TWI377174B - Apparatus for adsorbing metal and method for the same - Google Patents
Apparatus for adsorbing metal and method for the same Download PDFInfo
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- TWI377174B TWI377174B TW096150243A TW96150243A TWI377174B TW I377174 B TWI377174 B TW I377174B TW 096150243 A TW096150243 A TW 096150243A TW 96150243 A TW96150243 A TW 96150243A TW I377174 B TWI377174 B TW I377174B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45514—Mixing in close vicinity to the substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45559—Diffusion of reactive gas to substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Recrystallisation Techniques (AREA)
- Thin Film Transistor (AREA)
- Electroluminescent Light Sources (AREA)
Description
1377174 九、發明說明： 【發明所屬之技術領域】 技術領域1377174 IX. Description of the invention: [Technical field to which the invention pertains] Technical field
本發明係有關於一種適用於液晶顯示器（Liquid Cryst 5 al Display ; LCD)、有機發光顯示器（Organic Light Emit ting Display ; OLED )等所使用之薄膜電晶體（Thin Film Transistor ; TFT )之.多晶石夕薄膜之製造，更詳而言之，其 係有關於一種形成TFT多結矽薄膜時，將金屬或金屬有機化 合物吸附至非晶矽之薄膜上，以降低結晶化溫度，提高結 10 晶化之特性的裝置及吸附方法。 【先前技術】 背景技術- TFT大體分為非晶矽TFT及多結矽TFT。TFT之特性以 電子移動率之值評價。由於非晶矽TFT之電子移動率大約為 15 lcm2/Vs，多結矽TFT之電子移動率大約為l〇〇cm2/Vs左右，The present invention relates to a thin film transistor (TFT) suitable for use in a liquid crystal display (LCD), an organic light emitting display (OLED), or the like. The manufacture of Shixi film, in more detail, relates to a method of adsorbing a metal or a metal organic compound onto a film of amorphous germanium when forming a TFT multi-junction film to reduce the crystallization temperature and increase the junction crystal 10 Device and adsorption method. [Prior Art] BACKGROUND OF THE INVENTION TFTs are roughly classified into amorphous germanium TFTs and multijunction germanium TFTs. The characteristics of the TFT are evaluated by the value of the electron mobility. Since the electron mobility of the amorphous germanium TFT is about 15 lcm2/Vs, the electron mobility of the multi-junction TFT is about l〇〇cm2/Vs.
故高性能之LCD宜採用多晶矽TFT。多晶矽TFT係於玻璃或 石英等透明基板蒸鍍非晶矽，使其多結晶化後，形成閘極 氧化膜及閘極電極，將摻雜劑注入至源極及汲極後，形成 絕緣層而製成。 20 製造多晶矽TFT時，主要之程序係使非晶矽之薄膜多 結晶化之步驟。特別是以降低結晶化溫度為佳。若結晶化 溫度非常南’製造TFT時，便無法使用炫融點低之玻璃基 板’而有TFT之製造成本大幅上升之問題點。考慮使用此種 玻璃基板之可能性’最近提出如下述可在低溫且短時間内 5 也成多結晶薄膜之多種步驟β 準刀子缉射結晶化（Excimer Laser Crystallization )法 係利用瞬間照射雷射，熔融非晶矽，使其再結晶化之方法， 可防止因急速加熱而造成之玻璃基板之損傷，具有多晶矽 之結晶性優異之優點。然而有再現性降低，裝備結構複雜 之缺點。 急速熱處理法係利用IR燈泡，將非晶矽急速熱處理之 方法’具有生產速度快，生產成本低廉之優點，伹具有因 急迷加熱造成之熱撞擊及玻璃基板之變形產生等之缺點。 10 金屬誘發結晶化（Metal Induced Crystallization ; MIC ) 法係將Ni、Cu、A1等金屬觸媒塗布至非晶矽，在低溫結晶 化之方法’具有可在低溫結晶化之優點，但具有漏電流因 '舌化區域所含之相當量之金屬而大幅增加之缺點。 金屬誘發側向結晶化（Metal Induced Lateral Crystall 13 · » 1Zatlon ; MILC)法係為防止以MIC方法產生之金屬污染而 開發者，於源極/汲極區域蒸鍍金屬觸媒，而優先誘發MIc， 將此作為晶種’使多結晶矽於閘極下部之活化區域側向成 長之方法。MILC法具有在側向成長之結晶化區域中金屬污 染較MIC法少之優點，但仍留有漏電流之問題。漏電流之 20產生引起在顯示器（LCD等）之各像素充電之資料電壓變 化之問題等，而降低全體顯示器之特性。 如此’ TFT製造時之金屬導入具有降低非晶矽之結晶 化溫度’可使用玻璃基板之優點，反之，卻具有因金屬污 染’而降低TFT之特性之缺點，故將金屬觸媒導入至非晶矽 6 =i導入置之調節非常重要。即，為降低結晶化溫度， 入非常多之金屬觸媒時，產生金屬污染等嚴重之問題。 為防止此種金屬污染之問題，導入非常少之金屬觸媒時， 則無法達成導入金屬觸媒原本之目的之降低結晶化溫度。 5結果，以儘量導人少量金屬觸媒，且降低結晶化溫度為佳。 、通常製造TFT時，將金屬觸媒導人至非晶㈣膜上之 方法係使用賤鍍方法或旋轉塗布法等，特別是基於金屬塗 布過程之谷易性等之理由，主要使用賤鑛法。然而，在習 知濺鍍法中，無法將導入至非晶石夕薄膜上之金屬觸媒之量 10 2量調節為少量。舉例言之，以濺鑛法塗布金屬觸媒時， 右要儘里使塗布量小，必須將塗布速度及塗布時間等儘量 、’隹持在小範圍。然而，若塗布速度及塗布時間在非常小之 範圍，有非常不易將塗布條件維持一定之問題點。 【發明内容】 15 發明揭示 為解決前述習知技術之問題點之本發明目的在於提供 可將金屬或金屬有機化合物吸附至非晶矽薄膜上，俾以金 屬誘發結晶化方式使矽結晶化之裝置及方法。 又’本發明之目的在於提供將適當濃度之金屬或金屬 20有機化合物吸附至非晶矽薄膜上，以使降低半導體或顯示 器各特性之金屬污染最小化之裝置及吸附方法。 為達成前述目的，本發明之金屬吸附裝置係將金屬吸 附至非晶矽上，俾以金屬誘發結晶化方式使矽結晶化者， 其包含有供踡含有金屬之來源氣體之來源氣體供給部；供 輔助氣體之獅氣體供給部；藉由前述來源氣體與前述 輔助氣體之反應，使金屬吸附至前述非晶矽上之室；及藉 調節吸Μ力' 吸附時間及吸附溫度中之至少丨個控制吸 附至刖述非晶；5夕之金屬量之控制部。 5 為達成刖述目的，本發明之金屬吸附裝置係將金屬吸 附至非晶石夕上，俾以金属誘發結晶化方式使石夕結晶化者， 其包含有供給含有金屬之來源氣體者來源氣體供給部；使 金屬及附至刖述非晶石夕上之室；及藉調節吸附壓力、吸附 時間及吸附溫度中之至少1個，控制吸附至前述非晶矽之金 10屬量之控制部。 為達成前述目的，本發明之金屬吸著方法係將金屬吸 附至非晶矽上，俾以金屬誘發結晶化方式使矽結晶化者， 其具有以下步驟：（1)將非晶矽配置於室内；（2)使含有 金屬之來源氣體流入前述室内；（3)藉調節吸附壓力、吸 15附時間及吸附溫度中之至少1個，將預定量之來源氣體吸附 至前述非晶矽上；（4)從前述室排出未吸附至前述非晶矽 上之來源氣體；（5)使輔助氣體流入前述室内；（6)藉吸 附至前述非晶矽上之來源氣體及前述輔助氣體反應，最後 將預定量金屬吸附至前述非晶矽上。 20 為達成前述目的，本發明之金屬吸附方法係將金屬吸 附至非晶矽上，俾以金屬結晶化方式使矽結晶化者，其具 有以下步騾：（1)將非晶矽配置於室内；（2)使含有金屬 之來源氣體流入前述室内；（3)藉調節吸附壓力、吸附時 間及吸附溫度中之至少1個，將預定量之來源氣體吸附至前 1377174 述非晶^夕上。 根據本發明，具以下之效果，即，可將吸附至非晶矽 之薄膜上之金屬量調節成適當且微小量，而可降低非晶矽 結晶化時之結晶化溫度，而可防止金屬污染，提高半導體 5 或顯示器之各特性。 又，根據本發明，由於可適用於大面之基板，故具有 可增加LCD等平板顯示器之生產性，減低生產成本之效果。 【實施方式】Therefore, high-performance LCDs should use polycrystalline germanium TFTs. The polycrystalline germanium TFT is formed by depositing an amorphous germanium on a transparent substrate such as glass or quartz, and polycrystallizing it to form a gate oxide film and a gate electrode, and implanting a dopant into the source and the drain to form an insulating layer. production. 20 When manufacturing a polycrystalline germanium TFT, the main procedure is a step of polycrystallizing a film of amorphous germanium. In particular, it is preferred to lower the crystallization temperature. If the crystallization temperature is very high, when the TFT is fabricated, the glass substrate having a low melting point cannot be used, and the manufacturing cost of the TFT is greatly increased. Considering the possibility of using such a glass substrate, a multi-step process of forming a polycrystalline film at a low temperature and in a short time, as described below, has been proposed. The Excimer Laser Crystallization method utilizes an instantaneous irradiation laser. The method of recrystallizing molten amorphous yttrium prevents damage of the glass substrate due to rapid heating, and has the advantage of being excellent in crystallinity of polycrystalline germanium. However, there are disadvantages such as reduced reproducibility and complicated equipment structure. The rapid heat treatment method utilizes an IR bulb to rapidly heat-treat the amorphous crucible, which has the advantages of high production speed and low production cost, and has disadvantages such as thermal shock caused by sudden heating and deformation of the glass substrate. 10 Metal Induced Crystallization (MIC) method is a method in which a metal catalyst such as Ni, Cu or A1 is applied to an amorphous crucible, and the method of crystallization at a low temperature has the advantage of being crystallizable at a low temperature, but has a leakage current. The disadvantage of a significant increase due to the considerable amount of metal contained in the tongue area. The metal induced lateral crystallization (Metal Induced Lateral Crystall 13 · » 1Zatlon; MILC) system is developed to prevent metal contamination caused by the MIC method, and the metal catalyst is vapor-deposited in the source/drain region, and the MIc is preferentially induced. This is used as a method for seed crystals to grow polycrystals in the active region of the lower portion of the gate. The MILC method has the advantage that the metal contamination is less than the MIC method in the laterally grown crystallization region, but there is still a problem of leakage current. The leakage current 20 causes a problem such as a change in the voltage of the data charged by each pixel of the display (LCD or the like), and the characteristics of the entire display are lowered. Thus, the fact that the metal introduction during TFT fabrication has the effect of lowering the crystallization temperature of the amorphous germanium can use the advantage of the glass substrate, and conversely, it has the disadvantage of lowering the characteristics of the TFT due to metal contamination, so the metal catalyst is introduced into the amorphous state.矽6 =i The adjustment of the import is very important. That is, in order to lower the crystallization temperature, when a large amount of the metal catalyst is introduced, serious problems such as metal contamination occur. In order to prevent the problem of such metal contamination, when a very small amount of metal catalyst is introduced, the crystallization temperature for the purpose of introducing the metal catalyst is not achieved. 5 results, in order to lead a small amount of metal catalyst, and reduce the crystallization temperature is better. When a TFT is usually produced, a method of introducing a metal catalyst onto an amorphous (tetra) film is by using a ruthenium plating method or a spin coating method, and the like, in particular, based on the susceptibility of a metal coating process, etc., mainly using a bismuth ore method. . However, in the conventional sputtering method, the amount of the metal catalyst introduced into the amorphous film cannot be adjusted to a small amount. For example, when the metal catalyst is applied by the sputtering method, the coating amount is small to the right, and the coating speed and the coating time must be kept as small as possible. However, if the coating speed and the coating time are in a very small range, there is a problem that it is extremely difficult to maintain the coating conditions constant. SUMMARY OF THE INVENTION In order to solve the problems of the prior art described above, an object of the present invention is to provide a device capable of adsorbing a metal or a metal organic compound onto an amorphous germanium film and crystallizing the germanium by metal induced crystallization. And methods. Further, it is an object of the present invention to provide a device and an adsorption method for adsorbing a metal or a metal compound of an appropriate concentration onto an amorphous germanium film to minimize metal contamination which lowers the characteristics of the semiconductor or the display. In order to achieve the above object, the metal adsorption device of the present invention adsorbs a metal to an amorphous crucible, and crystallizes the crucible by a metal-induced crystallization method, which comprises a source gas supply portion for supplying a source gas containing a metal; a lion gas supply unit for assisting gas; adsorbing the metal to the chamber on the amorphous crucible by the reaction of the source gas and the auxiliary gas; and adjusting at least one of the adsorption time and the adsorption temperature Control the adsorption to the amorphous state; the control unit of the metal amount of the 5th. 5 For the purpose of achieving the above description, the metal adsorption device of the present invention adsorbs a metal to an amorphous stone, and cerium is crystallized by a metal-induced crystallization method, and includes a source gas for supplying a source gas containing a metal. a supply unit; a metal and a chamber attached to the amorphous stone; and at least one of the adsorption pressure, the adsorption time, and the adsorption temperature are controlled to control the adsorption of the gold to the amorphous 10 . In order to achieve the above object, the metal sorption method of the present invention adsorbs a metal to an amorphous crucible, and crystallizes the crucible by a metal-induced crystallization method, which has the following steps: (1) disposing the amorphous crucible in the chamber (2) causing a source gas containing a metal to flow into the chamber; (3) adsorbing a predetermined amount of the source gas to the amorphous crucible by adjusting at least one of an adsorption pressure, a suction time, and an adsorption temperature; 4) discharging a source gas that is not adsorbed onto the amorphous crucible from the chamber; (5) flowing an auxiliary gas into the chamber; (6) reacting the source gas adsorbed onto the amorphous crucible and the auxiliary gas, and finally A predetermined amount of metal is adsorbed onto the aforementioned amorphous crucible. In order to achieve the above object, the metal adsorption method of the present invention adsorbs a metal to an amorphous crucible, and crystallizes the crucible by metal crystallization, which has the following steps: (1) disposing the amorphous crucible in the chamber (2) causing a source gas containing a metal to flow into the chamber; (3) adsorbing a predetermined amount of the source gas to the first 1377174 by adjusting at least one of the adsorption pressure, the adsorption time, and the adsorption temperature. According to the present invention, the amount of metal adsorbed onto the amorphous ruthenium film can be adjusted to an appropriate and minute amount, and the crystallization temperature at the time of crystallization of the amorphous ruthenium can be reduced, and metal contamination can be prevented. Improve the characteristics of the semiconductor 5 or display. Moreover, according to the present invention, since it can be applied to a substrate having a large surface, it is possible to increase the productivity of a flat panel display such as an LCD and to reduce the production cost. [Embodiment]
用以實施發明之最佳形態 10 以下，參照附加圖式，就本發明之實施形態詳細說明。 第1圖係顯示本發明金屬或金屬有機化合物吸附裝置 10之概念圖。如第1圖所示，金屬吸附裝置10包含來源氣體 供給部11、輔助氣體供給部12、搬運氣體供給部13、氣體 流入部14、氣體排出部15、吸附室16、加熱部17及控制部 15 18。 來源氣體供給部11發揮將相當於吸附至非晶矽薄膜上 之金屬原料之來源氣體（即，金屬有機化合物）供給至吸 附室16内之作用。由於金屬有機化合物一般在常溫以固態 或液態之形態存在，故來源氣體供給部11可具有使固態或 20 液態金屬有機化合物以氣體形態氣化之來源加熱部。 為以金屬誘發結晶化方式使矽結晶化，從來源氣體供 給部11供給之來源氣體可含有Ni、A卜Ti、Ag、Au、Co、 Sb、Pd、Cu中之任一個或二個以上。如本發明般，金屬觸 媒使用Ni時，來源氣體（含有Ni之金屬有機化合物）宜使 9 用 Ni (CP) 2[—環戊二稀錦(n)(Di ( cyclopentadienyl) nick el (Π)) ’ 一茂鎖(Nickelocene)]或Ni (dmamb) 2[1-二甲胺 -2-甲基 _2· 丁醇 g旨（1 -dimethylamino-2-methyl-2-butanolate)] 中之任一個。 輔助氣體供給部12發揮將可與來源氣體反應之輔助氣 體供給至吸附室16内，以於最後將金屬吸附至非晶矽薄膜 上之作用。即，來源氣體含有金屬以外之成份[舉例言之， 若為Ni (cp) 2時，即為Cp成份]’為將Ni吸附至非晶矽薄膜 上，必須去除Ni以外之成份，可以輔助氣體去除該種成份。 換言之，藉使來源氣體之Ni (cp) 2與輔助氣體反應，去除 cp成份’可將Ni吸附至非晶矽薄膜上[舉例言之’ Ni (cp) 2 + H2-_>Ni+mCnH2n+2] 0 輔助氣體可使用H2、NH3等還原性氣體；02、n2〇、Η 2〇、臭氧等氧化性氣體；Ar、N2等惰性氣體。另一方面， 當將未去除金屬以外之成份之來源氣體直接吸附至非晶矽 薄膜上時，由於未使用輔助氣體’故亦有不需輔助氣體供 給部之情形。 搬運氣體供給部13發揮供給搬運氣體，以順利地將來 源氣體供給至吸附室16内之作用。藉搬運氣體，來源氣體 更順利地移動，流入吸附室16内。亦有從搬運氣體供給部1 3供給之搬運氣體通過來源氣體供給部Π後’流入吸附室16 之情形’亦有直接流入吸附室16内之情形，以兩者兼具之 情形為佳。當來源氣體之移動率充分時’亦可不使用搬運 氣體。搬運氣體可兼具將吸附室16内沖洗之沖洗氣體之作 1377174 用。搬運氣體可使用Ar、Ne、He、N2中任一個或二個以上 之惰性氣體。 氣體流入部14及氣體排出部15設置於吸附室16之前端 或後端，為氣體流入吸附室16内或氣體從吸附室16排出之 5 部份。經由氣體流入部14及氣體排出部15流入或排出之氣 體包含來源氣體、輔助氣體（必要時）、搬運氣體（必要時）、 無法吸附至非晶矽薄膜上之來源氣體、因來源氣體及輔助 氣體之反應產生之副產物氣體。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Fig. 1 is a conceptual view showing a metal or metal organic compound adsorption device 10 of the present invention. As shown in Fig. 1, the metal adsorption device 10 includes a source gas supply unit 11, an assist gas supply unit 12, a carrier gas supply unit 13, a gas inflow unit 14, a gas discharge unit 15, an adsorption chamber 16, a heating unit 17, and a control unit. 15 18. The source gas supply unit 11 serves to supply a source gas (i.e., a metal organic compound) corresponding to a metal raw material adsorbed onto the amorphous germanium film to the adsorption chamber 16. Since the metal organic compound is generally present in a solid or liquid form at normal temperature, the source gas supply portion 11 may have a source heating portion for vaporizing a solid or a 20 liquid metal organic compound in a gaseous form. In order to crystallize ruthenium by metal induced crystallization, the source gas supplied from the source gas supply unit 11 may contain any one or two or more of Ni, A, Ti, Ag, Au, Co, Sb, Pd, and Cu. As in the present invention, when the metal catalyst uses Ni, the source gas (metal organic compound containing Ni) is preferably made of Ni (CP) 2 [-cyclopentadienyl nick el (Π) )) 'Nickelocene' or Ni (dmamb) 2[1-dimethylamino-2-methyl-2-butanolate] One. The assist gas supply unit 12 functions to supply an auxiliary gas that can react with the source gas into the adsorption chamber 16 to finally adsorb the metal onto the amorphous tantalum film. That is, the source gas contains a component other than a metal [for example, if Ni (cp) 2 is a Cp component], in order to adsorb Ni onto the amorphous tantalum film, it is necessary to remove components other than Ni to assist the gas. Remove this ingredient. In other words, by reacting Ni (cp) 2 of the source gas with the auxiliary gas, the removal of the cp component 'can adsorb Ni onto the amorphous germanium film [for example, 'Ni (cp) 2 + H2-_>; Ni+mCnH2n+ 2] 0 The auxiliary gas may be a reducing gas such as H2 or NH3; an oxidizing gas such as 02, n2 〇, Η 2 〇, or ozone; or an inert gas such as Ar or N 2 . On the other hand, when the source gas of the component other than the metal is directly adsorbed onto the amorphous ruthenium film, there is no need for the auxiliary gas supply portion since the auxiliary gas is not used. The carrier gas supply unit 13 functions to supply the carrier gas to smoothly supply the source gas into the adsorption chamber 16. By carrying the gas, the source gas moves more smoothly and flows into the adsorption chamber 16. In the case where the carrier gas supplied from the carrier gas supply unit 13 passes through the source gas supply unit and then flows into the adsorption chamber 16, it may flow directly into the adsorption chamber 16, and it may be preferable to have both. When the movement rate of the source gas is sufficient, the carrier gas may not be used. The carrier gas can be used as a flushing gas for rinsing in the adsorption chamber 16 for 1377174. Any one or two or more of Ar, Ne, He, and N2 may be used as the carrier gas. The gas inflow portion 14 and the gas discharge portion 15 are provided at the front end or the rear end of the adsorption chamber 16, and are a portion where the gas flows into the adsorption chamber 16 or the gas is discharged from the adsorption chamber 16. The gas that flows in or out through the gas inflow portion 14 and the gas discharge portion 15 includes a source gas, an auxiliary gas (if necessary), a carrier gas (if necessary), a source gas that cannot be adsorbed onto the amorphous germanium film, a source gas, and an auxiliary gas. A by-product gas produced by the reaction of a gas.
吸附室16發揮將金屬吸附至非晶矽薄膜上之作用。在 10 此，吸附係指化學吸附（chemisorption)者，並非排除物 理吸附（physisorption)之概念。 非晶矽薄膜形成於可適用於LCD等TFT基板之玻璃基 板19上。暫時配置於吸附室16内之玻璃基板數可為1片（牧 葉式吸附室），亦可為2片以上之複數片（批次式吸附室）， 15 若考慮生產性，批次式吸附室較佳。 當直接吸附流入吸附室16内之來源氣體時，便將金屬 有機化合物吸附至非晶矽薄膜上。此時，即使吸附來源氣 體，使其與輔助氣體反應時，結果僅將金屬吸附至非晶矽 薄膜上。 20 吸附室16可具有加熱部17。此加熱部17發揮供給將金 屬或金屬有機化合物吸附至非晶矽薄膜上所需之熱能之作 用。在本發明之吸附步驟中，宜將非晶矽薄膜之溫度維持 在100至250°C之範圍内。惟，亦有將金屬有機化合物吸附 至非晶矽薄膜上時，完全不需熱能之情形。此時，亦可不 11 1377174The adsorption chamber 16 functions to adsorb metal to the amorphous germanium film. In this case, adsorption refers to chemisorption, and does not exclude the concept of physical adsorption. The amorphous germanium film is formed on a glass substrate 19 which can be applied to a TFT substrate such as an LCD. The number of glass substrates temporarily disposed in the adsorption chamber 16 may be one (grass type adsorption chamber), or may be two or more sheets (batch type adsorption chamber), 15 if productivity is considered, batch adsorption The room is preferred. When the source gas flowing into the adsorption chamber 16 is directly adsorbed, the metal organic compound is adsorbed onto the amorphous tantalum film. At this time, even if the source gas is adsorbed and reacted with the assist gas, only the metal is adsorbed onto the amorphous germanium film. The adsorption chamber 16 may have a heating portion 17. This heating portion 17 serves to supply heat energy required for adsorbing a metal or a metal organic compound onto the amorphous germanium film. In the adsorption step of the present invention, it is preferred to maintain the temperature of the amorphous ruthenium film in the range of 100 to 250 °C. However, there is also a case where the metal organic compound is adsorbed onto the amorphous germanium film without any heat energy. At this time, it is not 11 11377174
ίο 15Ίο 15
20 使加熱部17運作或不一開始便將加熱部設於吸附室16内。 控制部18發揮在吸附過程中，調節吸附室16内之氣體 壓力（吸附壓力）、可維持壓力之時間（吸附時間）及非晶 矽薄膜之溫度（吸附溫度）等的作用。在本發明中為使所 吸附之金屬或金屬有機化合物之量（吸附濃度）儘量為少 量，以可使用金屬誘發結晶化方式，降低矽之結晶化溫度， 且使金屬污染最小化，乃經由控制部18，調節吸附壓力、 吸附時間及吸附溫度中之至少1個。 吸附至非晶矽薄膜上之金屬或金屬有機化合物之量係 當吸附壓力及吸附時間越多，便越多者。因而，當調節吸 附壓力及吸附時間時，可調節金屬或金屬有機化合物之吸 附濃度。 藉調節從來源氣體供部11供給之來源氣體之流量、經 由氣體流入部14，流入吸附室16之氣體總流量及經由氣體 排出部5，從吸附室16排出之氣體總流量中之至少1個，可 控制吸附壓力。在吸附窒16流入或排出之氣體含有輔助氣 體或搬運氣體。因而，從輔助氣體供給部12供給之輔助氣 體之流量及從搬運氣體供給部13供給之搬運氣體之流量亦 可藉控制部18控制。 由於在吸附過程中需熱能，故藉由控制部18，調節吸 附過程之吸附溫度時，可調節金屬或金屬有機化合物之吸 附濃度。藉調節吸附室16内之加熱部17之溫度，可控制吸 附溫度。在第1圖中，控制部與以此控制部控制之各構成要 件間以虛線顯示，以供參考。 12 137717420 The heating unit 17 is operated or the heating unit is placed in the adsorption chamber 16 without starting. The control unit 18 functions to adjust the gas pressure (adsorption pressure) in the adsorption chamber 16, the time during which the pressure can be maintained (adsorption time), and the temperature (adsorption temperature) of the amorphous germanium film during the adsorption process. In the present invention, in order to minimize the amount (adsorption concentration) of the adsorbed metal or metal organic compound, it is possible to use a metal-induced crystallization method, reduce the crystallization temperature of the ruthenium, and minimize metal contamination by controlling The portion 18 adjusts at least one of the adsorption pressure, the adsorption time, and the adsorption temperature. The amount of metal or organometallic compound adsorbed onto the amorphous germanium film is the more the adsorption pressure and the adsorption time, the more. Thus, when the adsorption pressure and the adsorption time are adjusted, the adsorption concentration of the metal or organometallic compound can be adjusted. At least one of the flow rate of the source gas supplied from the source gas supply unit 11 , the total gas flow rate flowing into the adsorption chamber 16 through the gas inflow portion 14 , and the total gas flow rate discharged from the adsorption chamber 16 via the gas discharge unit 5 , can control the adsorption pressure. The gas flowing into or discharged from the adsorption crucible 16 contains an auxiliary gas or a carrier gas. Therefore, the flow rate of the assist gas supplied from the assist gas supply unit 12 and the flow rate of the transport gas supplied from the transport gas supply unit 13 can be controlled by the control unit 18. Since heat energy is required during the adsorption process, the adsorption concentration of the metal or organometallic compound can be adjusted by adjusting the adsorption temperature of the adsorption process by the control unit 18. The adsorption temperature can be controlled by adjusting the temperature of the heating portion 17 in the adsorption chamber 16. In Fig. 1, the control unit and each of the constituent elements controlled by the control unit are shown by broken lines for reference. 12 1377174
以下，就利用本發明之吸附裝置ίο，吸附金屬或金屬 有機化合物之方法詳細說明。 首先，於吸附室16内配設形成有非晶矽薄膜之玻璃基 板19。於配置玻璃基板19後，以真空泵（圖中未示）使吸 5 附室16排氣，以使吸附室16内之基本壓力在lOOmTorr左右。 接著，從來源氣體供給室11將相當於吸附至非晶矽薄 膜上之金屬原料之來源氣體（即，金屬有機化合物）經由 氣體流入部4，供給至吸附室16内。當金屬有機化合物在常 溫以固態或液態之形態存在時，將固態或液態之金屬有機 10 化合物以較常溫高之溫度加熱而氣體化。此時，來源氣體 含有Ni、Al、Ti、Ag、Au、Co、Sb、Pd、Cu中之任一個或 二個以上。當使用Ni作為金屬觸媒時，來源氣體使用Ni (c p ) 2 或 Ni (dmamb) 2。 接著，從搬運氣體供給部13供給搬運氣體，以使來源 15 氣體經由氣體流入部14，順利地供給至吸附室16内。搬運 氣體可使用Ar、Ne、He、N2中之任一個或二個以上之惰性 氣體。搬運氣體可使從來源氣體供給部11供給之來源氣體 順利地移動。此時，來源氣體與搬運氣體宜一同流入吸附 室16内。當搬運氣體通過來源氣體供給部1時，來源氣體之 20 移動率更有效率地增加。惟，當來源氣體之移動率足夠時， 亦可不使用搬運氣體。 接著，流入吸附室16内之來源氣體（金屬有機化合物） 吸附至非晶矽薄膜上。舉例言之，當使用Ni (cp) 2或Ni (d mamb) 2作為來源氣體時，該等金屬有機化合物直接吸附 13 1377174Hereinafter, a method of adsorbing a metal or a metal organic compound by the adsorption device ίο of the present invention will be described in detail. First, a glass substrate 19 on which an amorphous germanium film is formed is disposed in the adsorption chamber 16. After the glass substrate 19 is placed, the suction chamber 16 is evacuated by a vacuum pump (not shown) so that the basic pressure in the adsorption chamber 16 is about 100 mTorr. Then, a source gas (i.e., a metal organic compound) corresponding to the metal raw material adsorbed onto the amorphous crucible film is supplied from the source gas supply chamber 11 to the adsorption chamber 16 through the gas inflow portion 4. When the metal organic compound is present in a solid or liquid form at normal temperature, the solid or liquid metal organic compound 10 is heated and gasified at a temperature higher than normal temperature. At this time, the source gas contains one or more of Ni, Al, Ti, Ag, Au, Co, Sb, Pd, and Cu. When Ni is used as the metal catalyst, Ni (c p ) 2 or Ni (dmamb) 2 is used as the source gas. Then, the carrier gas is supplied from the carrier gas supply unit 13 so that the source 15 gas is smoothly supplied into the adsorption chamber 16 via the gas inflow portion 14. Any one or two or more of Ar, Ne, He, and N2 may be used as the carrier gas. The carrier gas can smoothly move the source gas supplied from the source gas supply unit 11. At this time, the source gas and the carrier gas preferably flow into the adsorption chamber 16 together. When the carrier gas passes through the source gas supply portion 1, the shift rate of the source gas 20 is more efficiently increased. However, when the movement rate of the source gas is sufficient, the carrier gas may not be used. Next, the source gas (metal organic compound) flowing into the adsorption chamber 16 is adsorbed onto the amorphous germanium film. For example, when Ni (cp) 2 or Ni (d mamb) 2 is used as the source gas, the metal organic compounds directly adsorb 13 13377174
55
10 1510 15
20 至非晶矽薄膜上。在本發明中，在含有吸附室16内之來源 氣體之氣體環境下，藉使玻璃基板19待機，可將金屬有機 化合物吸附至形成於玻璃基板19上之非晶矽薄膜上。此過 程為將金屬有機化合物之金屬（例如鎳）化學吸附至非晶 矽薄膜之矽上之化學吸附過程。然而，在實際之吸附過程 中，亦有將金屬以物理吸附（physisorption)至非晶石夕薄膜 之過程。如此以物理吸附之金屬亦可發揮降低矽結晶化溫 度之觸媒作用。 吸附之金屬有機化合物之量（吸附濃度）直接受到吸 附室16内之氣體壓力（吸附壓力 >、可維持壓力之時間（吸 附時間）及非晶矽薄膜之溫度（吸附溫度）之影響。因而， 藉控制部18適當地控制吸附壓力、吸附時間及吸附溫度 時，可細微地調節吸附濃度。 首先，可控制吸附壓力，調節金屬有機化合物之吸附 濃度。由於吸附壓力與從來源氣體供給部11供給之來源氣 體流量直接具關聯，故當減少來源氣體之供給流量時，可 減少吸附壓力，藉此，可減少吸附濃度。相對於此，當來 源氣體之供給流量增加時，可增加吸附濃度。 又，藉調節經由氣體流入部14，流入吸附室16之氣體 總流量及經由氣體排出部5，從吸附室16排出之氣體總流 量，可控制吸附壓力。舉例言之，藉調節流入吸附室16之 氣體之總流量與從吸附室16排出之氣體總流量之差，控制 吸附壓力，藉此，可控制吸附濃度。當然前述方法亦包含 當吸附室16内部到達預定吸附壓力時，封閉氣體流入部14 14 137717420 to amorphous film. In the present invention, the metal organic compound can be adsorbed onto the amorphous germanium film formed on the glass substrate 19 by the standby of the glass substrate 19 in a gas atmosphere containing the source gas in the adsorption chamber 16. This process is a chemisorption process in which a metal of a metal organic compound (e.g., nickel) is chemically adsorbed onto a crucible of an amorphous germanium film. However, in the actual adsorption process, there is also a process of physically absorbing a metal to an amorphous film. Such a physically adsorbed metal can also exert a catalytic effect of lowering the crystallization temperature of ruthenium. The amount of adsorbed organometallic compound (adsorption concentration) is directly affected by the gas pressure (adsorption pressure >, the time during which the pressure can be maintained (adsorption time) and the temperature of the amorphous tantalum film (adsorption temperature) in the adsorption chamber 16 When the adsorption pressure, the adsorption time, and the adsorption temperature are appropriately controlled by the control unit 18, the adsorption concentration can be finely adjusted. First, the adsorption pressure can be controlled to adjust the adsorption concentration of the metal organic compound. The adsorption pressure and the source gas supply unit 11 Since the source gas flow rate of the supply is directly related, when the supply flow rate of the source gas is reduced, the adsorption pressure can be reduced, whereby the adsorption concentration can be reduced. On the other hand, when the supply flow rate of the source gas is increased, the adsorption concentration can be increased. Further, by adjusting the total flow rate of the gas flowing into the adsorption chamber 16 through the gas inflow portion 14 and the total flow rate of the gas discharged from the adsorption chamber 16 via the gas discharge portion 5, the adsorption pressure can be controlled. For example, the flow into the adsorption chamber 16 is regulated. The difference between the total flow rate of the gas and the total flow rate of the gas discharged from the adsorption chamber 16 controls the adsorption pressure , Whereby the concentration can be controlled attraction. Of course the method also includes the interior of the chamber 16 when the adsorption reaches a predetermined adsorption pressure, closing the gas inlet 14141377174
10 1510 15
20 及氣體排出部15，控制吸附壓力之方式。 藉控制吸附時間，亦可調節金屬有機化合物之吸附濃 度。舉例言之，當維持吸附壓力之吸附時間越短時，可更 減少金屬有機化合物之吸附濃度。 當控制吸附溫度時，可調節吸附濃度。由於一般在吸 附過程，需預定之熱能，故當降低吸附溫度時，可減少金 屬有機化合物之吸附濃度。惟，當吸附溫度非常低時，有 不產生吸附現象之可能性，當吸附溫度非常高時，亦有所 吸附之金屬有機化合物從非晶矽薄膜分離之可能性。吸附 溫度之控制係藉控制部18調節加熱部17之溫度而進行。 於開始吸附步驟前，宜使非晶矽薄膜之溫度維持在預 定之吸附溫度。吸附溫度以維持在100至250°c之範圍内為 佳。依來源氣體種類，吸著時非全體皆需熱能時（例如可 常溫吸附時），控制成吸附溫度為常溫即可。 另一方面，當將已結晶化之矽應用於TFT等時，為防 止金屬污染造成之半導體或顯示器之特性降低時，必須使 吸附濃度最小化。因此，需調節為金屬以小於1個原子層（〇 ne atomic layer )之狀態吸附至非晶石夕之薄膜上。在此，小 於1個原子層係指金屬觸媒無法以1個原子層完全覆蓋非晶 矽薄膜全體面積時，即，非連續地將金屬吸附至全體非晶 矽薄膜上，而是到處吸附之情形（覆蓋率<1)。此時，本 發明之金屬吸附裝置10藉控制吸附壓力、吸附時間及吸著 溫度中之至少1個，可細微地調節吸附溫度，故具有可調節 吸附濃度成如前述覆蓋率小於1之優點。 15 1377174 接著，在吸附步驟，使未吸附至非晶矽薄膜上之來源 氣體（金屬有機化合物）從吸附室16經由氣體排出部6排出 (沖洗）。在此過程中排出之來源氣體包含最初被吸附至非 晶矽膜上，但吸附程度弱（例如以物理吸附至非晶矽薄膜 5 上之來源氣體），而從非晶矽薄膜分離而去除之來源氣體。 當此步驟結束時，將來源氣體（金屬化合物）吸附至非晶 矽薄膜上之過程便結束。此時，從搬運氣體供給部12供給 之搬運氣體流入吸附室16内，而可利用於排出來源氣體。20 and the gas discharge unit 15 control the manner of adsorption pressure. The adsorption concentration of the organometallic compound can also be adjusted by controlling the adsorption time. For example, when the adsorption time for maintaining the adsorption pressure is shorter, the adsorption concentration of the metal organic compound can be further reduced. When the adsorption temperature is controlled, the adsorption concentration can be adjusted. Since the predetermined heat energy is required during the adsorption process, the adsorption concentration of the metal organic compound can be reduced when the adsorption temperature is lowered. However, when the adsorption temperature is very low, there is a possibility that adsorption does not occur, and when the adsorption temperature is very high, there is a possibility that the adsorbed metal organic compound is separated from the amorphous germanium film. The control of the adsorption temperature is performed by the control unit 18 adjusting the temperature of the heating unit 17. It is preferred to maintain the temperature of the amorphous tantalum film at a predetermined adsorption temperature before starting the adsorption step. The adsorption temperature is preferably maintained in the range of 100 to 250 °C. Depending on the type of gas source, when heat is not required for all of the sorption (for example, when it is adsorbed at room temperature), the adsorption temperature is controlled to normal temperature. On the other hand, when the crystallized crucible is applied to a TFT or the like, it is necessary to minimize the adsorption concentration in order to prevent deterioration of the characteristics of the semiconductor or the display due to metal contamination. Therefore, it is necessary to adjust the metal to be adsorbed onto the amorphous film in a state of less than one atomic layer. Here, less than one atomic layer means that the metal catalyst cannot completely cover the entire area of the amorphous germanium film with one atomic layer, that is, non-continuously adsorbing the metal onto the entire amorphous germanium film, but adsorbing it everywhere. Situation (coverage <1). At this time, the metal adsorption apparatus 10 of the present invention can finely adjust the adsorption temperature by controlling at least one of the adsorption pressure, the adsorption time, and the adsorption temperature, so that the adsorption concentration can be adjusted to have an advantage that the coverage is less than 1. 15 1377174 Next, in the adsorption step, the source gas (metal organic compound) not adsorbed onto the amorphous tantalum film is discharged (flush) from the adsorption chamber 16 through the gas discharge portion 6. The source gas discharged during this process contains the first adsorbed onto the amorphous germanium film, but the degree of adsorption is weak (for example, the source gas physically adsorbed onto the amorphous germanium film 5), and is removed from the amorphous germanium film. Source gas. At the end of this step, the process of adsorbing the source gas (metal compound) onto the amorphous germanium film is completed. At this time, the carrier gas supplied from the carrier gas supply unit 12 flows into the adsorption chamber 16, and can be used to discharge the source gas.
接著，將金屬吸附至非晶矽薄膜上。因此，先從輔助 10 氣體供給部12使輔助氣體經由氣體流入部14供給至吸附室Next, the metal is adsorbed onto the amorphous germanium film. Therefore, the assist gas is supplied from the auxiliary gas supply unit 12 to the adsorption chamber via the gas inflow portion 14 first.
16内。如此供給至吸附室16内之輔助氣體與吸附至非晶矽 薄膜上之來源氣體（金屬有機化合物）反應，最後，將金 屬吸附至非晶矽之薄膜上。舉例言之，藉使來源氣體Ni (c P) 2與輔助氣體反應，去除cp成份，而將Ni吸附至非晶矽 15 薄膜上[即，Ni ( cp ) 2+H2—Ni+mCnH2n+2]。輔助氣體可使用 H2、NH3等還原性氣體；02、N20、H20、臭氧等氧化性氣 體；Ar、N2等惰性氣體。 最後，使藉來源氣體與輔助氣體之反應結果產生之副 產物氣體從吸附室16經由氣體排出部15排出（沖洗）。當此 20 步驟結束時，將金屬吸附至非晶矽薄膜上之過程便結束。 此時，從搬運氣體供給部12供給之搬運氣體流入吸附室16 内，可利用於排出副產物氣體。 根據本發明，由於可適用於大面之基板，故可增加LC D等平板顯示器之生產性，減低生產成本。因而，本發明之 16 1377174 產業利用性可謂極高。 另一方面，在本說明書内，以數個較佳實施形態記述 本發明，只要為該業者，應可知在不脫離申請專利範圍所 揭示之本發明之範疇及思想下，進行多種變形及修正。 【囷式簡單說明】 第1圖係顯示本發明金屬或金屬有機化合物吸附裝置 之概念圖。 【主要元件符號說明】Within 16. The assist gas thus supplied to the adsorption chamber 16 is reacted with a source gas (metal organic compound) adsorbed onto the amorphous germanium film, and finally, the metal is adsorbed onto the amorphous germanium film. For example, if the source gas Ni(c P) 2 reacts with the auxiliary gas, the cp component is removed, and Ni is adsorbed onto the amorphous ruthenium 15 film [ie, Ni ( cp ) 2+H2—Ni+mCnH2n+2 ]. The assist gas may be a reducing gas such as H2 or NH3; an oxidizing gas such as 02, N20, H20 or ozone; or an inert gas such as Ar or N2. Finally, the by-product gas generated as a result of the reaction between the source gas and the assist gas is discharged (flush) from the adsorption chamber 16 via the gas discharge portion 15. At the end of this 20 step, the process of adsorbing the metal onto the amorphous germanium film ends. At this time, the carrier gas supplied from the carrier gas supply unit 12 flows into the adsorption chamber 16 and can be used to discharge the by-product gas. According to the present invention, since it can be applied to a substrate of a large surface, the productivity of a flat panel display such as LC D can be increased, and the production cost can be reduced. Therefore, the industrial utilization of the 16 1377174 of the present invention is extremely high. On the other hand, the present invention will be described in detail in the preferred embodiments of the invention, and it is understood that various modifications and changes can be made without departing from the scope and spirit of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view showing a metal or metal organic compound adsorption device of the present invention. [Main component symbol description]
15.. .氣體流出部 16.. .吸附室 17···加熱部 18.. .控制部 19.. .玻璃;14¾ 10...金屬吸附裝置 11…來源氣體供給部 12…輔助氣體供給部 13···搬運氣體供給部 14···氣體流入部15.. Gas outflow portion 16.. Adsorption chamber 17··· Heating unit 18: Control unit 19: Glass; 143⁄4 10... Metal adsorption device 11... Source gas supply unit 12... Auxiliary gas supply Part 13···Transportation gas supply unit 14···Gas inflow unit
17 c S )17 c S )
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