TW524713B - Method and device for treatment and recovery of CVD waste gas - Google Patents
Method and device for treatment and recovery of CVD waste gas Download PDFInfo
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524713 A7 B7524713 A7 B7
File:7666pif.doc/009 五、發明說明Π ) 發明領域 (請先閱讀背面之注意事項再填寫本頁) 本發明是關於化學氣相沈積（Chemieal vapQF Deposition; CVD)排氣之處理回收方法及裝置，詳細的§兌， 係關於在半導體製造過程中，使用氫鹵^石夕 (hydrohalogenated silicon)氣體以形成矽（sinc〇n)的嘉晶膜 (epitaxial film)、多晶膜或非晶膜，並將由化學氣相沈積 (CVD)裝置排出之排氣進行處理回收的方法&^_。 發明背景 經濟部智慧財產局員工消費合作社印製 矽的化學氣相沈積製程之一係爲磊晶（單晶成長）製 程，係使用以製作場效型金氧半電晶體(Field Effect Metal Oxide Semiconductor transistor)(金屬-氧化膜一石夕）之基板 或形成雙載子電晶體（bipolar transistor)之射極（emitter) 層。晶晶製程通常係使用砂（代）氯仿（trichlorosilane，TCS) 或二氯矽烷（dichlorosilane，DCS)等的氫鹵化矽氣體作爲 原料風體’並於氣的稀釋下導入製程室（process chamber) 中’於製程室內所設置之基板上加熱至攝氏1100度左右 以使原料氣體發生熱分解，而於基板上進行砂的堆積。此 時的製程條件通常爲在一大氣壓至lOOPa左右的壓力範圍 內進行。 另一方面，多晶成長製程係使用以形成場效型金氧半 電晶體之閘電極或電容器之底層。多晶成長製程通常係將 使用砂（代）氯仿或二氯砂院等的氫鹵化砂氣體利用氫進 行稀釋後，導入設置於製程室內的基板上並加熱至攝氏800 度左右，使原料氣體進行熱分解而堆積於基板上。此時的 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 524713File: 7666pif.doc / 009 V. Description of the invention Π) Field of invention (please read the precautions on the back before filling out this page) The present invention relates to a chemical vapour deposition (Chemieal vapQF Deposition; CVD) exhaust gas treatment and recovery method and The device, detailed §, relates to the use of hydrohalogenated silicon gas to form an epitaxial film, polycrystalline film, or amorphous film of silicon during the semiconductor manufacturing process. And a method for treating and recovering exhaust gas discharged from a chemical vapor deposition (CVD) device & ^ _. BACKGROUND OF THE INVENTION One of the chemical vapor deposition processes for the production of silicon by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics is an epitaxial (single crystal growth) process, which is used to make Field Effect Metal Oxide Semiconductors. A transistor (metal-oxide film), or an emitter layer forming a bipolar transistor. The Jingjing process usually uses silicon (hydrogen halide) gas such as trichlorosilane (TCS) or dichlorosilane (DCS) as the raw material air body and is introduced into the process chamber under the dilution of the gas. 'Heated on the substrate set in the process chamber to about 1100 degrees Celsius to thermally decompose the raw material gas, and sand was deposited on the substrate. The process conditions at this time are usually carried out in a pressure range from atmospheric pressure to about 100 Pa. On the other hand, the polycrystalline growth process is used to form the gate electrode or the bottom layer of a capacitor of a field-effect metal-oxide semiconductor. The polycrystalline growth process usually involves diluting a hydrohalogenated sand gas such as sand (substituting) chloroform or dichloro sand factory with hydrogen, and then introducing it onto a substrate installed in the process chamber and heating it to about 800 degrees Celsius to allow the raw material gas to be processed. Pyrolyzed and deposited on a substrate. At this time, the 4 paper sizes are in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524713
File：7666pif.doc/009 A7 B7 五、發明說明（z) 製程條件通常在lOOPa左右之壓力下進行。 又，在上述製程之下，爲了在晶圓（wafer)搬入搬出製 程室之過程中伴隨著晶圓吸附水分的管理，因此在排氣管 路系統中設有水分測定裝置，例如安裝有傅立葉變換紅外 線（Fourier transform infrared，FT-IR)分光儀等之情形。 在上述之結晶成長製程之中，實際上有助於矽之堆積 的热體重約爲全部導入量的5 %左右’剩餘的大部分原料 氣體對堆積並無任何幫助，中間產物（全部量的數％左右） 與排氣一同自室中排出。由室內排出之排氣在經由除害裝 置去除原料氣體或中間產物而無害化之後，利用載氣之氫 或淸除氣體之氮氣排出至大氣中。 此時，於磊晶製程中，發生於此製程之中間產物（副 生成物）會有附著•堆積於排氣管路之內面的問題，而導 致堆積物堵塞排氣管路。此中間產物，包括矽與氯之化合 物或是矽與氫之化合物。於常溫下在排氣管路之內面上形 成聚合物。所形成之聚合物係爲與大氣中的水分反應性（自 燃性或***性）高的物質，例如是，變化成聚矽氧烷 (polysiloxane)。因而，爲了去除附著於排氣管路內面的聚 合物，由排氣管路分解至開放的大氣之際，必須有各式各 樣的準備與竅門，導致降低化學氣相沈積裝置的工作效 率。 又，爲去除聚合堆積物使用三氟化氯（chl〇rine trifluoride)等的蝕刻氣體進行排氣管路的通虱’以此方法 可以去除於管路內面所堆積的中間產物或聚合物，然由於 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） ------J----i 裝--------訂--------- (請先閱讀背面之注咅？事項再填寫本頁) 524713 A7 B7File: 7666pif.doc / 009 A7 B7 V. Description of the Invention (z) The process conditions are usually performed under a pressure of about 100 Pa. In addition, under the above-mentioned process, in order to accompany the management of wafer adsorption of moisture during wafer transfer into and out of the process chamber, a moisture measurement device is provided in the exhaust pipe system, for example, a Fourier transform is installed In the case of infrared (Fourier transform infrared, FT-IR) spectrometer. In the above-mentioned crystal growth process, the thermal weight that actually contributes to the accumulation of silicon is about 5% of the total introduction amount. Most of the remaining raw material gases do not help the accumulation, and the intermediate products (the total amount %) Is discharged from the chamber together with the exhaust gas. The exhaust gas exhausted from the room is detoxified by removing the raw material gas or intermediate products through the harm removal device, and then exhausted to the atmosphere by using the hydrogen of the carrier gas or the nitrogen of the degassing gas. At this time, in the epitaxial process, the intermediate products (by-products) that occur during this process may adhere to and accumulate on the inner surface of the exhaust pipe, causing the accumulation to block the exhaust pipe. The intermediate products include silicon and chlorine compounds or silicon and hydrogen compounds. A polymer was formed on the inner surface of the exhaust pipe at normal temperature. The polymer formed is a substance that is highly reactive (self-igniting or explosive) with moisture in the atmosphere, for example, it is changed to polysiloxane. Therefore, in order to remove the polymer adhering to the inner surface of the exhaust pipe, when the exhaust pipe is decomposed to the open atmosphere, various preparations and tips must be prepared, which will reduce the working efficiency of the chemical vapor deposition device. . In addition, in order to remove the polymer deposits, using an etching gas such as chlorine trifluoride to carry out the blemishes of the exhaust pipe can remove the intermediate products or polymers deposited on the inner surface of the pipe. However, since 5 paper sizes are applicable to China National Standard (CNS) A4 (210 x 297 mm) ------ J ---- i Packing -------- Order ------ --- (Please read the note on the back? Matters before filling out this page) 524713 A7 B7
File:7 666pif. doc/009 五、發明說明（3 ) 強烈的蝕刻性而導致排氣管路受到腐蝕，且於此情形下會 有管路產生孔洞的問題存在。另外，三氟化氯之蝕刻氣體 與磊晶製程所使用之原料氣體通常無法僅使用一個除害裝 置處理，必須在各自的氣體進行通氣之情形下切替使用各 自對應的除害裝置。 另一方面，爲了防止中間產物附著•堆積於排氣管路 中，而提出有經常將管路加熱至攝氏150度左右的溫度的 方法。但，在此方法之下，當一部份的管路溫度較低之情 形時，中間產物會選擇性地堆積於低溫部分。通常，位於 除害裝置與化學氣相沈積裝置之間的管路，會因爲降低設 置面積的要求而形成複雜的彎曲部份，進而使管路系統難 以均一地加熱•保溫，且實際上，在前述之敘述中，係取 下管路再去除堆積於低溫部分的中間產物以進行保養維 修。 又，在進行矽（代）氯仿或二氯矽烷無害化之情形下， 大多使用使用水的洗滌器（scrubber)，利用水與矽（代）氯 仿或二氯矽烷反應生成固體的二氧化矽，在洗滌器中設有 使用循環水去除二氧化矽的手段。但，去除二氧化矽時， 由於其內部含有氫，因此在原有之排出過程中，二氧化砂 會與氟化氫產生反應。此作業由於需對除害裝置進行定期 的保養維修，而導致降低化學氣相沈積裝置之工作效率、 且由於去除所產生的二氧化矽的藥品費用或人爲費用，因 而產生額外的成本。 本發明之目的係提供一種化學氣相沈積排氣之處理回 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----,---d---·-裝--------訂---------Αφ (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 524713File: 7 666pif. Doc / 009 V. Description of the Invention (3) Exhaust pipelines are corroded due to strong etchability, and in this case, the problem of holes in the pipelines exists. In addition, the etching gas of chlorine trifluoride and the raw material gas used in the epitaxial process cannot usually be treated with only one detoxification device, and the corresponding detoxification device must be used instead when the respective gases are vented. On the other hand, in order to prevent the adhesion and accumulation of intermediate products in the exhaust pipe, a method has been proposed in which the pipe is often heated to a temperature of about 150 degrees Celsius. However, under this method, when the temperature of a part of the pipeline is relatively low, intermediate products are selectively accumulated in the low-temperature part. Generally, the pipeline between the detoxification device and the chemical vapor deposition device will form a complex curved part due to the reduction of the installation area requirement, which makes it difficult to uniformly heat and keep the pipeline system. In the foregoing description, the pipeline is removed and the intermediate products accumulated in the low temperature part are removed for maintenance. In addition, in the case of detoxification of silicon (generation) chloroform or dichlorosilane, a scrubber using water is mostly used, and water is reacted with silicon (generation) chloroform or dichlorosilane to form solid silicon dioxide. The scrubber is provided with a means for removing silicon dioxide using circulating water. However, when silicon dioxide is removed, because it contains hydrogen, sand dioxide will react with hydrogen fluoride during the original discharge process. This operation requires regular maintenance of the detoxification device, which reduces the working efficiency of the chemical vapor deposition device, and incurs additional costs due to the drug cost or human cost of removing the generated silicon dioxide. The purpose of the present invention is to provide a chemical vapor deposition exhaust gas treatment. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----, --- d --- ·- Packing -------- Order --------- Αφ (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524713
File:7666pif.d〇c/〇〇9 A7 —---—-— B7 五、發明說明（4 ) 收方法及裝置，係於結晶成長過程中，將所使用之原料氣 體或於此製程中所產生的具高揮發性之鹵化物的中間產物 進行轉化反應，以使到分離回收裝置之排氣不會附著•堆 積於排氣系統管路上，而得到具有再利用價値的資源與分 離回收物，並可使排氣管路或除害裝置之定期保養次數減 少或變成不必要。 發明槪| 爲了達到上述目地’本發明之化學氣相沈積排氣之處 理回收方法，係使用氫鹵化矽氣體形成矽薄膜後，對由化 學氣相沈積裝置排出之排氣進行處理的方法，係具有將前 述排氣中所含有之未反應的原料氣體及中間產物進行分解 處理或轉化反應處理，並於分解一部份之後，對氫鹵化矽 氣體與氯化氫進行分離回收的特徵，前述轉化反應處理係 加熱至攝氏4〇〇度以上，再與鐵反應劑接觸以進行反應， 且對進行前述轉化反應處理之後的排氣進行精餾分離。 又，本發明之方法，係使用氫鹵化矽氣體形成矽薄膜 後’對由化學氣相沈積裝置排出之排氣進行處理的方法， 係具有將前述排氣中所含有之未反應的原料氣體及中間產 物全部進行分解處理，並對分解生成物之氯化氫進行回收 的特徵，前述分解處理係在常溫至攝氏500度之間，使用 鐵反應劑進行熱脫附。 本發明之化學氣相沈積排氣之處理回收裝置，係使用 氫鹵化ΐ夕氣體形成砂薄膜後，對由化學氣相沈積裝置排出 之排氣進行處理的裝置，係設有將前述排氣中所含有之未 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 tT--------- 經濟部智慧財產局員工消費合作社印製 524713 A7 B7File: 7666pif.d〇c / 〇〇9 A7 --------- B7 V. Description of the invention (4) The collection method and device are used in the process of crystal growth, and the raw material gas used or in this process The generated highly volatile halide intermediate product undergoes a conversion reaction, so that the exhaust gas to the separation and recovery device does not adhere to and accumulate on the exhaust system pipeline, so as to obtain a resource and separation and recovery material with a high recycling price. , And can reduce the number of regular maintenance of exhaust lines or harm removal devices or become unnecessary. Invention 槪 | In order to achieve the above-mentioned purpose, the method for treating and recovering the chemical vapor deposition exhaust gas of the present invention is a method for treating the exhaust gas discharged from the chemical vapor deposition device after forming a silicon film by using a silicon hydrohalide gas. It has the characteristics that the unreacted raw material gas and intermediate products contained in the exhaust gas are subjected to decomposition treatment or conversion reaction treatment, and after a part of the decomposition, the silicon hydrohalide gas and hydrogen chloride are separated and recovered. It is heated to more than 400 degrees Celsius, and then brought into contact with an iron reactant for reaction, and the exhaust gas after the aforementioned conversion reaction treatment is subjected to rectification separation. In addition, the method of the present invention is a method for processing an exhaust gas discharged from a chemical vapor deposition device after forming a silicon thin film using a silicon hydrohalide gas, and includes an unreacted raw material gas contained in the exhaust gas and All the intermediate products are decomposed and the hydrogen chloride of the decomposed product is recovered. The aforementioned decomposition treatment is performed at a temperature between normal temperature and 500 degrees Celsius, and is thermally desorbed with an iron reactant. The chemical vapor deposition exhaust gas treatment and recovery device of the present invention is a device for processing the exhaust gas discharged from the chemical vapor deposition device after forming a sand film by using a hydrohalide gas, and is provided with Contains less than 7 paper sizes that are in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling this page). TT --------- Ministry of Economic Affairs Printed by the Intellectual Property Bureau Employee Consumer Cooperative 524713 A7 B7
File:7666pif.doc/〇〇9 五、發明說明（b ) 反應的原料氣體及中間產物之一部份進行分解的分解反應 手段、自由前述分解反應手段所導出之排氣中分離氫鹵化 矽與氯化氫的分離手段、將在前述分離手段下所分離出的 氯化氫與水接觸的氣液接觸手段、以及使氫鹵化矽再使用 的氣體回收手段。 又’本發明之化學氣相沈積排氣之處理回收裝置，係 使用氫鹵化矽氣體形成矽薄膜後，對由化學氣相沈積裝置 排出之排氣進行處理的裝置，係設有將前述排氣中所含有 之未反應的原料氣體及中間產物完全分解成氯化氫的分解 反應手段、以及將由前述分解反應手段所導出的氯化氫與 水接觸的氣液接觸手段。 圖式之簡裏銳明 第1圖所示爲本發明之第一較佳實施例之化學氣相沈 積排氣之處理回收裝置的系統圖。 第2圖所示爲本發明之第一較佳實施例之反應器之一 例的槪略系統圖。 第3圖所示爲本發明之第二較佳實施例的系統圖。 第4圖所示爲本發明之第三較佳實施例的系統圖。 第5圖所示爲本發明之第三較佳實施例之反應器之一 例的槪略系統圖。 第6圖所示爲在第一實例中自反應器流出之氣體成分 變化的測量結果圖。 第7圖所示爲在第二實例中自反應器流出之氣體成分 變化的測量結果圖。 / 一 I I · I I I--I I 訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 524713File: 7666pif.doc / 〇〇9 V. Description of the invention (b) Decomposition reaction means for decomposing a part of the raw material gas and intermediate products of the reaction, separating silicon hydrohalide from the exhaust gas derived from the aforementioned decomposition reaction means A means for separating hydrogen chloride, a gas-liquid contact means for contacting the hydrogen chloride separated by the aforementioned means with water, and a gas recovery means for reusing silicon hydrohalide. Also, the chemical vapor deposition exhaust gas treatment and recovery device of the present invention is a device for processing the exhaust gas discharged from the chemical vapor deposition device after forming a silicon film by using a silicon hydrohalide gas, and is provided with the aforementioned exhaust gas Decomposition reaction means for completely decomposing unreacted raw material gas and intermediate products contained therein into hydrogen chloride, and gas-liquid contact means for contacting hydrogen chloride derived from the aforementioned decomposition reaction means with water. The figure is simple and sharp. Figure 1 shows a system diagram of a chemical vapor deposition exhaust gas treatment and recovery device according to the first preferred embodiment of the present invention. Fig. 2 is a schematic system diagram showing an example of the reactor of the first preferred embodiment of the present invention. Fig. 3 shows a system diagram of a second preferred embodiment of the present invention. FIG. 4 shows a system diagram of a third preferred embodiment of the present invention. Fig. 5 is a schematic system diagram showing an example of a reactor according to a third preferred embodiment of the present invention. Fig. 6 is a graph showing the measurement results of changes in the gas composition flowing out of the reactor in the first example. Fig. 7 is a graph showing measurement results of changes in gas composition flowing out of the reactor in the second example. / 一 I I · I I I--I I Order --------- (Please read the notes on the back before filling this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 524713
File:7666pif.doc/009 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（G ) 圖式之標記說明 10 :化學氣相沈積裝置 11 :基板（晶圓） 12 :製程室 12a :氣體導入部 12b :導出部 13 :氣體供給裝置 14 :排氣泵 15 :加熱台 16 :水分測量手段 17 :加熱或保溫手段 21，31 :反應器 22 :分離器 23 :回收管路 24，32 :氣液接觸槽 25，26，27，33 :管路 較佳實施例之詳細說明 第1圖所示爲本發明之第一較佳實施例之化學氣相沈 積排氣之處理回收裝置的系統圖。第2圖所示爲本發明之 第一較佳實施例之反應器之一例的槪略系統圖。又，本發 明之設備對象係爲化學氣相沈積裝置，即，對使用氫鹵化 矽氣體形成矽薄膜之化學氣相沈積裝置進行說明。本較佳 實施例所示之化學氣相沈積裝置1〇，一般稱爲單一照射器 (lamp)加熱式磊晶矽裝置，係包括設置有基板（晶圓）11 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------y----I 裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 524713File: 7666pif.doc / 009 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (G) Marking of the drawings 10: Chemical vapor deposition device 11: Substrate (wafer) 12: Process room 12a : Gas introduction part 12b: lead-out part 13: gas supply device 14: exhaust pump 15: heating stage 16: moisture measuring means 17: heating or holding means 21, 31: reactor 22: separator 23: recovery line 24, 32: Gas-liquid contact tanks 25, 26, 27, 33: Detailed description of the preferred embodiment of the pipeline. FIG. 1 shows a chemical vapor deposition exhaust gas treatment and recovery device of the first preferred embodiment of the present invention. System diagram. Fig. 2 is a schematic system diagram showing an example of a reactor according to the first preferred embodiment of the present invention. The object of the present invention is a chemical vapor deposition apparatus, that is, a chemical vapor deposition apparatus for forming a silicon thin film using a silicon hydrohalide gas. The chemical vapor deposition device 10 shown in this preferred embodiment is generally referred to as a single-lamp-heated epitaxial silicon device, and includes a substrate (wafer) 11 9 This paper size is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm) -------- y ---- I installed -------- order --------- (Please read the back first (Please fill in this page again) 524713
File:7666pif.doc/009 A7 B7 五、發明說明（7 ) 的製程室12、提供製程室I2內的原料氣體、洗滌用氣體、 淸除氣體及載氣氣體的氣體供給裝置1 3、以及將氣體由製 程室12排出的排氣泵14。 前述製程室12係經由閘閥（未圖示）而與負載室 (Loading Chamber)(未圖示）連接。又，在製程室I2中’ 設有將搭載有晶圓11之加熱台（suSCept〇r)15或晶圓Π加 熱至所定溫度之加熱手段（照射器：未圖示）° 此化學氣相沈積裝置1〇係利用在稀釋氣體下使原料 氣體流動而稀釋之排氣，並維持製程室12內之壓力於一 大氣壓左右以在晶圓11上進行磊晶的成長。例如’以進 行p型磊晶成長之際的典型序列（sequence)進行說明，又， 藉由提供流量爲2L (升(liter)，以下皆同）/分之含有淸除 氣體的氮氣至製程室內，將晶圓藉由閘閥搬入，並載置於 加熱台上。在關閉閘閥之後，將供給氣體由氮氣切換成氯 ' 、，當製程室內置換成氫氣氛之後將晶 氣（流量：1.5L/分） 圓加熱至攝氏1200度 在攝氏1200度、 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -大氣壓之氫氣氛下，奸 晶圓平坦化處理之後，於晶圓之加熱溫度爲攝氏i 乂 及一大氣壓下，開始提供磊晶成長氣體，此處理15() 2分鐘。通常，使用混合在7L/分之氫氣 度 分鐘。通常，使用混合在7L/分之氫氣中含有^^Π進行 比率tcs (矽（代）氯仿）的氣體、及在l4 g/分之 刀之氮氣 斤得的混含今 體。又，在使用DCS (二氯矽烷）替代TCS之情形下 中含有l5〇cc/分之乙硼烷（diborane)的氣 之流量爲l〇g/分，且晶圓11之溫度爲攝氏1〇8q 度 DCS又， .裝--------^--------- 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 524713File: 7666pif.doc / 009 A7 B7 V. Process chamber 12 of the invention description (7), a gas supply device 1 for supplying raw material gas, washing gas, scavenging gas and carrier gas in the process chamber I2 1 and The gas is discharged from an exhaust pump 14 of the process chamber 12. The process chamber 12 is connected to a loading chamber (not shown) via a gate valve (not shown). In addition, in the process chamber I2, a heating means (irradiator: not shown) for heating the heating table (suSCeptor 15) on which the wafer 11 is mounted or the wafer Π to a predetermined temperature is provided. ° This chemical vapor deposition The device 10 uses an exhaust gas that is diluted by flowing a source gas under a diluent gas, and maintains the pressure in the process chamber 12 at about one atmosphere to perform epitaxial growth on the wafer 11. For example, 'a typical sequence for p-type epitaxial growth will be described, and by providing a flow rate of 2L (liter (the same applies hereinafter)) per minute of nitrogen containing scavenging gas into the process chamber The wafer is carried in through a gate valve and placed on a heating table. After closing the gate valve, switch the supply gas from nitrogen to chlorine. When the process chamber is replaced with a hydrogen atmosphere, heat the crystal gas (flow rate: 1.5L / min) to a temperature of 1200 ° C at 1200 ° C. (Please read first Note on the back, please fill out this page again.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-Atmospheric pressure in a hydrogen atmosphere. After flattening the wafer, the wafer will be heated at a temperature of 1 ° C and atmospheric pressure. Provide epitaxial growth gas, this process is 15 () 2 minutes. Normally, mix at 7 L / min hydrogen for minutes. Generally, a gas containing ^^ Π with a ratio of ^^ Π in 7 L / min of hydrogen and a nitrogen gas at 14 g / min of nitrogen is used. In the case where DCS (dichlorosilane) is used instead of TCS, the flow rate of the gas containing 150 cc / diborane is 10 g / min, and the temperature of the wafer 11 is 1 ° C. 8q degree DCS, and installed -------- ^ --------- 10 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperative 524713
File:7666pif.doc/009 A7 _____ B7 五、發明說明（8 ) 使用η型代替P型之際，則需提供磷化氫（phosphine)取代 乙硼烷。此時’流量約與使用乙硼烷之情形相同。 在處理完成後’供給氣體由磊晶反應氣體切換成10L/ 分之氮氣，並將已完成所定處理之晶圓搬出。接著，將供 給氣體切換成氮氣與氯化氫氣體之混合氣體，藉由維持流 率爲7〜15L/分之混合氣體之氣氛，且維持於攝氏11 5〇度， 一大氣壓之下，以去除製程室內之附著物或堆積物。 最後，供給氣體回到10L/分之氮氣，並將加熱台之溫 度降溫至常溫附近。如此一個循環之處理製程即結束，而 回到最初之晶圓搬入。 在以上所述中’各個步驟所使用之種種氣體皆由氣體 供給裝置Π導入製程室12中，以進行製程。氣體切換之 際伴隨著氣體的自身分解反應，特別是，可防止些微的水 分與TCS或DCS等的原料氣體之反應而將原料氣體分解 進而吸附於管路之表面，且由氣體混合部開始至製程室入 口爲止’較佳係爲將不绣鋼在弱氧化性•強還原性之氣氛 下施加攝氏400度左右的熱處理以於其內表面形成氧化鉻 膜或者是將含有數％鋁的不銹鋼在弱氧化性•強還原性之 氣氛下施加攝氏900度左右的熱處理以於其內表面形成氧 化鋁膜。 又’伴隨著此分解反應之有無或是晶圓之搬入·搬出， 爲了監測製程室內的水分濃度，而於製程室12之氣體導 入部12a及導出部12b設置使用光學手段的水分測量手段 16 ’特別是，水分測量手段16較佳係爲使用光源對半導 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） ---1----7---裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 524713File: 7666pif.doc / 009 A7 _____ B7 V. Description of the invention (8) When using η type instead of P type, phosphine should be provided instead of diborane. At this time, the 'flow rate is about the same as in the case of using diborane. After the processing is completed, the supply gas is switched from the epitaxial reaction gas to 10 L / min nitrogen, and the wafer having completed the predetermined processing is carried out. Next, the supply gas was switched to a mixed gas of nitrogen and hydrogen chloride gas, and the atmosphere of the mixed gas with a flow rate of 7 to 15 L / min was maintained, and maintained at 11 to 50 degrees Celsius under one atmosphere of pressure to remove the process chamber Attachments or deposits. Finally, the supply gas was returned to 10 L / min of nitrogen, and the temperature of the heating table was lowered to near normal temperature. The processing process of such a cycle is ended, and the original wafer is moved in. The various gases used in the above steps are introduced into the process chamber 12 by the gas supply device Π to perform the process. Gas switching is accompanied by the gas's own decomposition reaction. In particular, it can prevent the reaction of a small amount of moisture with the raw material gas such as TCS or DCS to decompose the raw material gas and adsorb it on the surface of the pipeline. Up to the entrance of the process room, it is preferred that the stainless steel be subjected to a heat treatment of about 400 degrees Celsius in a weakly oxidizing and strong reducing atmosphere to form a chromium oxide film on its inner surface or a stainless steel containing a few percent aluminum. In a weakly oxidizing and strong reducing atmosphere, a heat treatment of about 900 degrees Celsius is applied to form an aluminum oxide film on the inner surface. In addition, in accordance with the presence or absence of this decomposition reaction or the loading and unloading of wafers, in order to monitor the moisture concentration in the process chamber, a gas measurement unit 16 using optical means is installed in the gas introduction part 12a and the lead-out part 12b of the process chamber 12. In particular, the moisture measuring means 16 is preferably a light source that applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) to the paper size of the semiconducting paper. ------- Order --------- (Please read the notes on the back before filling this page) 524713
File:7666pif.doc/009 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明) 體激光測量的激光分光度計。如此，可確實掌握與控制_ 程室內之氣氛，進而可降低仿真線（dummy wire)之現象。 另一方面，對由製程室12排出之排氣中所含有之未 反應之原料氣體及中間產物進行處理與回收之處理回收裝 置係爲前述排氣泵14，例如是，設置含有螺旋泵（screw pump)之排氣系統管路係設有具有將排氣中所含有之未反 應原料氣體或高沸點中間產物分解或反應轉化的分解反應 手段的反應器21、具有將經前述反應器21處理後所導出 之排氣精餾分離成分離的氫鹵化矽氣體與氯化氫的分離手 段的分離器22、具有將經由前述分離器22精餾分離之氫 鹵化矽氣體利用例如是前述氣體供給裝置13中的TCS回 收再使用的氣體回收手段的回收管路23、以及具有使精餾 分離後分離之氯化氫與水接觸之氣液接觸手段的氣液接觸 槽24 〇 在前述序列之中，由化學氣相沈積裝置10於各步驟 中之各式各樣的氣體成分經由排氣系統管路排出，藉由排 氣泵14流入前述反應器21中。此反應器21在前述敘述 中，係對排氣中所含有之未反應原料氣體或中間產物進行 分解處理或轉化反應處理，並對成爲對象之氣體成分進行 適當的處理，並對過渡金屬反應劑加熱至所定溫度，例如 較佳爲利用鐵（Fe)加熱至攝氏400度以上形成鐵反應劑， 且與排氣接觸之方法。 對前述過渡金屬反應劑加熱之加熱手段係可使用電加 熱器等任意器具。在此加熱手段中加熱溫度係隨著對象成 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) T裝---- 1T--------- 524713 A7 B7File: 7666pif.doc / 009 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention) Laser spectrophotometer for volume laser measurement. In this way, the atmosphere in the process chamber can be accurately grasped and controlled, thereby reducing the phenomenon of dummy wires. On the other hand, a processing and recovery device for processing and recovering unreacted raw material gas and intermediate products contained in the exhaust gas discharged from the process chamber 12 is the aforementioned exhaust pump 14. For example, a screw pump (screw) The exhaust system piping of the pump) is provided with a reactor 21 having a decomposition reaction means for decomposing or reacting the unreacted raw material gas or high-boiling intermediate products contained in the exhaust gas, and having been processed by the aforementioned reactor 21 The separator 22 for separating the derived exhaust gas rectification into separated silicon hydrohalide gas and hydrogen chloride, and a method for using the silicon hydrohalide gas separated by rectification through the separator 22, for example, are used in the gas supply device 13. A recovery line 23 of a gas recovery means for TCS recovery and reuse, and a gas-liquid contact tank 24 having a gas-liquid contact means for contacting the separated hydrogen chloride with water after rectification. In the foregoing sequence, chemical vapor deposition Various gas components of the apparatus 10 in each step are discharged through the exhaust system pipe, and flowed into the aforementioned reactor 21 through the exhaust pump 14. In the foregoing description, the reactor 21 performs a decomposition treatment or a conversion reaction treatment on an unreacted raw material gas or an intermediate product contained in the exhaust gas, and appropriately processes a target gas component and a transition metal reactant. Heating to a predetermined temperature is preferably a method in which iron (Fe) is heated to 400 ° C or more to form an iron reactant and is in contact with the exhaust gas. The heating means for heating the transition metal reactant may be any device such as an electric heater. In this heating method, the heating temperature is in accordance with the cost of the paper. The Chinese national standard (CNS) A4 specification (210 X 297 mm) is applied (please read the precautions on the back before filling this page). --------- 524713 A7 B7
File:7666pif.doc/009 i、發明說明（\0 ) (請先閱讀背面之注意事項再填寫本頁) 分而異，通常係在攝氏4〇〇度以上，例如較佳爲介於攝氏 4〇〇度至攝氏500度之間。又，形成反應器21之材料或反 應劑之耐熱溫度等皆會對加熱條件予以限制，當加熱至必 須溫度以上時，會減少處理效率之上昇效果，但會增加能 源的損失。又，當反應器21使用不銹鋼之情形下，加熱 至攝氏500度以上，會使氯化氫氣體或氫氣解離而生成具 有活性之氫自由基，進而發生助長脆化之情形。 另外，反應器21在考慮保養維護（反應劑之交換或 活性化）等問題之下，如第2圖所示，多個反應器21、21 藉由閥而並列設置，可適於作爲切換使用。又，至反應器 21之排氣系統管路，即，來自製程室12之出口部經由排 氣泵I4而至反應器21之排氣管路，爲了防止在前述管路 內產生附著物，因此設有覆蓋於此之加熱手段或保溫手段 17 ’以使排氣管路維持於適當溫度，例如較佳爲加熱或保 温於攝氏150度左右。又，當製程室12之氣體溫度較高 時’加熱手段不需使用高容量的加熱器，於排氣管路之外 周捲繞絕熱材料即可有完全保溫之效果。但，需對應排氣 管路之長度或材質等使用適當的加熱手段或保溫手段，當 經濟部智慧財產局員工消費合作社印製 排氣管路較短，且流入反應器之氣體溫度足夠時即可省略 不使用。 在則述排氣管路中，較佳係使用前述在表面所形成氧 化鉻吴或氧化鋁膜。此時對管路通路施加熱處理，即使在 活性氯自由基等存在之下也不會發生腐蝕等不適合之情 形。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 524713File: 7666pif.doc / 009 i. Description of the invention (\ 0) (Please read the notes on the back before filling this page) It varies, usually it is above 400 ° C, for example, it is preferably between 4 ° C 〇〇 degrees to 500 degrees Celsius. In addition, the material forming the reactor 21 or the heat-resistant temperature of the reactant will limit the heating conditions. When the temperature is higher than the necessary temperature, the effect of increasing the processing efficiency will be reduced, but the energy loss will be increased. When stainless steel is used in the reactor 21, heating to 500 degrees Celsius or more will dissociate hydrogen chloride gas or hydrogen gas to generate active hydrogen radicals, which may promote embrittlement. In addition, the reactor 21 is considered for maintenance (exchange or activation of reactants), and as shown in FIG. 2, a plurality of reactors 21 and 21 are arranged in parallel by a valve, which is suitable for switching. . In addition, the exhaust system pipeline to the reactor 21, that is, the outlet from the process chamber 12 to the exhaust pipeline of the reactor 21 through the exhaust pump I4, in order to prevent adhesions from occurring in the aforementioned pipeline, A heating means or a thermal insulation means 17 'is provided to cover the exhaust pipe at an appropriate temperature, for example, heating or thermal insulation is preferably about 150 degrees Celsius. In addition, when the gas temperature of the process chamber 12 is high, the heating means does not need to use a high-capacity heater, and a heat-insulating material can be wound around the exhaust pipe to obtain a complete thermal insulation effect. However, it is necessary to use appropriate heating methods or insulation methods corresponding to the length or material of the exhaust pipe. When the exhaust pipe printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is short, and the temperature of the gas flowing into the reactor is sufficient, Can be omitted and not used. In the exhaust pipe described above, it is preferable to use the aforementioned chromium oxide or aluminum oxide film formed on the surface. At this time, heat treatment is applied to the pipeline path, and even in the presence of active chlorine radicals, unsuitable situations such as corrosion do not occur. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 524713
File:7666pif.doc/009 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（\\) 此時，將由化學氣相沈積裝置10所形成之排氣導入 反應器21中，含有未反應原料氣體之TCS或DCS之一部 份與其副產物反應或轉化，以將所產生之氯化氫與砂利用 過渡金屬反應劑等產生轉化反應而結合去除。同樣地’乙 硼院或磷化氫中的硼或磷與反應劑結合而去除。 在此反應中氫是必須的，雖然TCS或DCS本身具有 氫原子，又，在前述之敘述中，通常的磊晶成長過程中， 氣氛氣體或稀釋氣體爲使用氫氣之情形下，反應進行之全 部問題，係爲使轉化反應容易進行。但，爲輔助成長反應 而使用等離子(plasma)之情形等，致使排氣中之氫氣不足 之情形之下，於反應器21之前斷的排氣管路中，較佳係 設置可添加氫氣於排氣中的氫氣添加手段，以添加適當量 的氫氣。 將由反應器21所排出之排氣導入分離器22中，以將 具有原料氣體之TCS或DCS與氯化氫分離。此分離器22 之結構或操作方法係爲對應排氣之組成、回收之原料氣體 種類、回收率、純度，以適當地選擇操作壓力、精餾分離 溫度、精餾分離器之層段數等。例如，使用層段數爲七段 的精餾筒，保持壓力爲150kPa、溫度爲283K之狀態下， 導入來自反應器21之排氣，氯化氫濃度爲lpprn以下之TCS 由分離器22之上半部取出，此時，可回收大約99%左右 之TCS導入量。又分離所得之TCS等的氫鹵化矽氣體經 由前述回收管路23循環回前述氣體供給裝置13以再使 用。 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝--------訂---------線一 524713File: 7666pif.doc / 009 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (\\) At this time, the exhaust gas formed by the chemical vapor deposition device 10 is introduced into the reactor 21, which contains A part of the TCS or DCS of the reaction raw material gas is reacted or transformed with its by-products to combine the generated hydrogen chloride and sand with a transition metal reactant or the like to generate a conversion reaction for removal. Similarly, boron or phosphorus in the 'diborium compound' or phosphine is removed by combining with the reagent. In this reaction, hydrogen is necessary. Although TCS or DCS itself has a hydrogen atom, in the foregoing description, during the normal epitaxial growth process, the atmosphere or diluent gas is the case where hydrogen is used. The problem is to make the conversion reaction easier. However, in the case where plasma is used to assist the growth reaction, etc., in the case where the hydrogen in the exhaust gas is insufficient, it is preferable to add hydrogen to the exhaust gas in the exhaust line that is cut off before the reactor 21. Means of adding hydrogen in the gas to add an appropriate amount of hydrogen. The exhaust gas discharged from the reactor 21 is introduced into a separator 22 to separate TCS or DCS having a raw material gas from hydrogen chloride. The structure or operation method of the separator 22 is to appropriately select the operating pressure, the rectification separation temperature, the number of stages of the rectification separator, etc., according to the composition of the exhaust gas, the type of the recovered raw gas, the recovery rate, and the purity. For example, using a rectification cylinder with seven stages and maintaining a pressure of 150 kPa and a temperature of 283 K, the TCS from the reactor 21 with a hydrogen chloride concentration of lpprn or less is introduced from the upper half of the separator 22 Take out, at this time, about 99% of the TCS introduction amount can be recovered. The silicon hydrohalide gas such as TCS obtained by separation is recycled to the gas supply device 13 through the recovery line 23 for reuse. 14 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page). -------- Order ------- --Line one 524713
File:7 666pif.doc/00 9 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（\不）File: 7 666pif.doc / 00 9 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (\ No)
另一方面，經分離器22精餾分離所得之氯化氫氣體， 由分離益2 2之底部導出以導入藏液接觸槽2 4中，跑水接 觸形成鹽酸溶液後由管路2 5取出。又，此時所使用之水， 例如是使用相對電阻爲18ΜΩ · cm左右之純水，以生成 高純度的鹽酸溶液，並使此鹽酸溶液具有再利用之可能。 又，水在與氯化氫反應後也可以精製得到不溶之無害物 質Q 又，由分離器22之底部會有極少量未使用之乙硼烷 或磷化氫、或含有硼或磷之分解生成物或反應生成物等不 純物成分經由管路26排出。 在反應器21內，矽與例如是鐵的過渡金屬反應劑結 合，形成無害的矽化鐵，於轉化反應結束後可直接由反應 器21取出。此時，反應劑之純度高時，例如是使用純度97 %以上的鐵，可以得到高純度的矽化鐵，進而可再利用作 爲鐵素體鋼（ferritic steel)。 第3圖所示爲本發明之第二較佳實施例的系統圖。又， 在以下之說明中，與前述第一較佳實施例之組成要素相同 之組成要素係使用相同之符號表示，且省略其詳細之說 明。 在本較佳實施例中，與第一較佳實施例相同，將由反 應器21導出經由分離器22分離所得到之氯化氫氣體導入 管路27以取代前述氣液接觸槽24，而循環回前述氣體供 給裝置13，以作爲再使用之洗滌用氣體。如此，可大幅降 低所需之氯化氫成本。 --------訂---------參 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 524713On the other hand, the hydrogen chloride gas obtained by the rectification separation by the separator 22 is led out from the bottom of the separation benefit 22 to be introduced into the storage liquid contact tank 24, and is contacted by running water to form a hydrochloric acid solution, and then taken out from the pipeline 25. Moreover, the water used at this time is, for example, pure water having a relative resistance of about 18 MΩ · cm to generate a high-purity hydrochloric acid solution, and this hydrochloric acid solution may be reused. In addition, water can be purified to obtain insoluble harmless substance Q after reacting with hydrogen chloride. In addition, a small amount of unused diborane or phosphine, or a decomposition product containing boron or phosphorus, or Impurities such as reaction products are discharged through the pipe 26. In the reactor 21, silicon is combined with a transition metal reactant such as iron to form harmless iron silicide, which can be directly taken out from the reactor 21 after the conversion reaction is completed. In this case, when the purity of the reactant is high, for example, iron with a purity of 97% or more can be used to obtain high-purity iron silicide, which can be reused as ferritic steel. Fig. 3 shows a system diagram of a second preferred embodiment of the present invention. In the following description, the same components as those of the first preferred embodiment are denoted by the same symbols, and detailed descriptions thereof are omitted. In this preferred embodiment, as in the first preferred embodiment, the hydrogen chloride gas introduction pipe 27 led out from the reactor 21 and separated by the separator 22 is used to replace the gas-liquid contact tank 24 and circulate the gas back. The device 13 is supplied as a washing gas for reuse. In this way, the cost of hydrogen chloride required can be significantly reduced. -------- Order --------- Refer to (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 524713
File:7666pif.doc/009 A7 B7 五、發明說明) (請先閱讀背面之注意事項再填寫本頁) 第4圖所示爲本發明之第三較佳實施例的系統圖。第 5圖所示爲本發明之第三較佳實施例之反應器之一例的槪 略系統圖。本較佳實施例係以在排氣系統管路中連接有具 有可對排氣中所含有之未反應原料氣體或高沸點中間產物 進行分解或轉化反應之分解反應手段的反應器31、以及可 將由前述反應器31所導出之氯化氫氣體與水接觸形成鹽 酸溶液的氣液接觸槽32爲例進行說明。 在此所使用之反應器31係可對排氣中之未反應原料 氣體或中間產物之全部進行分解處理，且使用充塡例如是 鐵的過渡金屬反應劑，及使用熱脫附對反應劑加熱，使其 由常溫至攝氏500度爲止的加熱手段，與第一較佳實施例 之反應器相同，可使用任意的電加熱器。 又，前述反應器31未考慮維修保養與熱脫附之間的 切換，如第5圖所示，至少設置有3筒以上之藉由閥而並 列之反應器31、31，較佳係爲可個別對昇溫製程、降溫製 程、待機製程等三製程依序切換的反應器。 經濟部智慧財產局員工消費合作社印製 在由上述所構成之反應器31中導入來自化學氣相沈 積裝置10之排氣，以與TCS、DCS或其副產物反應分解 或轉化，以大部分之氯氣變成氯化氫，並使矽與反應劑中 的過渡金屬結合。 同樣地，藉由與乙硼烷或磷化氫中的硼或磷等的反應 劑結合而去除。此時，由反應器31排出之氣體幾乎已轉 換成氯化氫氣體。且，由反應器31所排出之氯化氫氣體 與連接於反應器31下游之氣液接觸槽32中的水相接觸形 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 524713File: 7666pif.doc / 009 A7 B7 V. Description of the invention) (Please read the notes on the back before filling out this page) Figure 4 shows the system diagram of the third preferred embodiment of the present invention. Fig. 5 is a schematic system diagram showing an example of a reactor according to a third preferred embodiment of the present invention. In the preferred embodiment, a reactor 31 having a decomposition reaction means capable of decomposing or converting the unreacted raw material gas or high-boiling intermediate products contained in the exhaust gas is connected to the exhaust system pipeline, and The gas-liquid contact tank 32 in which the hydrogen chloride gas derived from the reactor 31 is in contact with water to form a hydrochloric acid solution will be described as an example. The reactor 31 used here can decompose all the unreacted raw material gas or intermediate products in the exhaust gas, and use a transition metal reactant filled with, for example, iron, and use thermal desorption to heat the reactant. The heating means from normal temperature to 500 degrees Celsius is the same as the reactor of the first preferred embodiment, and any electric heater can be used. In addition, the reactor 31 does not consider switching between maintenance and thermal desorption. As shown in FIG. 5, at least three cylinders of reactors 31 and 31 arranged in parallel by a valve are preferably provided. Individual reactors that sequentially switch the three processes of heating process, cooling process, and waiting process. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the introduction of the exhaust gas from the chemical vapor deposition device 10 into the reactor 31 constituted above to decompose or convert it with TCS, DCS or its by-products. Chlorine becomes hydrogen chloride and binds silicon to the transition metal in the reactant. Similarly, it is removed by combining with a reagent such as boron or phosphorus in diborane or phosphine. At this time, the gas discharged from the reactor 31 was almost converted into hydrogen chloride gas. In addition, the hydrogen chloride gas discharged from the reactor 31 is in contact with the water in the gas-liquid contact tank 32 connected downstream of the reactor 31. The paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). 524713
File:7666pif.doc/009 A7 B7 五、發明說明（丨4) 成有用的鹽酸溶液，再由管路33取出。 (請先閱讀背面之注意事項再填寫本頁) 又，當反應器31中反應所必須之氫氣不足之情形下， 可利用前述之通路添加適當的氫氣。又，在反應器31內 矽與鐵結合後，與前述相同形成矽化鐵，可再利用作爲鐵 素體鋼原料。另外，在氣液接觸槽32中所使用之水，與 前述相同，係使用相對電阻爲18ΜΩ · cm左右之純水， 以得到高純度的鹽酸溶液。 以上，於各較佳實施例中所示之對化學氣相沈積排氣 所進行之處理，以防止在排氣系統管路之內面附著堆積 物，且可不需進行定期去除堆積物的保養維修，而提高化 學氣相沈積裝置之工作效率，又，原料氣體之再利用或將 處理後之產物使用於其他用途等更可大幅降低化學氣相沈 積排氣之除害所需的成本。例如，第一較佳實施例之結構 之除害成本約可降低至習知之除害成本的50%左右，第二 較佳實施例之結構之除害成本約可降低至習知之除害成本 的40%左右，第三較佳實施例之結構之除害成本約可降低 至習知之除害成本的30%左右。 (實例） 經濟部智慧財產局員工消費合作社印製 實例1 在第一較佳實施例中所記載構成之裝置中，在充塡有 鐵反應劑之反應器的下游側安裝FT-IR ’以對由反應器流 出之氣體成分進行分析。在化學氣相沈積裝置中，流入含 有2000ppm之TCS的氫氣作爲測試氣體，進行成膜，並 保持反應器之溫度於攝氏450度，以測量由反應器流出之 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐） 524713File: 7666pif.doc / 009 A7 B7 V. Description of the invention (丨 4) A useful hydrochloric acid solution is prepared, and then taken out through the pipeline 33. (Please read the precautions on the back before filling this page.) In addition, when the hydrogen necessary for the reaction in the reactor 31 is insufficient, appropriate hydrogen can be added by using the aforementioned pathway. Further, after silicon and iron are combined in the reactor 31, iron silicide is formed in the same manner as described above, and it can be reused as a ferritic steel raw material. In addition, as for the water used in the gas-liquid contact tank 32, pure water having a relative resistance of about 18 MΩ · cm is used in the same manner as described above to obtain a high-purity hydrochloric acid solution. Above, the treatment of the chemical vapor deposition exhaust gas shown in the preferred embodiments to prevent deposits from adhering to the inner surface of the exhaust system piping, and the need to perform periodic maintenance to remove the deposits And, to improve the working efficiency of the chemical vapor deposition device, and the reuse of the raw material gas or the use of the processed product for other purposes can greatly reduce the cost required for the removal of the chemical vapor deposition exhaust gas. For example, the harm removal cost of the structure of the first preferred embodiment can be reduced to about 50% of the conventional harm removal cost, and the harm removal cost of the structure of the second preferred embodiment can be reduced to about 50% of the conventional harm removal cost. About 40%, the harm removal cost of the structure of the third preferred embodiment can be reduced to about 30% of the conventional harm removal cost. (Example) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Example 1 In the device described in the first preferred embodiment, an FT-IR 'is installed on the downstream side of a reactor filled with an iron reactant. The composition of the gas flowing from the reactor was analyzed. In a chemical vapor deposition device, a hydrogen gas containing 2000 ppm of TCS was used as a test gas to form a film, and the temperature of the reactor was maintained at 450 degrees Celsius to measure 17 out of the reactor. CNS) A4 size (210 X 297 meals) 524713
File:7666pif.doc/009 A7 __B7 五、發明說明（\S ) (請先閱讀背面之注意事項再填寫本頁) 氣體成分的變化。其結果如第6圖所示，在反應器工作的 初期，在反應使用鐵的時間效果（aging)(氫氣去除氣化 鐵膜）之內只觀測得水分，當水分之發生減少時之測試氣 體之流入，可觀測得到TCS與氯化氫達到一定之濃度。又， 完全檢測不出中間產物。 接著將由前述反應器所流出之氣體保持在l5〇kpa之 壓力、283K之溫度下導入分離器中，進行精餾分離以確 認分離性能。所使用之分離器係爲筒高6m、層數爲7餍、 以及筒徑爲180mm。TCS之回收量係進行TCS中的氯化 氫濃度及回收流量之計測。其結果顯示在回收的TCS中氯 化氫的濃度係在檢出界限以下（lppm以下），由第6圖 所估計之分離器入口的TCS流量與回收流量計算得到約90 %之回收率。 實例2 經濟部智慧財產局員工消費合作社印製 在第三較佳實施例中所記載構成之裝置中，在充塡有 鐵反應劑之反應器的下游側安裝FT_IR，以對由反應器流 出之氣體成分進行分析。在化學氣相沈積裝置中，流入含 有25〇PPm之TCS的氫氣作爲測試氣體，進行成膜，並保 持反應器之溫度於攝氏6〇0度，以測量由反應器流出之氣 體成分的變化。其結果如第7圖所示，由第7圖可明顯地 看出，當使用超過攝氏4〇0度之溫度範圍時，TCS會迅速 分解而生成氯化氫。又，在此情形下，完全檢測不出中間 產物。 由反應器所流出之氯化氫與相對電阻爲17ΜΩ · cm 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 524713File: 7666pif.doc / 009 A7 __B7 V. Description of the Invention (\ S) (Please read the notes on the back before filling this page) Changes in gas composition. The results are shown in Fig. 6. In the initial stage of the reactor operation, only moisture was observed within the aging effect of the reaction using iron (hydrogen removal of the vaporized iron film), and the test gas was used when the occurrence of moisture was reduced. It can be observed that TCS and hydrogen chloride reach a certain concentration. Moreover, no intermediate product was detected at all. Then, the gas flowing out of the foregoing reactor was introduced into the separator at a pressure of 150 kpa and a temperature of 283 K, and was subjected to rectification separation to confirm the separation performance. The separator used is a cylinder with a height of 6m, a number of layers of 7 餍, and a cylinder diameter of 180mm. The recovered amount of TCS is measured by measuring the hydrogen chloride concentration and recovered flow rate in TCS. The results showed that the concentration of hydrogen chloride in the recovered TCS was below the detection limit (less than 1 ppm), and the recovery rate of about 90% was calculated from the TCS flow rate and the recovered flow rate of the separator inlet estimated in Fig. 6. Example 2 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the device described in the third preferred embodiment. FT_IR was installed on the downstream side of the reactor filled with iron reactant to prevent the flow from the reactor. The gas composition is analyzed. In a chemical vapor deposition apparatus, hydrogen gas containing TCS containing 25 PPm was used as a test gas for film formation, and the temperature of the reactor was maintained at 600 degrees Celsius to measure the change in the composition of the gas flowing out of the reactor. The results are shown in Fig. 7. It is obvious from Fig. 7 that when the temperature range exceeding 400 ° C is used, TCS decomposes rapidly to generate hydrogen chloride. In this case, no intermediate product was detected at all. The hydrogen chloride flowing out of the reactor and the relative resistance are 17MΩ · cm. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 524713
File：7666pif.doc/009 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（\u ) 之純水進行氣液接觸而生成鹽酸溶液。當鹽酸濃度爲35wt %時，鹽酸中的矽濃度約爲2ppm，且檢測不出鐵等金屬 污染物。 在上述說明中，本發明之化學氣相沈積排氣之處理回 收方法及裝置係爲在化學氣相沈積裝置中對未反應之原料 氣體的一部份或中間產物進行輕易地處理以分解或轉化反 應成氯化氫，以使排氣系統管路之內面不會附著堆積物， 而不需進行定期去除堆積物之保養維護，以提高化學氣相 沈積裝置之工作效率。又，對來自反應器之排氣進行精餾 分離以在進行有效率之分離的同時，可使原料氣體再次使 用。另外，氯化氫等無法再使用之氣體，在與純水進行氣 液接觸之後可輕易的無害化，且反應所產生之鹽酸溶液成 爲可再使用之新資源。 又，在反應器中使用熱脫附之方式可將原料氣體完全 分解而得到氯化氫氣體，進而不需進行保養維護。在此情 形下，氯化氫與純水反應後得到可再使用之高純度鹽酸溶 液。 且，對化學氣相沈積排氣進行有效率的處理，可提高 化學氣相沈積裝置之工作效率、降低除害成本、以及提高 生產性，以得到全體成本的降低。 19 —;—.—^裝--------訂---------^wi (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）File: 7666pif.doc / 009 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (\ u) Pure water is contacted with gas and liquid to generate hydrochloric acid solution. When the hydrochloric acid concentration is 35 wt%, the silicon concentration in hydrochloric acid is about 2 ppm, and metal contaminants such as iron cannot be detected. In the above description, the method and apparatus for treating and recovering the chemical vapor deposition exhaust gas of the present invention is to easily treat a part or intermediate products of unreacted raw gas in a chemical vapor deposition device to decompose or convert It reacts to hydrogen chloride, so that no deposits can be attached to the inner surface of the exhaust system pipeline, and regular maintenance is not required to remove the deposits, so as to improve the working efficiency of the chemical vapor deposition device. Further, the exhaust gas from the reactor is subjected to rectification and separation, so that the raw material gas can be reused while performing efficient separation. In addition, gases that can no longer be used, such as hydrogen chloride, can be easily harmless after being brought into gas-liquid contact with pure water, and the hydrochloric acid solution produced by the reaction becomes a new resource that can be reused. In addition, the method of thermal desorption in the reactor can completely decompose the raw material gas to obtain hydrogen chloride gas, and thus no maintenance is required. In this case, hydrogen chloride is reacted with pure water to obtain a reusable high-purity hydrochloric acid solution. Moreover, the efficient treatment of the chemical vapor deposition exhaust gas can improve the working efficiency of the chemical vapor deposition device, reduce the cost of harm removal, and improve the productivity to achieve a reduction in the overall cost. 19 —; —.— ^ 装 -------- Order --------- ^ wi (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standards (CNS ) A4 size (210 X 297 mm)
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| JP5991677B2 (en) * | 2012-09-24 | 2016-09-14 | 三菱重工環境・化学エンジニアリング株式会社 | Exhaust gas treatment equipment |
| DE112015000485T5 (en) | 2014-01-24 | 2017-02-23 | Hanwha Chemical Corporation | Cleaning method and cleaning device for exhaust gas |
| JP7328840B2 (en) | 2019-09-11 | 2023-08-17 | オルガノ株式会社 | Gas-dissolved water production device and method |
| CN114293173B (en) * | 2021-12-17 | 2024-02-09 | 厦门钨业股份有限公司 | Device for carbon doped chemical vapor deposition tungsten coating |
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| JPH04265113A (en) * | 1991-02-20 | 1992-09-21 | Mitsui Toatsu Chem Inc | Treatment of fluorine-containing gas |
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