200932965 六、發明說明： 【發明所屬之技術領域] 本發明關於半導體材料所用的矽之單晶成長裝置及單 晶成長方法。 【先前技術】 以往至今’作爲半導體用的矽單晶成長方法，廣泛使 用査克洛斯基法（CZ法）。特別地，該CZ法在進行大口徑 結晶的成長時優異’被廣泛使用。然而，隨著量産的進展 ’希望更提高結晶收率，而且從省資源.節能的觀點來看 ，必須提高消耗很多電力的CZ法之結晶收率。 例如’於矽單晶拉拔裝置、矽單晶拉拔方法的專利文 獻1中’記載結晶良率或運轉率高的單晶拉拔裝置或矽單 晶拉拔方法。記載原料多晶供給裝置。 又’於矽單晶的製造方法之專利文獻2中，記載施加 磁場而抑制石英坩堝內表面的劣化，延長坩堝的壽命，防 止坦渦的劣化所造成的錯位（dislocation)之方法。 另外’於與單晶的成長方法及其實施所使用的裝置有 關的專利文獻3中，記載將固體層與熔融層的界面保持平 坦’使電阻率成爲均一，以高良率得到單晶的方法。 [專利文獻1] 特開2004-338978 [專利文獻2] 特開2000-247788 [專利文獻3] 特開平09-208374 於前述習知例中，例如於專利文獻1中，作爲結晶良 率或運轉率高的單晶拉拔裝置或矽單晶拉拔方法，雖然有 200932965 記載原料的原料多晶烘給裝置，但對於結晶會多晶化或異 物的落下所致的攣晶之問題等的對策係沒有書寫，於專利 文獻2中’雖然有記載在單晶拉拔中施加磁場，而抑制石 英坦摘內表面的劣化，延長坩堝的壽命，防止坩堝的劣化 所造成的錯位之方法，但是沒有記載防止爐內氣氛所造成 的錯位之方法等，沒有解決基本的錯位之問題。 又’專利文獻3中雖然有記載電阻率的成長方向分布 或良率提高方法，但對於太陽電池用結晶等電阻率幅度大 ® 的製品，並沒有對策。 如此’在提高結晶良率方面，重要的是首先要求對於 成長結晶的多晶化或錯位之對策。 【發明內容】 發明所欲解決的問顯 本發明之目的爲例如在單晶成長法之中，於用CZ法使 矽單晶成長的過程，改善成長結晶的多晶化比率。又，同 時地’目的爲解決以下問題：於爐的開放時，爐內零件吸 附水分’其影響爲碳零件的消耗變激烈，爐的經時變化之 影響，或碳混入到結晶中，熔融矽與碳反應，生成SiC， 其混入成長中的結晶而有錯位等的問題。 解決問顆的丰段 本發明爲了達成上述目的，提供可保持高真空的爐體 ’及防止水分吸附到爐內零件，使殘留吸附物化學地積極 反應、無害化、真空排氣，防止成長中的矽單晶之錯位， 以高良率得到高品質結晶的單晶成長裝置及單晶成長方法 200932965 申請專利範圍第1項中記載單晶成長方法及單晶成長 裝置，其特徵爲在常壓、減壓或真空環境下進行結晶成長 的結晶成長爐，在具有用於短時間提高真空度的真空排氣 裝置以及可維持爐內極限真空度的真空密封材之結晶成長 爐中，具備減低爐內零件或原料結晶的水分吸附之預備過 熱裝置，邊真空排氣邊使初期真空到達度成爲1(Τ4托以上 。即，爲了減低真空延遲，在凸緣的精度或真空密封材料 ❹ 或例如在轉軸的密封中，使用磁性流體密封等等亦有效， 謀求真空洩漏的減低後，達成水分吸附的減低》 申請專利範圍第2項中記載如申請專利範圍第1項之 單晶成長方法及單晶成長裝置，其中爲了在爐的開放時不 在室內壁發生結露或吸附，具備將爐的內壁保持在室溫以 上的機構。即，通常冷卻水大多變成比室溫低，會在構成 爐的室內壁產生結露。但是該室若爲室溫以上，則可減低 吸附。 © 申請專利範圍第3項中記載如申請專利範圍第2項之 單晶成長方法及單晶成長裝置，其中將溫水供應給爐室的 水冷夾套內部，以將爐的內壁保持在室溫以上。具體地， 藉由溫度控制系統，在爐的拆卸中或在準備步驟中爐的內 面暴露於大氣時，爲了在室的內壁不產生結露，供應溫水 申請專利範圍第4項中記載如申請專利範圍第1至3 項之單晶成長方法及單晶成長裝置，其中在關閉爐，進行 200932965 真空抽吸時，使水冷夾套內部的溫度進一步上升，進行真 空抽吸。 於與真空抽吸的同時，亦比大氣暴露中還高地將爐壁 升溫，進行吸附水分的去除。 申請專利範圍第5項中記載如申請專利範圍第1至4 項之單晶成長方法及單晶成長裝置，其中使經加熱的惰性 沖洗氣體流到爐內而去除吸附水分。 即，去除氣體通路的吸附水分。 申請專利範圍第6項中記載如申請專利範圍第1至5 項之單晶成長方法及單晶成長裝置，其中藉由預備加熱裝 置將爐內零件加熱以去除吸附水分。進行保溫筒的預備過 熱。 申請專利範圍第7項中記載如申請專利範圍第1至6 項之單晶成長方法及單晶成長裝置，其中惰性供給氣體的 加熱控制、水冷夾套內的溫水溫度控制、爐內補助加熱裝 置及主加熱源的加熱器係各自按照真空度水平來控制。亦 含有主加熱器，進行升溫、吸附水分的除去。 申請專利範圍第8項中記載單晶成長方法及單晶成長 裝置，其特徵爲在供應給單晶成長爐的惰性氣體供給時， 於惰性氣體中混合0.01至3%的甲矽烷氣體或矽烷氣體， 供應給爐內。於使用微量的甲矽烷氣體或矽烷氣體時，依 照下述的化學反應式1或式2，爐內零件或矽原料的吸附 水分轉化成其它物質，可有效地去除單晶成長爐內氣氛的 水分。 200932965200932965 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a single crystal growth apparatus and a single crystal growth method for a semiconductor material. [Prior Art] The Chuckowski method (CZ method) is widely used as a method for growing a germanium single crystal for semiconductors. In particular, the CZ method is excellent in the growth of large-diameter crystals. However, with the progress of mass production, it is desired to increase the crystallization yield more, and from the viewpoint of saving resources and energy saving, it is necessary to increase the crystallization yield of the CZ method which consumes a lot of electric power. For example, 'Patent Document 1 of a bismuth single crystal pulling device and a bismuth single crystal pulling method' describes a single crystal pulling device or a singular crystal pulling method having a high crystallization yield or a high operating rate. A raw material polycrystal supply device is described. Further, Patent Document 2, which is a method for producing a single crystal, describes a method of applying a magnetic field to suppress deterioration of the inner surface of the quartz crucible, prolonging the life of the crucible, and preventing dislocation caused by deterioration of the vane vortex. Further, in Patent Document 3 relating to a method for growing a single crystal and an apparatus for performing the same, a method of maintaining a uniformity in the resistivity by making the interface between the solid layer and the molten layer uniform, and obtaining a single crystal at a high yield is described. [Patent Document 1] JP-A-2004-338978 [Patent Document 2] JP-A-2000-247788 [Patent Document 3] JP-A-09-208374 In the aforementioned conventional example, for example, Patent Document 1, as a crystal yield or operation A high-rate single crystal drawing device or a ruthenium single crystal drawing method, although there is a raw material polycrystalline baking device for raw materials described in 200932965, the problem of twinning due to crystal crystallization or falling of foreign matter is considered. In the case of the patent document 2, there is a method of applying a magnetic field in the drawing of a single crystal, suppressing the deterioration of the inner surface of the quartz stripping, prolonging the life of the crucible, and preventing the misalignment caused by the deterioration of the crucible. A method of preventing misalignment caused by the atmosphere in the furnace, etc., does not solve the problem of basic misalignment. Further, Patent Document 3 describes a growth direction distribution of the resistivity or a method for improving the yield. However, there is no countermeasure for a product having a large resistivity such as crystal for solar cells. Thus, in terms of improving the crystallization yield, it is important to first require countermeasures against polycrystallization or dislocation of the grown crystal. SUMMARY OF THE INVENTION The object of the present invention is to improve the polycrystallization ratio of a grown crystal in a process of growing a germanium single crystal by a CZ method, for example, in a single crystal growth method. At the same time, the purpose of the problem is to solve the following problem: when the furnace is opened, the parts in the furnace absorb moisture. The effect is that the consumption of the carbon parts becomes intense, the influence of the time change of the furnace, or the carbon is mixed into the crystal, and the melting is performed. It reacts with carbon to form SiC, which is mixed with a growing crystal and has a problem of dislocation. In order to achieve the above object, the present invention provides a furnace body capable of maintaining a high vacuum and prevents moisture from being adsorbed into the furnace parts, so that the residual adsorbate is chemically positively reacted, harmless, and evacuated to prevent growth. A single crystal growth apparatus and a single crystal growth method for obtaining high quality crystals at a high yield, and a single crystal growth method, and a single crystal growth apparatus, characterized in that at normal pressure, A crystal growth furnace that performs crystal growth under reduced pressure or a vacuum atmosphere, and has a reduction in the furnace in a crystal growth furnace having a vacuum evacuation device for increasing the degree of vacuum for a short period of time and a vacuum seal member capable of maintaining the ultimate vacuum degree in the furnace. The preliminary superheating device for moisture adsorption of the crystal of the part or the raw material, the initial vacuum reaching degree is 1 (Τ4 Torr or more) while vacuum evacuating. That is, in order to reduce the vacuum delay, the precision of the flange or the vacuum sealing material 或 or, for example, the rotating shaft In the sealing, the use of magnetic fluid seals, etc. is also effective, and after the reduction of vacuum leakage is achieved, the reduction of moisture absorption is achieved. The single crystal growth method and the single crystal growth apparatus according to claim 1, wherein the inner wall of the furnace is kept in the chamber in order to prevent condensation or adsorption from occurring on the inner wall when the furnace is opened. In other words, the cooling water is usually lower than room temperature, and dew condensation occurs in the inner wall of the furnace. However, if the chamber is at room temperature or higher, the adsorption can be reduced. © Patent Application No. 3 The single crystal growth method and the single crystal growth apparatus of claim 2, wherein warm water is supplied to the inside of the water-cooled jacket of the furnace chamber to maintain the inner wall of the furnace above room temperature. Specifically, by temperature In the control system, in the disassembly of the furnace or in the preparation step, when the inner surface of the furnace is exposed to the atmosphere, in order to prevent condensation from occurring on the inner wall of the chamber, the supply of warm water is disclosed in item 4 of the patent application scope as claimed in claim 4 A three-dimensional single crystal growth method and a single crystal growth apparatus in which the temperature inside the water-cooled jacket is further raised and vacuum suction is performed when the vacuum is sucked at 200932965 in the furnace. At the same time as the suction, the furnace wall is heated higher than the atmospheric exposure to remove the adsorbed water. The single crystal growth method and the single crystal growth device according to the scope of the patent application No. 1 to 4 are described in the fifth application of the patent application. , wherein the heated inert gas is flowed into the furnace to remove the adsorbed moisture. That is, the adsorbed moisture of the gas passage is removed. The method for growing a single crystal according to the scope of claim 1 and 5 is described in A single crystal growth apparatus in which a furnace heating part is used to heat the inside of the furnace to remove the adsorbed moisture. The preheating cylinder is preheated. The single crystal growth method as described in claim 7 of the patent application range 1 to 6 is described. And a single crystal growth apparatus in which the heating control of the inert supply gas, the warm water temperature control in the water-cooled jacket, the furnace auxiliary heating device, and the heater of the main heating source are each controlled according to the degree of vacuum. The main heater is also included to carry out the temperature rise and the removal of moisture. Patent Document No. 8 discloses a single crystal growth method and a single crystal growth apparatus characterized in that 0.01 to 3% of a gas or a gas of decane is mixed in an inert gas when supplied to an inert gas supplied to a single crystal growth furnace. , supplied to the furnace. When a trace amount of methanol or gas is used, according to the following chemical reaction formula 1 or formula 2, the moisture adsorbed in the furnace or the raw material of the crucible is converted into other substances, and the moisture in the atmosphere of the single crystal growth furnace can be effectively removed. . 200932965
SiH4 + 2H20 = Si〇2 + 4H2 -1 S1CIH3 + 2H2〇 = Si02 + HC1+ 3H2 -2 依照本發明，由於確實進行真空水平的提高、短時間 內可達到高真空度、及吸附物質的水分等之去除，可確實 地防止單晶成長時的錯位或多晶化，故可謀求結晶良率的 提高。 發明的效果 依照本發明，由於在單晶拉拔的開始前，去除爐內所 殘留的空氣、水分或烴化合物，在達到矽的溶解步驟之前 ，可容易去除與矽容易反應的此等物質，故妨礙單晶成長 的矽之碳化物、氧化物等的異物之生成係變沒有，因此得 到能改善結晶成長的良率之效果。又，以往在爐內的碳零 件有水分時，發生烴化、形狀劣化。又，由於殘留氧而二 氧化碳化，有縮短碳零件壽命的不良狀況，但依照本發明 ，藉由去除殘留氣體或殘留水分，而得到能實現長壽命化 的效果。又，由於可減少成長中的結晶中碳混入的量，故 在其後的晶圓製程之熱處理時，可減低所產生的碳所致的 氧析出。 再者，依照本發明，更由於爐內零件不會劣化，可抑 制以往製程條件的經時變化，故得到能實現品質的安定化 之效果。 【實施方式】 實施發明的最佳形熊 以下，以實施例爲基礎來說明實施本發明的最佳形態 200932965 【實施例】 藉由第1圖至第4圖來說明本發明的實施例。 第1圖係本發明中的單晶成長裝置之模型圖。 圖中，真空室1係成爲水冷夾套構造，遮蔽爐內加熱 時的熱，藉由將水冷夾套內的冷卻水進行冷卻的冷卻水結 合配管2，進行處理、冷卻。作爲環境氣體，使用氬氣或 氦氣等的惰性氣體。前述惰性氣體係經由氣體流量計3供 ❹應給爐內。 以往，惰性氣體係大略常溫供給，但於本發明中，經 由升溫熱交換器4，經過氣體閥5控制所供給的氣體，而 供應給爐內。 主控制裝置係管理單晶拉拔步驟的全部區間，在拉拔 準備步驟的室內壁暴露於空氣中的狀況下，代替冷卻水， 經由溫水閥7，將升溫熱交換器9所溫熱的溫水供應給水 _ 冷夾套內。藉由溫度計6來監視該溫水的溫度，與室溫比 〇 較下，以成爲5 °c以上的溫度之方式，將溫水加熱。將爐 關閉’完全置換空氣或水分後，一旦進入將原料多晶溶解 的步驟，則打開冷水閥8，藉由泵21從冷卻水槽14抽取 冷卻水，使水通往室。又，一般地使用複數的爐之冷卻用 循環水的情況，於爐的運轉時，可再利用溫水化的來自爐 的冷卻排水之溫度高者。 爐的真空排氣係經由真空排氣閥10，藉由真空泵11來 真空排氣’但邊保持減壓狀態，邊進行結晶成長時，以真 200932965 空排氣閥ίο當作壓力調整閥使用，進行壓 必要的減壓狀態。閥12係用於控制來置換秦 換氣體供給之控制閥。例如，於以惰性氣體 ，以乾燥氮氣體進行氣體置換，可進行與爐 留氧之置換。進行爐之冷卻的冷卻水路徑， 槽1 4到冷水閥8，溫度計6所計測的冷卻水 室1，冷卻水結合配管2係從上部的室到主 到下部室，再回到冷卻水槽1 4。冷卻水槽1 升，則藉由急冷器等的熱交換器來冷卻，以 的溫度。 爐係在大氣開放的爐之清除或原料進給 冷水閥8，打開溫水閥7，從泵22經由升溫 使比室溫高的溫度之溫水流到室中，以便在 結露。 第2圖係本發明中的保溫筒之預備過熱 〇 圖中，保溫環15係使用於遮蔽來自加熱 爐內於高溫。於本發明中，藉由來自爐內零 源16的電力，加熱預備加熱器18，促進吸 。於保溫環15爲導電性碳纖維時，絕緣材】 絕緣材。 第3圖係本發明中的單晶成長裝置之氣 〇 作爲惰性氣體，使用氦氣或氬氣，但此 力調整，成爲 [體源13的置 進行置換之前 內的水分或殘 係經由冷卻水 係供應給真空 室，然後供應 4的水溫若上 保持一定範圍 步驟中，關閉 熱交換器9， 室內壁不發生 機能的模型圖 器的熱，保持 件預備加熱電 附水分的置換 I 7係不通電的 體供給路徑圖 處顯示氣氣使 -10- 200932965 用例。氬氣通常係邊將液態氬氣化邊使用，但供應給的真 空室1的氬氣係由氬氣閥19來供給。所供給的氬氣之露 點爲-8〇°c程度，不含有水分，爐內零件放置大氣中會吸附 某一程度的水分，因此所供給的氬氣係先通過升溫熱交換 器4而加熱，由氣體閥5供應給真空室1。照原樣的狀態 ，若與習知法比較，亦大幅改善吸附水分量的置換量，由 甲矽烷氣體閥20添加0.01%至3%左右的甲矽烷氣體（SiH4) ，藉由爐內零件預備加熱裝置18來加熱，若過熱到100 °C 以上，則可急劇地將水分排出。 第4圖係本發明中的單晶成長流程圖。 圖中，爐的自動控制單元係計測每一步驟的環境溫度 ，進行控制以使得真空室1中流到水冷夾套內部的冷卻水 溫度不在環境溫度以下。即，於冷卻水溫度比室溫低時， 在真空室1的內壁有發生結露的可能性。因此，爐壁的自 動控制單元係用冷卻水的升溫控制以使高於室溫（STEP-1 ) 〇 接著’將爐大氣開放，將所準備的原材料投入下一個 結晶成長。於結晶成長完成時，首先取出成長結晶。然後 ’通往爐內清除·原料進給作業。此處，結晶成長時所生 成的粉體或堆積物係從爐內去除。於此等作業之間、相當 多的時間及原材料的倂入作業時間之間，室內壁面係暴露 在大氣中，而發生水分吸附到室壁。 然後’進行爐的組裝，於進行真空抽吸的時間點，對 前述室壁的水分吸附係成爲快速達到指定真空度的弊病。 -11- 200932965 ' (STEP-2)。 因此，將爐大氣開放時，必須進行室爐壁面的升溫， 以謀求水分吸附的減低。 接著，將爐組裝’將爐密閉，開始真空粗抽吸。 (STEP-3) ° 再者，爲了快速去除前述室爐壁面的吸附水分，進一 步提高冷卻水溫。又，於使爐內成爲減壓狀態後，使置換 氣體流動，而且重複進行真空抽吸的動作，提高置換率。 β 再者，將高溫的置換氣體供應給爐內，以氣體置換爐 內零件表面的吸附水分，進行排氣，同時進行真空抽吸以 便快速達到目標設定真空度（STEP-4)。 在已進行置換氣體的階段，進入爐內零件預備加熱步 驟（STEP-5)。 例如’在爐內進行多孔質的爐內保溫材之保溫筒的預 備過熱。從l〇〇C起升溫到200°C，而且藉由惰性氣體的 供給或已升溫的惰性氣體之供給，進行水分或殘留氣體的 〇置換。 於殘留氣體的置換完成之時間點，停止惰性氣體的供 給，藉由真空抽吸’確認極限真空度。於極限真空度成爲 10E - 4托以下時’當作沒有真空洩漏者，轉移到結晶成長 製程（STEP-6)。 接著，停止爐內零件的預備加熱（STEP-7)。 預備加熱裝置之目的基本上爲藉由多孔質的爐內保溫 材之升溫來促進吸附物的蒸發，雖然在單晶成長程序中停 -12- 200932965 止，但視情況而定’亦可挪用於爐內的溫度分布改善。 接著，轉移到單晶成長程序（STEP-8)。 於單晶成長程序中’首先進行多晶原料的溶解、晶種 的成長’接著進行到目的之單晶成長步驟，若單晶成長程 序完成’則經過冷卻步驟，進行爐的拆卸 '結晶取出，成 爲由最初狀態起的重複作業。 於未順利地進行真空步驟時，進行真空密封保養作業 (STEP-9)。 於真空的保持狀態差的所謂真空爐有洩漏時，進行真 空密封材料的交換或凸緣的接合部分之夾緊等的保養作業 。於有極微量的洩漏時，由於惰性氣體中所添加的甲矽烷 氣體（SiHO與空氣或水分反應，排出爐外，故有效地提高 結晶的良率。 於本發明中，具有如此地改善單晶良率之優點。 於本發明的說明中，雖然對矽單晶作記載，但本發明 ❹ 中去除水分或氧等的吸附物之手法當然可適用於矽多晶或 其它無機單晶·多晶的製造時之品質改良、良率改善。又 ’除了結晶製造以外，於藉由真空蒸鍍法、化學氣相成長 法、分子線外延法等來形成無機材質或有機材質薄膜時， 亦使用真空室來進行製造，但於此情況下，亦可採用本發 明於去除裝置內部的吸附氣體或水分，有效地進行品質改 良或良率改善。 【圖式簡單說明】 第1圖係顯示本發明中的單晶成長裝置之模型圖。 -13- 200932965 第2圖係顯示本發明中的保溫筒之預備過熱機能的模 型圖。 第3圖係顯示本發明中的單晶成長裝置之氣體供給路 徑圖。 第4圖係顯示本發明中的單晶成長流程圖。 【主要元件符號說明】SiH4 + 2H20 = Si〇2 + 4H2 -1 S1CIH3 + 2H2 〇 = Si02 + HC1 + 3H2 -2 According to the present invention, since the vacuum level is actually increased, the high vacuum degree and the moisture of the adsorbed substance can be achieved in a short time. The removal can reliably prevent misalignment or polycrystallization during growth of the single crystal, so that the crystal yield can be improved. Advantageous Effects of Invention According to the present invention, since air, moisture or a hydrocarbon compound remaining in the furnace is removed before the start of single crystal pulling, such a substance which is easily reacted with hydrazine can be easily removed before the dissolution step of hydrazine is achieved. Therefore, the generation of foreign matter such as carbides and oxides which hinder the growth of the single crystal is not changed, and therefore an effect of improving the yield of crystal growth is obtained. Further, in the past, when there is moisture in the carbon parts in the furnace, hydrocarbonization and shape deterioration occur. Further, carbon dioxide is formed by residual oxygen, which may cause a problem of shortening the life of the carbon component. However, according to the present invention, the effect of prolonging the life can be obtained by removing residual gas or residual moisture. Further, since the amount of carbon mixed in the growing crystal can be reduced, the oxygen deposition by the generated carbon can be reduced during the subsequent heat treatment of the wafer process. Further, according to the present invention, since the components in the furnace are not deteriorated, the temporal change of the conventional process conditions can be suppressed, so that the effect of achieving the stability of the quality can be obtained. BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the invention will be described below on the basis of an embodiment. 200932965 [Embodiment] An embodiment of the present invention will be described with reference to Figs. 1 to 4 . Fig. 1 is a model diagram of a single crystal growth apparatus in the present invention. In the drawing, the vacuum chamber 1 is a water-cooled jacket structure, and the heat during heating in the furnace is shielded, and the cooling water is cooled by the cooling water in the water-cooled jacket to form a pipe 2 for processing and cooling. As the ambient gas, an inert gas such as argon gas or helium gas is used. The inert gas system described above is supplied to the furnace via a gas flow meter 3. Conventionally, the inert gas system is supplied at a normal temperature. However, in the present invention, the supplied gas is supplied to the furnace via the gas valve 5 via the temperature rising heat exchanger 4. The main control device manages all the sections of the single crystal pulling step, and in the condition that the inner wall of the drawing preparation step is exposed to the air, instead of the cooling water, the warming heat exchanger 9 is warmed via the warm water valve 7. The warm water is supplied to the water _ cold jacket. The temperature of the warm water is monitored by the thermometer 6, and the warm water is heated to a temperature of 5 ° C or more as compared with the room temperature ratio 〇. After the furnace is turned off to completely replace the air or moisture, once the step of dissolving the polycrystalline material is entered, the cold water valve 8 is opened, and the cooling water is extracted from the cooling water tank 14 by the pump 21 to allow the water to pass to the chamber. Further, in the case where a plurality of circulating water for cooling of the furnace is generally used, the temperature of the cooling water from the furnace which is warmed by the temperature can be reused during the operation of the furnace. The vacuum exhaust of the furnace is evacuated by the vacuum pump 11 through the vacuum exhaust valve 10, but while the crystal is grown while maintaining the reduced pressure state, the true 200932965 air vent valve is used as a pressure regulating valve. The pressure reduction state necessary for the pressure is performed. Valve 12 is used to control the control valve to replace the gas supply. For example, gas replacement with a nitrogen gas in an inert gas can be carried out in place of oxygen retention in the furnace. The cooling water path for cooling the furnace, the tank 14 to the cold water valve 8, the cooling water chamber 1 measured by the thermometer 6, and the cooling water combined piping 2 from the upper chamber to the main to the lower chamber, and then returned to the cooling water tank 1 4 . When the water tank is cooled by 1 liter, it is cooled by a heat exchanger such as a chiller. The furnace is purged from the furnace in which the atmosphere is open or the raw material is fed to the cold water valve 8, and the warm water valve 7 is opened, and warm water of a temperature higher than room temperature is supplied from the pump 22 to the chamber through condensation to allow condensation. Fig. 2 is a preliminary superheating of the heat insulating cylinder in the present invention. In the figure, the heat insulating ring 15 is used to shield the high temperature from the inside of the heating furnace. In the present invention, the preliminary heater 18 is heated by electric power from the zero source in the furnace to promote suction. When the heat insulating ring 15 is a conductive carbon fiber, the insulating material is an insulating material. In the third embodiment, the gas in the single crystal growth apparatus of the present invention is an inert gas, and helium gas or argon gas is used. However, this force is adjusted so that the water or the residual water before the replacement of the body source 13 is passed through the cooling water. Is supplied to the vacuum chamber, and then if the water temperature of the supply 4 is maintained in a certain range, the heat exchanger 9 is turned off, the heat of the model image of the function wall does not occur, and the replacement part of the holder is heated and attached with water. The gas supply is shown in the non-energized body supply path diagram to make the -10-200932965 use case. The argon gas is usually used while gasifying the liquid argon, but the argon gas supplied to the vacuum chamber 1 is supplied from the argon gas valve 19. The argon gas supplied has a dew point of about -8 〇 °c, does not contain water, and the inside of the furnace is placed in the atmosphere to adsorb a certain amount of moisture. Therefore, the supplied argon gas is first heated by the temperature rising heat exchanger 4. It is supplied to the vacuum chamber 1 by the gas valve 5. In the original state, if compared with the conventional method, the amount of substitution of the adsorbed water content is also greatly improved, and 0.01% to 3% of the methanol gas (SiH4) is added from the methane gas valve 20, and the parts are heated by the furnace. The device 18 is heated, and if it is overheated to 100 ° C or higher, the water can be discharged abruptly. Fig. 4 is a flow chart showing the growth of a single crystal in the present invention. In the figure, the automatic control unit of the furnace measures the ambient temperature of each step, and controls so that the temperature of the cooling water flowing into the water-cooled jacket inside the vacuum chamber 1 is not below the ambient temperature. That is, when the temperature of the cooling water is lower than room temperature, dew condensation may occur on the inner wall of the vacuum chamber 1. Therefore, the automatic control unit of the furnace wall is controlled by the temperature rise of the cooling water so as to be higher than the room temperature (STEP-1) 〇 Next, the furnace atmosphere is opened, and the prepared raw materials are put into the next crystal growth. When the crystal growth is completed, the grown crystals are first taken out. Then 'to the furnace to clear the raw material feed operation. Here, the powder or deposit generated during the growth of the crystal is removed from the furnace. Between these operations, a considerable amount of time and the time of entry of the raw materials, the indoor wall is exposed to the atmosphere, and moisture is adsorbed to the chamber wall. Then, the assembly of the furnace was carried out, and at the time of vacuum suction, the moisture adsorption system to the chamber wall quickly became a disadvantage of the specified degree of vacuum. -11- 200932965 ' (STEP-2). Therefore, when the furnace atmosphere is opened, it is necessary to raise the temperature of the chamber wall surface in order to reduce the moisture adsorption. Next, the furnace was assembled to seal the furnace and start vacuum suction. (STEP-3) ° Furthermore, in order to quickly remove the adsorbed moisture from the wall surface of the chamber, the cooling water temperature is further increased. Further, after the inside of the furnace is depressurized, the replacement gas is caused to flow, and the operation of vacuum suction is repeated to increase the replacement rate. Further, a high-temperature replacement gas is supplied to the furnace, and the moisture adsorbed on the surface of the furnace is replaced by a gas, and the vacuum is suctioned to quickly reach the target set vacuum (STEP-4). At the stage where the replacement gas has been carried out, the furnace is ready for the heating step (STEP-5). For example, the preheating of the heat-insulating cylinder of the porous heat insulating material in the furnace is performed. The temperature is raised from 200 ° C to 200 ° C, and the moisture or the residual gas is replaced by a supply of an inert gas or a supply of an inert gas which has been heated. At the point of completion of the replacement of the residual gas, the supply of the inert gas was stopped, and the ultimate vacuum was confirmed by vacuum suction. When the ultimate vacuum is 10E - 4 Torr or less, it is transferred to the crystallization growth process (STEP-6) as if there is no vacuum leakage. Next, the preliminary heating of the parts in the furnace is stopped (STEP-7). The purpose of the preliminary heating device is basically to promote the evaporation of the adsorbate by the temperature rise of the porous furnace heat insulating material, although it is stopped in the single crystal growth process, but it may be used as the case may be. The temperature distribution in the furnace is improved. Next, transfer to the single crystal growth program (STEP-8). In the single crystal growth process, 'the first dissolution of the polycrystalline raw material and the growth of the seed crystal are carried out', and then the single crystal growth step is carried out, and if the single crystal growth process is completed, the cooling step is performed, and the furnace is removed and the crystal is taken out. It becomes a repeat job from the initial state. Vacuum seal maintenance work (STEP-9) is performed when the vacuum step is not performed smoothly. In the case where there is a leak in the vacuum furnace in which the holding state of the vacuum is poor, maintenance work such as exchange of the vacuum sealing material or clamping of the joint portion of the flange is performed. In the case of a very small amount of leakage, since the methane gas (SiHO) which is added to the inert gas reacts with air or moisture and is discharged outside the furnace, the yield of the crystal is effectively improved. In the present invention, the single crystal is improved as described above. Advantages of yield. In the description of the present invention, although the single crystal is described, the method of removing adsorbate such as moisture or oxygen in the present invention is of course applicable to ruthenium polycrystal or other inorganic single crystal/polycrystal. In the manufacturing process, the quality is improved and the yield is improved. In addition to the crystal production, when a film of an inorganic material or an organic material is formed by a vacuum deposition method, a chemical vapor phase growth method, a molecular line epitaxy method or the like, a vacuum is also used. In this case, the present invention can also be used to remove the adsorbed gas or moisture inside the device, thereby effectively improving the quality or improving the yield. [Fig. 1] Fig. 1 shows the present invention. Model diagram of a single crystal growth apparatus. -13- 200932965 Fig. 2 is a model diagram showing the preliminary superheating function of the heat insulating cylinder of the present invention. Fig. 3 is a view showing the single sheet in the present invention. Gas supply path growth apparatus of FIG. 4. FIG flowchart based crystal growth in the present invention. The main element REFERENCE NUMERALS
1 真空室 2 3 冷卻水結合配管 氣體流量計 4 升溫熱交換器 5 氣體閥 6 溫度計 7 溫水閥 8 冷水閥 9 升溫熱交換器 10 真空排氣閥 11 真空泵 12 閥 13 置換氣體源 14 冷卻水槽 15 保溫環 16 爐內零件預備加熱電源 17 絕緣材 18 預備加熱器 -14- 200932965 19 氬氣閥 20 甲矽烷氣體閥 2 1 泵 22 溫水泵1 Vacuum chamber 2 3 Cooling water combined with piping gas flow meter 4 Heating heat exchanger 5 Gas valve 6 Thermometer 7 Warm water valve 8 Cold water valve 9 Heat exchanger 10 Vacuum exhaust valve 11 Vacuum pump 12 Valve 13 Replacement gas source 14 Cooling water tank 15 Insulation ring 16 In-furnace parts Preheating power supply 17 Insulating material 18 Preheating heater-14- 200932965 19 Argon gas valve 20 Formane gas valve 2 1 Pump 22 Warm water pump