out by controlling the supply flow rate of N2, H20 or carrier gas, the oxidation treatment temperature, the oxidation treatment time, and the like. The carrier gas is an inert gas such as nitrogen (N2) 'helium (He), argon (Ar), and the like. For spring, it is also possible to form a ruthenium oxide film containing an OH group using only moisture (H20) and a carrier gas without using an oxygen (〇2) gas. The method of oxidizing the surface of the support via H20 produced by the above-described H20 generating means 58 is used, and the fourth example has a method of combining dry oxidation and wet oxidation. That is, it supplies oxygen (02) and nitrogen (N2) to the reactor 40 accommodating the supporter 30, and performs the support at atmospheric pressure at a temperature of about 1, 〇〇〇1,200 °C. 30 surface oxidation treatment (dry oxidation). Through this treatment, an oxide film containing no OHS # can be formed on the surface of the support 30. Thereafter, oxidation treatment (wet oxidation) using moisture (H20) is carried out. Wet oxidation is, for example, high temperature oxidation as described above. Thereby, the tantalum oxide film containing an OH group can be formed on the surface of the holder 30. Further, the control of the 〇H group content in the ruthenium oxide film is carried out by controlling the supply flow rate of H2, N2 or H20, the oxidation treatment temperature, the oxidation treatment time, and the like in the wet oxidation performed after the dry oxidation. . Thus, by applying wet oxidation after dry oxidation, a ruthenium oxide film containing OH groups -26 - 1326109 can be formed in combination with the above treatment in a reaction furnace, and the results are shown in Fig. 8. First, in step S10, the empty holder 30 (the holder 3 to which the substrate is not mounted) is carried into the reaction furnace 40. In the next step S12, the moisture-containing gas obtained by the above method is supplied into the reactor 40 which has been carried into the empty support 30 to form an oxidized film containing OH groups in the holder 30. In the next step s 14 4, the support 30 which forms the tantalum oxide film containing the OH group is carried out from the reaction furnace 40. In the next step S16, the substrate 72 is supported on a holder 30 φ which is formed to form a tantalum oxide film containing a ruthenium H group. In the next step s 18, the support 30 in the state in which the substrate 72 has been supported is carried into the reaction furnace 40. In the next step S20, heat treatment is applied to the substrate 72 by the above method. In the next step S22, the holder 30 which has finished the heat treatment of the substrate 72 is carried out from the reaction furnace 40. In the next step S24', it is determined whether or not the number of times of heat treatment (the number of consecutive processes) applied to the substrate 72 has reached a certain number of times. In the step S24, if it is determined that the number of times of heat treatment applied to the substrate 72 has reached a certain number of times, the initial step S10 is returned to perform the reoxidation of the surface of the holder 30. Thereby, the OH group in the ruthenium oxide film on the surface of the support reduced by the continuous treatment can be restored. If it is determined in step S24 that the number of times of heat treatment on the substrate 72 has not reached a certain number of times, the process returns to step S1 6 to heat the substrate 72 until a certain number of times can be reached. Further, the specific frequency in step S24, i.e., the frequency of reoxidation treatment of the OH group in the tantalum oxide film on the surface of the support surface on which the supplementary substrate is reduced by continuous processing, is set in the following manner. That is, before performing the continuous processing of the substrate -27 - 1326109, the data of the 〇H group content (or reduction amount) in the ruthenium oxide film on the surface of the supporter relative to the number of substrate treatments (the number of batches) is obtained, and OH is detected. The base content is reduced to the specific number of treatments required. The number of times of the treatment is then set to the number of times from the start of the application of the oxidation treatment to the support to the application of the reoxidation treatment (the specific number of times in step S24). Further, the 〇H group content in the ruthenium oxide film is calculated, for example, by measuring the spectrum of the sand oxide film by a Fourier Transform Infrared Spectrometer (FTIR). At this time, the object to be inspected needs to be an optical surface (honing) on both sides. Therefore, the honing of the tantalum oxide film on the surface of the support is performed before the measurement to form an optical surface. The wavelength of the resulting spectrum is 2. At 73 microns, the absorption due to the "Si-OH" bond will occur, so the OH group content can be calculated from its peak. In the continuous processing of the substrate, it is set so that the OH group in the tantalum oxide film on the surface of the support can be subjected to a reoxidation treatment using water in accordance with a predetermined number of times of treatment. By this reoxidation treatment, the OH group in the tantalum oxide film on the surface of the support which is reduced by the continuous treatment can be replenished so that the OH content in the tantalum oxide film can be restored to be suitable before the continuous treatment. Further, it is preferable that the content of the ruthenium H group is set to be 20 ppm or more of the viscosity ratio of the ruthenium oxide film to the extent that the substrate is slipped, for example, 20 ppm. It may be set to, for example, 1 〇〇 ppm or more or 1,000,000 ppm or more in order to maintain a certain margin. Next, the experimental results carried out by the present inventors and the like will be described as follows. The inventors of the present invention have carried out a treatment temperature of 1,350 ° C in a state in which a support of a ruthenium oxide film is formed on the surface to support a substrate of -28 - 1326109, and in an atmosphere containing 〇 2 and N 2 . The substrate was heat treated for several hours. The experiment was carried out by varying the OH group content in the ruthenium oxide film in the range of 〇 ~ 10,000 ppm. As a result, when the OH group content was set to 0 ppm and 1 ppm, the substrate was slid, but when it was set to 20 ppm and 10 000 ppm, no slip occurred on the substrate. Therefore, it is known that the more the OH content, the slip is not likely to occur, and as long as it is at least 20 ppm or more, the sliding is almost no longer generated. The more the OH group content is, the more the viscosity of the ruthenium oxide film decreases, and the oxygen content of the OH group is at least 20 ppm, the viscosity of the 矽 φ φ film will not cause the substrate to slip. The degree of viscosity of the degree. Moreover, it has been confirmed that the OH group will enter at least several tens of ppm (e.g., 20,000 ppm to 30,000 ppm) in the tantalum oxide film. Therefore, the OH content in the tantalum oxide film is preferably set to 20 ppm or more, and practically, it is preferably from 20 ppm to several tens of ppm. Further, the OH group content may be set to 20 ppm to 10,000 ppm which has been confirmed by the experiment, and may be set to be more than 10,000 ppm or more in a range in which the viscosity is further lowered. Lu et al., in the above experiment, the water (H20) 1% and oxygen (〇2) generated by foaming pure water (H20) with nitrogen (N 2 ) were supplied to the holder. Oxidation treatment (wet oxidation) of the support surface was carried out in a reaction furnace at a temperature of 1,200 ° C under atmospheric pressure for 1 to 2 hours. Thereby, a tantalum oxide film containing 1 ppm, 20 ppm, and 10,000 ppm of ruthenium H groups is formed on the surface of the support. Relatively not containing a ruthenium oxide film of 〇H group (OH content of 0 ppm), oxygen (〇2) and nitrogen -29 - 1326109 (N2) are supplied to the reactor that has been housed in the support, and at a temperature Oxidation treatment of the surface of the supporter at 1,200 ° C under an atmospheric pressure for 1 to 2 hours to form (dry oxidation). Next, a second embodiment of a method for forming an oxide film containing an OH group in a support (including a boat or a holder) will be described below. The second embodiment is a person who adds a cold treatment to the tenth embodiment. That is, when the formation of the ITO-containing oxide film is completed, the opening and closing valves 66a and 66c are closed, and the opening and closing valve 66b is opened, and the reaction tube 42 containing the moisture gas is removed by N2, and then formed. The oxidized 0 film containing the OH group on the surface of the support was subjected to a quenching treatment. In the cold treatment, the opening and closing valve 66b or 66c is opened, and N2 gas and/or 02 gas are introduced into the reaction tube 42 to be carried out in an atmosphere containing no OH group. The cold treatment is preferably in the range of treatment temperature of 1,200 ° C to 1,4 ° ° C, and the treatment time is 0. It is implemented within the range of 5 hours to 10 hours. Further, the cold treatment may be carried out in the presence of an inert gas such as Ar or He or an atmosphere of the mixed gas in addition to the gas or the 02 gas. The above treatment in the reaction furnace was carried out, and the results are shown in Fig. 9. Lu First, in step S10, the empty holder 30 (the holder 30 on which the substrate is not mounted) is carried into the reaction furnace 40. In the next step S12, the gas containing water ' is supplied in the above-described method in the reactor 40 which has been carried into the empty supporter 30 to form an oxide film containing OH groups on the holder 30. In the next step S26, the ruthenium oxide film containing the OH group formed in the step S12 by the above method is subjected to a quenching treatment. In the next step S14, the support 30 which has formed the ruthenium oxide film containing the OH group is carried out from the reaction furnace 40 -30 - 1326109. In the next step S16, the substrate 72 is supported by a holder 30 on which a tantalum oxide film containing an OH group has been formed. In the next step S18, the holder 30 in a state in which the substrate 72 is supported is carried into the reaction furnace 40. In the next step S20, the substrate 72 is subjected to heat treatment in the above manner. In the next step S22', the support 3 that supports the heat treatment of the substrate 72 is carried out by the reaction furnace 40. After the heat treatment is completed, the substrate 72 is cooled to a specific temperature and then recovered. In the next step S24, it is determined whether the number of heat treatments for the substrate 72 (the number of times of continuous processing) has reached a certain number of times, that is, whether or not the OH group φ in the tantalum oxide film on the surface of the support is reduced to a specific (the extent of the need to supplement). In this step S24, if it is determined that the number of heat treatments for the substrate 72 has reached a certain number of times, that is, when the OH group in the ruthenium oxide film has been reduced to the extent that replenishment is required, the process returns to the initial step S10 to implement the support 30. Surface reoxidation treatment. By this, the OH group in the tantalum oxide film which is reduced by the continuous treatment can be restored. If it is determined in step S24 that the number of heat treatments for the substrate 72 has not reached a certain number of times, that is, if the OH group in the tantalum oxide film is not reduced to the extent that replenishment is required, the process returns to step S16 to process the new substrate. The heat treatment of the substrate 72 can be continued until the number of heat treatments reaches a certain number of times. Next, the experimental results performed by the inventors of the present invention are as follows. The inventors of the present invention have heat-treated the substrate at a processing temperature of 1,350 r and an atmosphere containing 〇2 and N2 in a state in which the substrate is supported by a support for forming a ruthenium oxide film containing an OH group on the surface. A few hours of experimentation. The experiment was carried out by changing the content of -31 - 1326109 OH group in the ruthenium oxide film in the range of 0 to 10,000 ppm. Further, the ruthenium oxide film containing an OH group is a reaction of supplying moisture (H20) 1% and oxygen (〇2) generated by foaming pure water (H20) with nitrogen (N2) to a storage support. In the furnace, at a temperature of 1,200 ° C, atmospheric pressure, the surface of the support is oxidized (wet oxidation) for 1 to 2 hours. As a result, after the tantalum oxide film containing an OH group of about 10,000 ppm is formed on the surface of the support, the heat treatment of the substrate is immediately applied, that is, after the oxide film containing the OH group is formed on the surface of the support, the first application is performed. When the base φ plate is heat-treated, the surface of the substrate after heat treatment by microscopic observation is also as shown in Fig. 2, and a plurality of sliding (striped patterns) are formed in the longitudinal and lateral directions. It is caused by the adhesion of the substrate to the adhesion of the ruthenium oxide film containing the OH group. There is no starting point for the occurrence of slips like scratches. On the other hand, after the ruthenium oxide film containing an OH group is formed on the surface of the support by the above method, the ruthenium oxide film containing the OH group is subjected to a quenching treatment, and after the heat treatment of the substrate is applied, the substrate after heat treatment is observed by a microscope. The results are shown in Figure 13. There is no sliding condition. Further, the cold-treating treatment of the ruthenium oxide film containing an OH group was carried out in an atmosphere containing no OH group, and the treatment temperature was set to 1,350 °C, and the treatment time was set to 10 hours. Further, in the above embodiment, the OH-oxide film (reoxidation treatment of the support) OH group formed on the surface of the support is applied to the heat treatment step of the substrate for each specific number of times of treatment. The case where the bis-32 - 1326109 plate is inserted in the reaction furnace and is carried out in the state in which the empty support is inserted is explained, but the OH group of the ruthenium oxide film may be supplemented by other timings. For example, even if the state in which the support of the substrate is supported is inserted into the reactor, that is, even if it is a step of applying a heat treatment step to the substrate, as long as it is a step which is not difficult in the heat treatment step, The OH group addition to the tantalum oxide film is carried out. The step of heat treatment is a step which is not difficult, and includes steps other than heat treatment at the highest processing temperature, that is, before the heat treatment at the highest processing temperature (substrate temperature rising step), after the heat treatment at the highest processing temperature (substrate) Cooling step) and so on. In these steps, the water of H2〇 or the like is circulated in the reaction furnace, and the OH group is added to the ruthenium oxide film formed on the supporter without affecting the heat treatment step, and after the OH group is supplemented, When the water supply of H20 or the like is stopped, and the gas of n2 or 〇2 is supplied, the cold treatment can be applied in an atmosphere containing no OH group. In addition, in the heat treatment step of the highest processing temperature, a small amount of h2o which does not cause an influence on the heat treatment step is circulated, whereby the ruthenium oxide film formed on the support can be prevented without affecting the heat treatment step. Supplement the OH group. In this case, it is also possible to carry out the steps other than the heat treatment step at the highest processing temperature, or before, for example, heat treatment at the highest processing temperature (substrate temperature rising step), or after heat treatment at the highest processing temperature (substrate cooling step) ) 'In the case of a small amount of h2o circulation. Further, a small amount of Η 2 Ο may be often circulated while the reactor is being loaded into the substrate until it is carried out. In addition, in this case, when the water supply of Η2 or 02 is stopped and the gas such as Ν2 or 02 is supplied, it is also possible to apply the cold under the dialysis of -33 - 1326109. In this way, when the support of the support substrate is inserted into the reactor, that is, during the application of the heat treatment step to the substrate, when the OH group is added to the tantalum oxide film formed on the support, it is not necessary to separately provide The yield can be improved by the support reprocessing step. Further, when the OH group is applied to the tantalum oxide film formed on the support, the same effect can be obtained by using a hydrogen-containing gas such as H2 (hydrogen) instead of H20. The heat treatment apparatus of the present invention is also applicable to the manufacturing steps of the substrate. · An example of a manufacturing step of a SIMOX (Separation by Implanted Oxygen) wafer that is a type of SOI (Silicon On Insulator) wafer is applicable to an example of the heat treatment apparatus of the present invention. as follows. First, oxygen ions are implanted into a single crystal germanium wafer by an ion implantation apparatus or the like. Thereafter, using the heat treatment apparatus of the above embodiment, the wafer implanted with oxygen ions is, for example, under an Ar ' 〇 2 atmosphere at 1,300 ° C to 1, 4 ° C, for example, at 1 Apply cold cooling at a high temperature above 3 50 °C. After the processing, a SIMOX wafer in which a SiO 2 layer (buried in a SiO 2 layer) is formed inside the wafer can be obtained. Further, in addition to SIMOX, the heat treatment apparatus of the present invention can be applied to one of the steps of the hydrogen-cold wafer fabrication step. In this case, the wafer is subjected to a cold treatment at a high temperature of 1,200 ° C or higher in a hydrogen atmosphere using the heat treatment apparatus of the present invention. Thereby, the crystal defects used as the surface layer of the wafer for manufacturing 1C (integrated circuit) can be reduced to improve the crystal integrity. Further, in addition to -34 - 1326109, the heat treatment apparatus of the present invention may be applied to one of the steps of the epitaxial wafer fabrication step. Even in the case of the high temperature quenching treatment which is carried out as one of the steps of the substrate manufacturing step as described above, the occurrence of sliding of the substrate can be prevented by using the heat treatment apparatus of the present invention. The heat treatment apparatus of the present invention is also applicable to the manufacturing steps of the semiconductor device. In particular, it is suitable for thermal oxidation at a higher temperature, such as wet oxidation, dry oxidation, hydrogen combustion oxidation (high temperature oxidation), thermal oxidation of HC1 (hydrochloric acid), or boron (B). It is preferable that impurities (dopants) such as phosphorus (P)·, arsenic (As) '锑(Sb), etc. are diffused in the thermal diffusion step of the semiconductor thin film. Even in the case of the heat treatment step which is carried out as one of the steps of manufacturing the semiconductor device as described above, the occurrence of slip can be prevented by using the heat treatment apparatus of the present invention. As described above, the present invention is characterized by the matters described in the claims, but includes the following embodiments. (1) In the heat treatment apparatus according to item 1 of the patent application, the heat treatment is carried out at a temperature of 1,000 ° C or higher. (2) In the heat treatment apparatus according to item 1 of the patent application, the oxirane film has an OH group content of 20 ppm to 10,000 ppm. (3) In the heat treatment apparatus according to the first aspect of the patent application, the OH group content in the ruthenium oxide film is 1 〇, 〇〇〇 ppm to tens of thousands ppm. (4) In the heat treatment apparatus according to item 2 of the patent application, the ruthenium oxide film is oxidized (dry oxidized) in an atmosphere containing oxygen (〇2) and not containing water (H20) -35 - 1326109 It is formed by oxidation (wet oxidation) in an atmosphere containing water (H20). (5) In the heat treatment apparatus according to the first aspect of the patent application, the holder is configured to support the plurality of substrates in a plurality of stages in a slightly horizontal state and with a gap therebetween. (6) A supporter characterized in that a substrate for supporting a substrate is formed, and at least a tantalum-containing oxide film is formed on a portion in contact with the substrate. [Industrial Applicability] The present invention is useful in a heat treatment apparatus that performs heat treatment in a state in which a substrate is supported by a support, and can be used for preventing damage or sliding of a substrate caused by contact between the substrate and the support. [Simple description of the figure] Fig. 1 is a graph showing the temperature dependence of the viscosity ratio of quartz due to the thiol content. Fig. 2 is a graph showing the temperature dependence of the thermal dissociation amount of quartz. Fig. 3 is a perspective view showing a heat treatment apparatus according to an embodiment of the present invention. Fig. 4 is a cross-sectional view showing a reaction furnace used in a heat treatment apparatus according to an embodiment of the present invention. Fig. 5 is a view showing an example of a support for use in a heat treatment apparatus according to an embodiment of the present invention, and is an example of directly supporting a substrate in a support, wherein (3) is a side view, (b) is an enlarged sectional view of the first example, ( c) is an enlarged cross-sectional view of the second example, (d) is an enlarged cross-sectional view of the third example, and (e) is an enlarged cross-sectional view of the fourth example. -36 - 1326109 Fig. 6 is a view showing an example of a support for use in a heat treatment apparatus according to an embodiment of the present invention, in which a substrate is supported by a holder via a holder, wherein (a) is a side view and (b) is a first example. The enlarged cross-sectional view 'c' is an enlarged cross-sectional view of the second example, (d) is an enlarged cross-sectional view of the third example, and (e) is an enlarged cross-sectional view of the fourth example. Fig. 7 is a view showing an apparatus for producing an H20 for use in a heat treatment apparatus according to an embodiment of the present invention, wherein (the lanthanum is an oxygen gas (〇2) and a hydrogen gas (H2) to form a H20, and (b) a genus is used to foam the pure water. Fig. 8 is a flow chart showing the control flow rate of the heat treatment apparatus according to the first embodiment of the present invention. Fig. 9 is a flow chart showing the control flow rate of the heat treatment apparatus according to the second embodiment of the present invention. It is used to illustrate the mechanism of the sliding of the substrate caused by the adhesion. Fig. 1 is a typical diagram for reducing the sliding of the substrate of the present invention. Fig. 12 is a photomicrograph showing the surface state of the substrate when the cold treatment is not performed. Fig. 13 shows a micrograph of the surface state of the substrate subjected to the cold treatment. [Main component symbol description] 10 Heat treatment device 12 Chassis 14 Closed pod container table 16 Closed pod container 1326109 18 20 22 24 Closed pod Container conveying device closed pod container shelf closed pod container opener substrate number detector 26 substrate transfer machine 28 30 32 groove aligner support 34 Upper plate 36 Lower plate 38 Pillar 40 Reactor 42 44 46 48 Reaction tube sealing cover uniform heating tube heater 50 52 54 56 58 60, 64b, 92 62, 84 64a Thermocouple inlet tube Exhaust pipe gas supply system H20 Device N2 gas source 〇2 gas source H2o supply line 1326109 64a, 64b, 64c supply line 66a, 66b, 66c, 88a, 88b '96 open and close valve 68a, 68b, 68c, 90a, 90b, 98 mass flow controller 70 support piece 72 substrate 74 tantalum oxide film 76 coating layer 80 holder 82 h2 gas source 86 external combustion device 94 pure water container 100, 100 protrusion 102 film 102