TWI377173B - Method for manufacturing crystalline silicon - Google Patents
Method for manufacturing crystalline silicon Download PDFInfo
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- TWI377173B TWI377173B TW096150242A TW96150242A TWI377173B TW I377173 B TWI377173 B TW I377173B TW 096150242 A TW096150242 A TW 096150242A TW 96150242 A TW96150242 A TW 96150242A TW I377173 B TWI377173 B TW I377173B
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C23C16/4412—Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
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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
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- 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
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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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Description
1377173 九、發明說明: 【發明所屬之技術領域】 技術領域1377173 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 5 Crystal Display ; LCD )' 有機發光顯示器(Organic Light Emitting 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者,更詳而言之, 其係有關於一種藉金屬誘發結晶化方式,於形成TFT多結矽 薄膜時,防止金屬污染,以提高TFT之特性的多晶矽薄膜之 10 製造方法。 【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The present invention relates to a polycrystalline silicon film suitable for a thin film transistor (TFT) used in a liquid crystal display (LCD) 'Organic Light Emitting Display (OLED). The manufacturer, more specifically, relates to a method for producing a polycrystalline germanium film which is formed by a metal-induced crystallization method and which prevents metal contamination during formation of a TFT multi-junction film to improve the characteristics of the TFT. [Prior Art] The TFT is roughly classified into an amorphous germanium TFT and a multi-junction TFT. The characteristics of TFT
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, 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。 2〇 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,便無法使用熔融點低之玻璃基 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 C S ) 形成多結晶薄膜之多種步驟。 準分子雷射結晶化(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 急速加熱造成之熱撞擊及玻璃基板之變形產生等之缺點。 金屬誘發結晶化(Metal Induced Crystallization ; MIC ) 法係將Νι、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 活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 izatwn ; 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M〗c, 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。ΜIL C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 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 1377173 薄膜時,導入量之調節非常重要。即,為降低結晶化溫度, 導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,以儘量導入少量金屬觸媒,且降低結晶化溫度為佳。Evaluation of the value of electronic mobility. Since the electron mobility of the amorphous germanium TFT is about 15 lcm2/Vs', the electron mobility of the multijunction TFT is about l〇〇cm2/vs, so the high performance LCD should adopt a polycrystalline germanium TFT. The polycrystalline germanium TFT is formed by depositing an amorphous germanium on a transparent substrate such as glass or quartz to form a gate oxide film and a gate electrode, and then implanting a dopant into the source and the drain to form an insulating layer. production. 2〇 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. When the crystallization temperature is very south, when a TFT is manufactured, a glass substrate having a low melting point cannot be used, and the manufacturing cost of the TFT is greatly increased. The possibility of using such a glass substrate is considered. Recently, various steps of forming a polycrystalline thin film at a low temperature and a short time 5 C S have been proposed. The Excimer Laser Crystallization method uses a method of instantaneously irradiating a laser to melt an amorphous crucible and recrystallizing it, thereby preventing damage to the glass substrate caused by rapid heating, and having crystallinity of polycrystalline germanium. Excellent advantages. 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 the disadvantages of thermal impact caused by rapid heating and deformation of the glass substrate. The Metal Induced Crystallization (MIC) method applies a metal catalyst such as Νι, Cu, or A1 to an amorphous yttrium, 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 substantial increase in the amount of metal contained in the activation zone. The Metal Induced Lateral Crystallization (MILC) method is developed to prevent the metal contamination caused by the MIC method, and the metal catalyst is vapor-deposited in the source/drain region, and M〗c is preferentially induced. This is used as a seed crystal to grow the polycrystal enthalpy in the activation region of the lower portion of the gate. The ΜIL C 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 occurrence of leakage current causes a problem of 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 metal introduction during TFT fabrication has the advantage of lowering the crystallization temperature of the amorphous germanium, and the advantages of the glass substrate can be used. Conversely, there is a disadvantage of reducing the characteristics of the TFT due to metal contamination, so the metal catalyst is introduced into the amorphous state. When 矽1377173 film, the adjustment of the introduction amount is very important. That is, in order to lower the crystallization temperature, when a large amount of 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 As a result, it is preferable to introduce a small amount of metal catalyst as much as possible and to lower the crystallization temperature.
通常製造TFT時,將金屬觸媒導入至非晶矽薄膜上之 方法係使用濺鍍方法或旋轉塗布法等,特別是基於金屬塗 布過程之容易性等理由,主要使用滅鍵法。然而,在習知 濺鍍法中,無法將導入至非晶矽薄膜上之金屬觸媒之量儘 10 量調節為少量。舉例言之,以濺鍍法塗布金屬觸媒時,若 要儘量使塗布量小,必須將塗布速度及塗布時間等儘量維 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 為解決前述習知問題點而發明之本發明目的在於提供 一種於以金屬誘發結晶化方式進行矽之結晶化時,可降低 結晶化溫度,且使金屬污染最小化,而可提高TFT特性之多 晶矽之製造方法。 20 為達成前述目的,本發明多晶矽之製造方法具有以下 步驟:(a)將含有金屬之來源氣體供給至非晶矽上;(b) 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述非晶矽上;(c)去除在前述(b) 未吸附至前述非晶矽上之來源氣體;(d)將輔助氣體供給 7 至吸附有别述來源氣體之非晶石夕上;(e)藉吸附至前述非 晶石夕上之來源氣體與前述辅助氣體反應,最後吸附預定量 之金屬至前述非晶石夕上;⑺將吸附有前述金屬之非晶石夕 熱處理。 為達成前述目的,本發明多晶矽之製造方法具有以下 步驟:(a)將含有金屬之來源氣體供給至非晶矽上 藉調節吸附麼力、吸附時間及吸附溫度中之至少㈠固,將預 定量之來源氣體吸附至前述非晶石夕上;(c)去除在前述⑻ 未吸附至前述非晶石夕上之來源氣體;⑷將吸附有前述來 源氣體之非晶矽熱處理。 前述來源氣體可含有Ni、A卜Ti、Ag、Au、Co、Sb、 Pd、Cu中之任一個或二個以上。 前述來源氣體可為Ni(cp)2或Ni(dmamb)2之任一個。 前述輔助氣體可含有H2、NH3等還原性氣體;〇2、n2〇、 H2〇、臭氧等氧化性氣體;Ar、N2等惰性氣體。 前述吸附溫度可控制在常溫至25(rC2範圍。 在前述(b)中,可將來源氣體以覆蓋率小於丨之狀態 吸附至前述非晶矽上。 在前述(f)中,熱處理溫度可為4〇〇S7〇(rc,熱處理 時間可為1至10小時,.熱處理環境為可包含Ar、Ne、He、 乂氣體之惰性氣體環境。 在前述(d)中,熱處理溫度可為4〇〇至7〇〇它,熱處理 時間可為1至10小時,熱處理環境可為包含Ar、Ne、He、 N2氣體之惰性氣體環境;〇2、N2〇、H2〇、臭氧等氧化性氣 1377173 體環境HNH3等還原性氣體環境中之至 本發明之發明人了解前述習知顺法題: 解決此問題點之結果,著眼於為細微調節導::: 之金屬濃度,而以化學吸附金屬觸媒之方法(化學二 chem丽和)為㈣之點而得叫到本發^因而本 發明之主要特徵在於導人方法係使用化學吸附方法,以儘 置將少量濃度之金屬觸媒導入至韭曰^ 非日日矽上。在此,吸附係In general, when a TFT is produced, a method of introducing a metal catalyst onto an amorphous germanium film is mainly a sputtering method, a spin coating method, or the like, and in particular, based on the easiness of the metal coating process, etc., a key-off method is mainly used. However, in the conventional sputtering method, the amount of the metal catalyst introduced onto the amorphous germanium film cannot be adjusted to a small amount. For example, when the metal catalyst is applied by sputtering, if the coating amount is as small as possible, 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 above-mentioned problems, the present invention has an object of providing a method for reducing crystallization temperature and minimizing metal contamination when crystallization of ruthenium by metal induced crystallization. A method of manufacturing a polysilicon which can improve TFT characteristics. In order to achieve the above object, the method for producing a polycrystalline silicon of the present invention has the following steps: (a) supplying a source gas containing a metal to an amorphous crucible; and (b) adjusting at least one of an adsorption pressure, an adsorption time, and an adsorption temperature. a predetermined amount of source gas is adsorbed onto the amorphous germanium; (c) removing the source gas that is not adsorbed onto the amorphous germanium in (b); (d) supplying the auxiliary gas to the adsorbed source (a) reacting the source gas adsorbed onto the amorphous stone with the auxiliary gas, and finally adsorbing a predetermined amount of the metal to the amorphous stone; (7) adsorbing the metal Amorphous stone heat treatment. In order to achieve the above object, the method for producing a polycrystalline silicon of the present invention has the following steps: (a) supplying a source gas containing a metal to an amorphous crucible by adjusting at least one of adsorption, force, and adsorption temperature, a predetermined amount The source gas is adsorbed onto the amorphous stone; (c) the source gas which is not adsorbed onto the amorphous stone in the above (8) is removed; and (4) the amorphous germanium adsorbed with the source gas is heat-treated. The source gas may contain any one or two or more of Ni, A, Ti, Ag, Au, Co, Sb, Pd, and Cu. The aforementioned source gas may be either Ni(cp)2 or Ni(dmamb)2. The auxiliary gas may contain a reducing gas such as H2 or NH3; an oxidizing gas such as 〇2, n2〇, H2〇, or ozone; or an inert gas such as Ar or N2. The adsorption temperature can be controlled at a normal temperature to 25 (rC2 range). In the above (b), the source gas can be adsorbed onto the amorphous crucible in a state where the coverage is less than 丨. In the above (f), the heat treatment temperature can be 4〇〇S7〇(rc, heat treatment time may be 1 to 10 hours, the heat treatment environment is an inert gas environment which may contain Ar, Ne, He, helium gas. In the above (d), the heat treatment temperature may be 4〇〇 To 7〇〇, the heat treatment time can be 1 to 10 hours, the heat treatment environment can be an inert gas environment containing Ar, Ne, He, N2 gas; 〇2, N2〇, H2〇, ozone and other oxidizing gas 1377173 In the reducing gas environment such as HNH3, the inventors of the present invention understand the aforementioned conventional method: the result of solving this problem, focusing on the method of chemically adsorbing the metal catalyst for finely adjusting the metal concentration of the guide:: The second feature of the present invention is that the chemical method is to use a chemical adsorption method to introduce a small amount of metal catalyst into the 韭曰^ non-day. In the sun, here, suck Department
指氣體、液體分子、原子、離子等附著於_表面之現象。 此時,將㈣與滅化學性結“物之㈣稱狀學吸 本發明之多晶石夕之製造方法具有以下效果即,可將 吸附至非晶石夕薄膜上之金屬量適當調節,降低非晶石夕之結 晶化時之結晶化溫度,且防止金屬之污染,以提高多晶石夕 TFT之特性。 15【實施方式】Refers to the phenomenon that gases, liquid molecules, atoms, ions, etc. adhere to the surface. At this time, the method for producing the polycrystalline stone of the present invention is the following method, which can appropriately adjust the amount of metal adsorbed onto the amorphous film and reduce the amount of the metal. The crystallization temperature at the time of crystallization of amorphous austenite, and prevention of metal contamination to improve the characteristics of the polycrystalline slab TFT. 15 [Embodiment]
用以實施發明之最佳形態 以下,就本發明之實施形態詳細說明。 第1,就在本發明第1實施形態中,將金屬吸附至非晶 石夕之薄膜上後’將其熱處理,而形成多晶矽薄膜之方法作 20 說明。 首先’準備形成有非晶矽薄膜之玻璃基板,將之配置 於進行金屬吸附過程之室内。在此,若為LCD等時,玻璃 基板便相當於形成TFT之TFT基板。配置玻璃基板後,以真 空泵使室排氣,以使室内之基本壓力在lOOmTorr左右。 (S ) 9 1377173BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. First, in the first embodiment of the present invention, a method of forming a polycrystalline tantalum film by heat-treating the metal onto the film of amorphous steel is described. First, a glass substrate on which an amorphous germanium film is formed is prepared and placed in a chamber where a metal adsorption process is performed. Here, in the case of an LCD or the like, the glass substrate corresponds to a TFT substrate on which a TFT is formed. After disposing the glass substrate, the chamber is evacuated by a vacuum pump so that the basic pressure in the chamber is about 100 mTorr. (S) 9 1377173
接者,將相當於吸附至非晶石夕薄膜上之金屬原料之來 源氣體(金屬有機化合物)供給至非晶矽薄膜上。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,故金 屬有機化合物以較常溫高之溫度加熱而氣體化。此時,金 5屬有機化合物可含有Ni、A卜Ti、Ag、Au、Co、Sb、Pd、 Cu中之任一個或二個以上之金屬。在本發明使用之金屬有 機化合物係含有金屬鎳者,使用Ni (cp) 2[二環戊二烯鎳(1 I)(Di (cyclopentadienyl) nickel (II));二茂鎳(Nickel〇ce ne)]或Ni (dmamb) 2[1-二甲胺-2-甲基-2-丁醇醋(1_dimethyl 10 amino-2-methyl-2-butanolate)] ° 在來源氣體供給步驟中’為將來源氣體順利地供給至 非晶石夕》專膜上(即’提奇來源氣體之移動率),可同時供給 搬運氣體。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。惟,當來源氣體之移動率充分時,亦 15 可不使用搬運氣體。 接者’所供給之來源氣體(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 ( dmamb ) 2作為來源氣體時,該等金屬有機化合物直接吸附至非晶石夕 薄膜上。在本發明中’在含有金屬化合物之氣體環境下之 2〇 室内’藉使玻璃基板待機,可將金屬有機化合物吸附至形 成於玻璃基板上之非晶矽薄膜上。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)至非晶矽薄膜之過程。如此以物 10 1377173 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)直接受到室 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,當適當 5 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。The source gas (metal organic compound) corresponding to the metal raw material adsorbed onto the amorphous film is supplied to the amorphous germanium film. Since the metal organic compound is generally present in a solid or liquid form at normal temperature, the metal organic compound is heated and gasified at a temperature higher than normal temperature. In this case, the gold 5 organic compound may contain any one or more of Ni, A, Ti, Ag, Au, Co, Sb, Pd, and Cu. In the case where the metal organic compound used in the present invention contains metallic nickel, Ni (cp) 2 [Di(cyclopentadienyl) nickel (II)); nickel (Nickel〇ce ne) )] or Ni (dmamb) 2[1-dimethylamine-2-methyl-2-butanolate] ° in the source gas supply step 'for the source The gas is smoothly supplied to the amorphous film (that is, the mobility of the Titch source gas), and the carrier gas can be supplied at the same time. Any one or two or more of Ar, Ne, He, and N2 may be used as the carrier gas. However, when the movement rate of the source gas is sufficient, the carrier gas may not be used. The source gas (metal organic compound) supplied by the carrier is adsorbed onto the amorphous germanium film. For example, when Ni (cp) 2 or Ni (dmamb) 2 is used as the source gas, the metal organic compounds are directly adsorbed onto the amorphous film. In the present invention, the metal substrate is allowed to adhere to the amorphous germanium film formed on the glass substrate by the standby of the glass substrate in a gas atmosphere in a gas atmosphere containing a metal compound. This process is a chemical adsorption 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 the metal to the amorphous germanium film. The metal adsorbed by the material 10 1377173 can also exert a catalytic action for lowering the crystallization temperature of the ruthenium. The amount of adsorbed organometallic compound (adsorption concentration) is directly affected by the gas pressure (adsorption pressure) in the chamber, the time during which the pressure can be maintained (adsorption time), and the temperature of the amorphous tantalum film (adsorption temperature). Therefore, when the adsorption pressure, the adsorption time, and the adsorption temperature are appropriately controlled, the adsorption concentration can be finely adjusted.
首先,可控制吸附壓力,調節金屬有機化合物之吸附 濃度。由於吸附壓力與供給至非晶矽薄膜上之來源氣體流 量直接具關聯,故當減少來源氣體之供給流量時,可減少 10 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,調節流入至室之氣體總流量及從室排出之氣體總 流量,可控制吸附壓力。舉例言之,藉調節流入至室之氣 體之總流量與從室排出之氣體總流量之差,控制吸附壓 15 力,藉此,可控制吸附濃度。當然前述方法亦包含當室内 部到達預定吸附壓力時,封閉室,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。 20 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 一開始即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 11 C S ) 1377173 能性。 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25〇。(: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 5 常溫吸附時),控制成吸附溫度為常溫即可。First, the adsorption pressure can be controlled to adjust the adsorption concentration of the organometallic compound. Since the adsorption pressure is directly related to the source gas flow supplied to the amorphous tantalum film, 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, the total pressure of the gas flowing into the chamber and the total flow rate of the gas discharged from the chamber can be adjusted to control the adsorption pressure. For example, by adjusting the difference between the total flow rate of the gas flowing into the chamber and the total flow rate of the gas discharged from the chamber, the adsorption pressure is controlled, whereby the adsorption concentration can be controlled. Of course, the foregoing method also includes a method of closing the chamber and controlling the adsorption pressure when the indoor portion reaches a predetermined 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. 20 When controlling the adsorption temperature, 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 no possibility of adsorption at the beginning. When the adsorption temperature is very high, the adsorbed metal organic compound can be separated from the amorphous germanium film by 11 C S ) 1377173. 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 maintained at 100 to 25 Torr. (The range is preferably within the range of the source gas. When the heat is required for all of the suctions (for example, when it is adsorbed at room temperature), the adsorption temperature is controlled to normal temperature.
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丨個原子層 (one atomic layer)之狀態吸附至非晶矽之薄臈上。在此, 10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,非將金屬連續地吸附至全體非 晶矽薄膜上,而是到處吸附之情形(覆蓋率、〗)。此時, 本發明之金屬吸附裝置1 〇鞛控制吸附壓力、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 15 郎吸附濃度成如前述覆蓋率小於1之優點。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 thin crucible of the amorphous crucible in a state of less than one atomic layer. Here, 10 or 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, the metal is not continuously adsorbed onto the entire amorphous germanium film, but is adsorbed everywhere. The situation (coverage, 〗). At this time, the metal adsorption device 1 of the present invention controls at least one of the adsorption pressure, the adsorption time, and the adsorption temperature, and the adsorption temperature can be finely adjusted, so that the adsorption concentration is adjusted to 15 Lang as the above coverage is less than 1 The advantages.
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)從室排出(沖洗)而去除。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上之來源氣 20體),而從非晶矽薄膜分離去除之來源氣體。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,使用以使來源氣體順利移動之搬運氣體 流入,而可利用於排出來源氣體。 接著’將金屬吸附至非晶矽薄膜上之過程係使吸附至 12 1377173 非晶石夕薄膜之金屬有機化合物與輔助氣體反應,而去除金 屬有機化合物令之有機化合物者Next, in the adsorption step, the source gas (metal organic compound) which is not adsorbed onto the amorphous tantalum film is discharged (rinsed) from the chamber to be removed. 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, physically adsorbed to the source gas 20 on the amorphous germanium film), and is separated from the amorphous germanium film. Source gas. When this step is completed, the process of adsorbing the source gas (metal compound) onto the amorphous germanium film is completed. At this time, it is possible to use a carrier gas for smoothly moving the source gas to flow, and it is possible to use the source gas. Then, the process of adsorbing the metal onto the amorphous germanium film is such that the metal organic compound adsorbed to the 12 1377173 amorphous film is reacted with the auxiliary gas to remove the metal organic compound and the organic compound.
。因此,將輔助氣體供給 至吸附有金屬有機化合物之非晶石夕薄膜上。如此供給之輔 助氣體與吸附至非晶矽薄膜上之金屬有機化合物反應,最 5後,將金屬吸附至非晶矽薄膜上。舉例言之,藉使來源氣 體Ni (cp) 2與輔助氣體反應,去除cp成份,而將Ni吸附至 非晶石夕薄膜上[即’ Ni ( cp ) 2+H2—Ni+mCnH2n+2] »在本發明 中,輔助氣體可使用Η2、NH3等還原性氣體、02、N2〇、H 2〇、臭氧等氧化性氣體、Ar、N2等惰性氣體。 10 接著,使藉來源氣體與輔助氣體之反應結果產生之副 產物氣體從室排出(排空)。當此步驟結束時,將金屬吸附 至非晶矽薄膜上之過程便結束。此時,使用以使來源氣體 順利移動之搬運氣體流人,可利用於排出副產物氣體。 接著,就將吸附有金屬之非晶矽薄膜熱處理,製造多 15晶石夕薄膜之過程作說明。此過程係以前述金屬誘發結晶化 方式使石夕結晶化者,亦有藉吸附至非晶石夕薄膜上之金屬觸 媒將矽之結晶化溫度降低至玻璃基板可使用之程度之情 形0 首先,本發明之熱處理係藉於維持在預定熱處理溫度 之室内使吸附有金屬之非晶石夕薄膜待機而進行。在此,亦 有室係與在金屬有機化合物之吸附步驟❹之室相同者之 情形,亦有為不同之室之情形。即,有吸附與熱處理過程 皆在1個㈣進行之情形’亦有吸附與熱處理過程分別在不 同之室進行之情形。 13 熱處理溫度以400至700〇c之範圍為佳。當熱處理溫度 非常低時,由於結晶化之時間增長,故必須考慮有關生產 性(處理量)之問題,當熱處理溫度非常高時,必須考慮 有關玻璃基板之變形之問題。熱處理時間以丨至⑺小時之範 圍為佳。當熱處理時間非常短時,必須考慮非晶矽之結晶 化不佳之問題’當熱處理時間非常長時,必須考慮生產性 問題。熱處理時之環境以惰性氣體環境為佳。在此,使用 之惰性氣體含有Ar、Ne、He、&氣體。藉此,藉第1實施 形態,完成形成TFT用多晶矽薄臈之過程。在本發明中,藉 將導入以降低結晶化溫度之金屬濃度儘量降低,具有可明 顯減低TFT之金屬污染,提高TFT之性能及採用ktft之半 導體或顯示器之各特性之優點。 第2 ’就在本發明第2實施形態中,將金屬有機化合物 吸附至非晶矽薄膜上後’將其熱處理,形成多晶矽薄膜之 方法作說明。在本發明第2實施形態中,至將金屬有機化合 物吸附至非晶質矽薄上之步驟為止皆與第1實施形態相 同。即’本發明第2實施形態係以與第1實施形態相同之方 法將金屬有機化合物吸附至非晶矽薄膜上後,即刻熱處 理’形成多晶矽薄膜之方法。在本發明第2實施形態中,省 略與第1實施形態相同之過程有關之詳細說明,在此,僅就 熱處理階段之差異點作說明。 第2實施形態之熱處理階段關於基本概念與熱處理條 件大致與第1實施形態相同。惟,在第2實施形態之熱處理 步驟中,去除吸附至非晶矽薄膜上之金屬有機化合物中之 關之過程與使非晶石夕結晶化之過程皆進行。因此 關聯性,第2竇0 環境有里形態相較於第1實施形態’熱處理時氣體 Λ Ρ在第2實施形態中,可在熱處理步驟使用 5第丨實知形態使用之輔助氣體,以促進從金屬有機化合物去 '、有機化δ物之反應。因*,在本發明第2實施形態中在 ^處理步驟’可使㈣2、ν2〇、Η2ο、臭氧等氧化輯體環 士見及Η2、而3等還原性氣體中之1個。當然在第2實施形態 中’亦可如第1實施形態般,在熱處理步驟,使用含有八!·、 Ne ' He、Ν2氣體之惰性氣體環境。 1〇 在第2實麵態巾,可在減理步驟,使用氧化性氣體 與惰性氣體之混合氣體環境及還原性氣體與惰性氣體之混 合氣體中之任一個。在第2實施形態之熱處理步驟使用混合 氣體時’混合氣體之比例以惰性氣體在5〇至99%之範圍為 佳。在第2實施形態之熱處理步驟,氣體環境之外之熱處理 15 溫度或熱處理時間宜與第1實施形態之條件範圍相同。藉 此,藉第2實施形態,完成形成TFT用多晶矽薄膜之過程。 與第1實施形態同樣地,藉將導入以降低結晶化溫度之金屬 濃度儘量降低,具有可明顯減低TFT之金屬污染,提高TFT 之性能及採用此TFT之半導體或顯示器之各特性之優點。. Therefore, the assist gas is supplied to the amorphous film which is adsorbed with the metal organic compound. The auxiliary gas thus supplied is reacted with the 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 (cp) 2 reacts with the auxiliary gas, the cp component is removed, and Ni is adsorbed onto the amorphous film (ie, 'Ni ( cp ) 2+H2—Ni+mCnH2n+2] In the present invention, the assist gas may be a reducing gas such as ruthenium 2 or NH3, an oxidizing gas such as 02, N 2 〇, H 2 〇 or ozone, or an inert gas such as Ar or N 2 . 10 Next, the by-product gas generated as a result of the reaction between the source gas and the assist gas is discharged (empty) from the chamber. At the end of this step, the process of adsorbing the metal onto the amorphous germanium film is completed. At this time, a carrier gas stream for smoothly moving the source gas can be used to discharge the by-product gas. Next, a process of heat-treating a metal-doped amorphous ruthenium film to produce a multi-fine crystal film will be described. This process is based on the metal induced crystallization method described above, and the crystallization temperature of the ruthenium is reduced to the extent that the glass substrate can be used by the metal catalyst adsorbed onto the amorphous film. The heat treatment of the present invention is carried out by waiting for the amorphous metal film adsorbed on the metal to stand by in the chamber maintained at the predetermined heat treatment temperature. Here, there are cases where the chamber is the same as the chamber in the adsorption step of the metal organic compound, and there are cases where the chamber is different. That is, there are cases where both adsorption and heat treatment processes are carried out in one (four)', and the adsorption and heat treatment processes are carried out in separate chambers, respectively. 13 The heat treatment temperature is preferably in the range of 400 to 700 〇c. When the heat treatment temperature is very low, since the crystallization time is increased, the problem of productivity (handling amount) must be considered. When the heat treatment temperature is very high, the problem of deformation of the glass substrate must be considered. The heat treatment time is preferably in the range of 丨 to (7) hours. When the heat treatment time is very short, the problem of poor crystallization of the amorphous ruthenium must be considered. When the heat treatment time is very long, the productivity problem must be considered. The environment during heat treatment is preferably an inert gas atmosphere. Here, the inert gas used contains Ar, Ne, He, & gas. As a result, in the first embodiment, the process of forming the polysilicon thin film for TFT is completed. In the present invention, the metal concentration introduced to lower the crystallization temperature is minimized, and there is an advantage that the metal contamination of the TFT can be remarkably reduced, the performance of the TFT can be improved, and the characteristics of the semiconductor or display using ktft can be obtained. In the second embodiment of the present invention, a method of forming a polycrystalline germanium film by heat-treating the metal organic compound onto the amorphous germanium film will be described. In the second embodiment of the present invention, the steps of adsorbing the metal organic compound onto the amorphous thin layer are the same as those in the first embodiment. That is, the second embodiment of the present invention is a method in which a metal organic compound is adsorbed onto an amorphous germanium film in the same manner as in the first embodiment, that is, a method of forming a polycrystalline germanium film by heat treatment. In the second embodiment of the present invention, the detailed description of the process similar to that of the first embodiment will be omitted. Here, only the differences in the heat treatment stage will be described. In the heat treatment stage of the second embodiment, the basic concept and the heat treatment conditions are substantially the same as those of the first embodiment. However, in the heat treatment step of the second embodiment, the process of removing the metal organic compound adsorbed onto the amorphous germanium film and the process of crystallizing the amorphous rock are carried out. Therefore, the relationship between the second sinus 0 environment and the first embodiment is different from that of the first embodiment. In the second embodiment, the auxiliary gas used in the 5th 丨 形态 在 can be used in the heat treatment step to promote From the metal organic compounds to ', the reaction of organic δ. In the second embodiment of the present invention, one of the reducing gases such as (4) 2, ν2〇, Η2ο, ozone, and the like, and 2, and 3, etc., may be used in the processing step. Of course, in the second embodiment, as in the first embodiment, an inert gas atmosphere containing VIII, Ne'He, and Ν2 gas may be used in the heat treatment step. 1〇 In the second solid surface towel, any one of a mixed gas atmosphere of an oxidizing gas and an inert gas and a mixed gas of a reducing gas and an inert gas may be used in the step of reducing the temperature. When the mixed gas is used in the heat treatment step of the second embodiment, the ratio of the mixed gas is preferably in the range of 5 Torr to 99% by inert gas. In the heat treatment step of the second embodiment, the heat treatment outside the gas atmosphere 15 is preferably the same as the temperature range of the first embodiment. Thus, in the second embodiment, the process of forming the polysilicon film for TFT is completed. As in the first embodiment, the metal concentration introduced to lower the crystallization temperature is reduced as much as possible, and the metal contamination of the TFT can be remarkably reduced, and the performance of the TFT and the characteristics of the semiconductor or display using the TFT can be improved.
20 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 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 15 1377173 揭示之本發明之範疇及思想下,進行多種變形及修正。 【圓式簡單說明】 (無) 【主要元件符號說明】 (無)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 applicability of the present invention is extremely high. In the meantime, the present invention has been described in a number of preferred embodiments, and it is to be understood that various modifications and changes can be made without departing from the scope and spirit of the invention as disclosed in the appended claims. Corrected. [Circular Simple Description] (None) [Main Component Symbol Description] (None)
16 (S )16 (S )
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