TW202026241A - Method of manufacturing silicon monoxide deposit by use of silicon kerf waste - Google Patents

Method of manufacturing silicon monoxide deposit by use of silicon kerf waste Download PDF

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TW202026241A
TW202026241A TW108100216A TW108100216A TW202026241A TW 202026241 A TW202026241 A TW 202026241A TW 108100216 A TW108100216 A TW 108100216A TW 108100216 A TW108100216 A TW 108100216A TW 202026241 A TW202026241 A TW 202026241A
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silicon
powders
powder
monoxide
remaining part
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TWI741247B (en
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藍崇文
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國立臺灣大學
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Abstract

The invention discloses a method of manufacturing a silicon monoxide deposit by use of a silicon kerf waste. The method according to the invention is to react a reaction portion of a plurality of silicon powders by acid and alkali solutions into a plurality of silicon dioxide powders, to utilize a retained portion of the plurality of silicon powders and the plurality of silicon dioxide powders to react into a silicon monoxide vapor, and to collect and cool the silicon monoxide vapor into the silicon monoxide deposit.

Description

以矽泥廢料製造一氧化矽沉積物之方法 Method for producing silicon monoxide deposit from silicon mud waste

本發明係關於一種製造一氧化矽沉積物之方法,並且特別地,關於以矽泥廢料來製造一氧化矽沉積物之方法。 The present invention relates to a method of manufacturing silicon monoxide deposits, and in particular, to a method of manufacturing silicon monoxide deposits from silicon sludge waste.

一氧化矽粉體是一種廣泛用於光學玻璃鍍膜和製作半導體的材料。例如,照明燈具、眼鏡、光學鏡頭、寶石、玩具等鍍膜以及IC產業的重要原料之一。一氧化矽的光學應用方面,可做為抗反射塗層、吸收塗層、保護塗層等。一氧化矽可做為用於液晶導電膜的保護絕緣塗層。一氧化矽可做為用於半導體元件的保護絕緣塗層。一氧化矽可做為用於薄膜電容器的介電層。一氧化矽可做為用於太陽能電池的抗反射塗層。一氧化矽可做為用於阻氣膜的沉積材料。一氧化矽可以用於鋰離子充電電池的負極材料 Silicon monoxide powder is a material widely used for coating optical glass and making semiconductors. For example, lighting lamps, glasses, optical lenses, gems, toys and other coatings and one of the important raw materials of the IC industry. In terms of optical applications, silicon monoxide can be used as anti-reflective coating, absorbing coating, protective coating, etc. Silicon monoxide can be used as a protective insulating coating for liquid crystal conductive films. Silicon monoxide can be used as a protective insulating coating for semiconductor components. Silicon monoxide can be used as a dielectric layer for thin film capacitors. Silicon monoxide can be used as an anti-reflective coating for solar cells. Silicon monoxide can be used as a deposition material for gas barrier films. Silicon monoxide can be used as a negative electrode material for lithium-ion rechargeable batteries

關於一氧化矽之製造方法的先前技術,請參閱中國大陸專利公開號1451057A以及美國專利公告號7,431,899B2。這些先前技術揭示將矽粉體與二氧化矽粉體混合,置於高溫下讓矽粉體與二氧化矽粉體反應成一氧化矽並昇華為一氧化矽蒸氣,再收集一氧化矽將其冷卻成一氧化矽沉積物。顯見地,矽粉體與二氧化矽粉體的取得成本影響一氧化矽沉積物的製造成本甚鉅。 For the prior art of the manufacturing method of silicon monoxide, please refer to Mainland China Patent Publication No. 1451057A and US Patent Publication No. 7,431,899B2. These previous technologies revealed mixing silicon powder and silicon dioxide powder, placing the silicon powder and silicon dioxide powder to react to form silicon monoxide and sublimate it into silicon monoxide vapor, and then collect silicon monoxide and cool it down. Into silicon monoxide deposits. Obviously, the cost of obtaining silicon powder and silicon dioxide powder affects the manufacturing cost of silicon monoxide deposits.

無論是供做太陽能電池或半導體元件之基材的矽晶圓,其製造上皆會產生大量的矽泥廢料。如何從矽泥廢 料回收矽料等材料已有不少技術被發展。然而,如何提升矽泥廢料回收的價值仍存有很大的改善空間。 Whether it is a silicon wafer used as a substrate for solar cells or semiconductor components, a large amount of silicon mud waste will be generated during its manufacturing. How to waste from silica mud Many technologies have been developed for recycling silicon and other materials. However, there is still much room for improvement in how to increase the value of the recycling of silica mud waste.

此外,目前尚未見到同時降低一氧化矽沉積物的製造成本以及提升矽泥廢料回收的價值之技術被提出。 In addition, there has not been any technology proposed to simultaneously reduce the manufacturing cost of silicon monoxide deposits and increase the value of silicon mud waste recycling.

因此,本發明所欲解決之一技術問題在於提供一種以矽泥廢料來製造一氧化矽沉積物之方法。根據本發明之方法可以同時降低一氧化矽沉積物的製造成本以及提升矽泥廢料回收的價值。 Therefore, one of the technical problems to be solved by the present invention is to provide a method for producing silicon monoxide deposits from silicon mud waste. The method according to the present invention can simultaneously reduce the manufacturing cost of silicon monoxide deposits and increase the value of silicon mud waste recycling.

本發明之一較佳具體實施例以矽泥廢料製造一氧化矽沉積物之製造方法。首先,根據本發明之製造方法係加入鹼液至基於矽泥廢料的初始漿料內。初始漿料包含多顆第一矽粉體。鹼液的pH值係控制讓多顆第一矽粉體之反應部份與鹼液反應成矽酸鹽。接著,根據本發明之製造方法係當多顆第一矽粉體之剩餘部份與矽酸鹽之Si/SiO4 2+比例達預定值時,加入酸液以中止多顆第一矽粉體之反應部份繼續與鹼液反應成矽酸鹽,並且控制酸液的pH值讓矽酸鹽與酸液反應成多顆二氧化矽粉體。接著,根據本發明之製造方法係倒出上述步驟所產生之液體,以保留多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體。接著,根據本發明之製造方法係以洗滌劑清洗並乾燥多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體。接著,根據本發明之製造方法係將多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體置於真空環境或鈍態氣氛中且加熱致使該多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體反應成一氧化矽且昇華成一氧化矽蒸氣。最後,根據本發明之製造方法係收集且冷卻一氧化矽蒸氣,即獲得一氧化矽沉積物。 A preferred embodiment of the present invention uses silicon mud waste to produce silicon monoxide deposits. First, the manufacturing method according to the present invention is to add lye to the initial slurry based on silicon mud waste. The initial slurry contains a plurality of first silicon powder bodies. The pH value of the lye is controlled so that the reaction part of the first silica powder reacts with the lye to form silicate. Next, the manufacturing method of the present invention when a remaining part of the line multiple pieces of a first silicon powder of silicate and Si / SiO 4 2+ ratio reached a predetermined value, acid is added to stop the first plurality pieces of silicon powder The reaction part continues to react with the lye to form silicate, and the pH of the acid is controlled so that the silicate reacts with the acid to form multiple silica powders. Then, according to the manufacturing method of the present invention, the liquid produced by the above steps is poured out to retain the remaining part of the first silicon powders and the silicon dioxide powders. Next, according to the manufacturing method of the present invention, the remaining parts of the first silicon powders and the silicon dioxide powders are washed and dried with detergent. Then, according to the manufacturing method of the present invention, the remaining parts of the plurality of first silicon powders and the plurality of silicon dioxide powders are placed in a vacuum or passive atmosphere and heated to cause the The remaining part and multiple silicon dioxide powders react to form silicon monoxide and sublimate into silicon monoxide vapor. Finally, the manufacturing method according to the present invention collects and cools silicon monoxide vapor to obtain silicon monoxide deposits.

於一具體實施例中,酸液可以是H2SO4、HCl、 HNO3、H3PO4等。 In a specific embodiment, the acid solution can be H 2 SO 4 , HCl, HNO 3 , H 3 PO 4, etc.

於一具體實施例中,酸液的pH值可以控制在等於或小於5。 In a specific embodiment, the pH value of the acid solution can be controlled to be equal to or less than 5.

於一具體實施例中,鹼液可以是KOH、NaOH、NH4OH等。 In a specific embodiment, the lye can be KOH, NaOH, NH 4 OH, or the like.

於一具體實施例中,鹼液的pH值可以控制在等於或大於7。 In a specific embodiment, the pH value of the lye can be controlled to be equal to or greater than 7.

於一具體實施例中,Si/SiO4 2+比例之預定值係介於0.8至1.2。 In a specific embodiment, the predetermined value of the ratio of Si/SiO 4 2+ is between 0.8 and 1.2.

進一步,根據本發明之製造方法加入將另一矽泥廢料沉降所得多顆第二矽粉體,將多顆第一矽粉體之剩餘部份、多顆第二矽粉體以及多顆二氧化矽粉體置於真空環境或鈍態氣氛中且加熱致使多顆第一矽粉體之剩餘部份、多顆第二矽粉體以及多顆二氧化矽粉體反應成一氧化矽且昇華成一氧化矽蒸氣。 Further, according to the manufacturing method of the present invention, a plurality of second silica powders obtained by sedimentation of another silica mud waste material are added, and the remaining part of the plurality of first silica powders, the plurality of second silica powders and the plurality of dioxide The silicon powder is placed in a vacuum environment or a passive atmosphere and heated to cause the remaining parts of the first silicon powders, the second silicon powders, and the silicon dioxide powders to react into silicon monoxide and sublime into oxide. Silicon vapor.

與先前技術不同,本發明之方法以矽泥廢料來製造一氧化矽沉積物。根據本發明之方法可以同時降低一氧化矽沉積物的製造成本以及提升矽泥廢料回收的價值。 Unlike the prior art, the method of the present invention uses silica mud waste to produce silicon monoxide deposits. The method according to the present invention can simultaneously reduce the manufacturing cost of silicon monoxide deposits and increase the value of silicon mud waste recycling.

關於本發明之優點與精神可以藉由以下的發明詳述及所附圖式得到進一步的瞭解。 The advantages and spirit of the present invention can be further understood from the following detailed description of the invention and the accompanying drawings.

1‧‧‧製造方法 1‧‧‧Manufacturing method

S10~S19‧‧‧流程步驟 S10~S19‧‧‧Process steps

圖1係根據本發明之一較佳具體實施例之製造方法的各個程序步驟流程圖。 Fig. 1 is a flowchart of various program steps of a manufacturing method according to a preferred embodiment of the present invention.

請參閱圖1,為根據本發明之一較佳具體實施例之製造方法1之流程圖。根據本發明之較佳具體實施例之製造方法1以矽泥廢料來製造一氧化矽沉積物。 Please refer to FIG. 1, which is a flowchart of a manufacturing method 1 according to a preferred embodiment of the present invention. According to the manufacturing method 1 of the preferred embodiment of the present invention, silicon monoxide deposits are manufactured from silicon mud waste.

如圖1所示,根據本發明之製造方法1,首先係執行步驟S10,加入鹼液至基於矽泥廢料之初始漿料內。初始漿料包含多顆第一矽粉體。鹼液的pH值係控制讓多顆第一矽粉體之反應部份與鹼液反應成矽酸鹽。 As shown in FIG. 1, according to the manufacturing method 1 of the present invention, step S10 is first performed to add lye to the initial slurry based on silicon mud waste. The initial slurry contains a plurality of first silicon powder bodies. The pH value of the lye is controlled so that the reaction part of the first silica powder reacts with the lye to form silicate.

於一具體實施例中,鹼液可以是KOH、NaOH、NH4OH等。鹼液的pH值可以控制在等於或大於7。 In a specific embodiment, the lye can be KOH, NaOH, NH 4 OH, or the like. The pH value of the lye can be controlled to be equal to or greater than 7.

接著,根據本發明之製造方法1係執行步驟S12,當多顆第一矽粉體之剩餘部份與矽酸鹽之Si/SiO4 2+比例達預定值時,加入酸液以中止多顆第一矽粉體之反應部份繼續與鹼液反應成矽酸鹽,並且控制酸液的pH值讓矽酸鹽與酸液反應成多顆二氧化矽粉體。 Next, according to the manufacturing method 1 of the present invention, step S12 is performed. When the ratio of the remaining part of the first silicon powder body to the silicate Si/SiO 4 2+ reaches a predetermined value, an acid solution is added to stop the plurality of particles The reaction part of the first silica powder continues to react with the alkali solution to form silicate, and the pH value of the acid solution is controlled to allow the silicate to react with the acid solution to form multiple silica powders.

於一具體實施例中,酸液可以是H2SO4、HCl、HNO3、H3PO4等。酸液的pH值可以控制在等於或小於5。 In a specific embodiment, the acid solution can be H 2 SO 4 , HCl, HNO 3 , H 3 PO 4, etc. The pH value of the acid solution can be controlled at 5 or less.

於一具體實施例中,Si/SiO4 2+比例之預定值係介於0.8至1.2。 In a specific embodiment, the predetermined value of the ratio of Si/SiO 4 2+ is between 0.8 and 1.2.

接著,根據本發明之製造方法1係執行步驟S14,倒出步驟S12所產生之液體,以保留多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體。 Next, according to the manufacturing method 1 of the present invention, step S14 is performed to pour out the liquid produced in step S12 to retain the remaining parts of the first silicon powders and the silicon dioxide powders.

接著,根據本發明之製造方法1係執行步驟S16,以洗滌劑清洗並乾燥多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體。 Next, according to the manufacturing method 1 of the present invention, step S16 is performed to clean and dry the remaining parts of the first silicon powders and the silicon dioxide powders with detergent.

於一具體實施例中,洗滌劑可以是水。 In a specific embodiment, the detergent may be water.

接著,根據本發明之製造方法1係執行步驟S18,將多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體置 於真空環境或鈍態氣氛中,並且加熱致使多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體反應成一氧化矽且昇華成一氧化矽蒸氣。 Next, according to the manufacturing method 1 of the present invention, step S18 is performed to place the remaining parts of the first silicon powders and the silicon dioxide powders In a vacuum environment or a passive atmosphere, heating causes the remaining parts of the first silicon powders and the silicon dioxide powders to react into silicon monoxide and sublimate into silicon monoxide vapor.

於一具體實施例中,加熱致使多顆第一矽粉體之剩餘部份以及多顆二氧化矽粉體反應成一氧化矽之溫度的範圍為從1200℃至1450℃。 In a specific embodiment, the temperature at which the remaining parts of the plurality of first silicon powders and the plurality of silicon dioxide powders react to form silicon monoxide by heating ranges from 1200°C to 1450°C.

於一具體實施例中,真空環境的真空度為小於1torr。 In a specific embodiment, the vacuum degree of the vacuum environment is less than 1 torr.

最後,根據本發明之製造方法1係執行步驟S19,收集且冷卻一氧化矽蒸氣,即獲得一氧化矽沉積物。 Finally, according to the manufacturing method 1 of the present invention, step S19 is performed to collect and cool silicon monoxide vapor to obtain silicon monoxide deposits.

於實際應用中,矽晶棒、矽晶鑄錠可以利用砂漿切割或鑽石線切割技術切削出矽晶圓,矽泥廢料可能還包含金屬物質、碳化矽粉體等。但是,在根據本發明之方法執行過程中,金屬物質溶於酸、鹼液中,碳化矽粉體其本身的熔點高(碳化矽的熔點為2730℃)。所以,原矽泥廢料中的金屬物質、碳化矽粉體不會參與矽粉體之剩餘部份與二氧化矽粉體的反應。 In practical applications, silicon crystal rods and silicon crystal ingots can be cut into silicon wafers using mortar cutting or diamond wire cutting technology. The silicon mud waste may also contain metal substances, silicon carbide powder, etc. However, during the execution of the method according to the present invention, the metal substance is dissolved in acid and lye, and the melting point of silicon carbide powder itself is high (the melting point of silicon carbide is 2730°C). Therefore, the metal substances and silicon carbide powder in the original silicon mud waste will not participate in the reaction between the remaining part of the silicon powder and the silicon dioxide powder.

於實際應用中,根據本發明之方法可以在矽晶圓製造廠內實施,免除將矽泥廢料運出矽晶圓製造廠,進而降低汙染,降低成本。 In practical applications, the method according to the present invention can be implemented in a silicon wafer manufacturing plant, eliminating the need to transport silicon mud waste out of the silicon wafer manufacturing plant, thereby reducing pollution and reducing costs.

實務上,矽泥廢料包含多顆第一矽粉體以及添加劑。一般情形,添加劑包含切削液、界面活性劑等。 In practice, silicon mud waste contains multiple first silicon powders and additives. In general, additives include cutting fluids, surfactants, etc.

若Si/SiO4 2+比例略低,根據本發明之製造方法1可以加入將另一矽泥廢料沉降所得多顆第二矽粉體,將多顆第一矽粉體之剩餘部份、多顆第二矽粉體以及多顆二氧化矽粉體置於真空環境或鈍態氣氛中且加熱致使多顆第一矽粉體之剩餘部份、多顆第二矽粉體以及多顆二氧化矽粉體反應成 一氧化矽且昇華成一氧化矽蒸氣。 If the ratio of Si/SiO 4 2+ is slightly lower, according to the manufacturing method 1 of the present invention, multiple second silicon powders obtained by sedimentation of another silicon mud waste can be added, and the remaining part of the multiple first silicon powders The second silicon powders and the multiple silicon dioxide powders are placed in a vacuum or passive atmosphere and heated to cause the remaining parts of the multiple first silicon powders, multiple second silicon powders and multiple silicon dioxides The silicon powder reacts into silicon monoxide and sublimates into silicon monoxide vapor.

與先前技術相比較,根據本發明之方法以矽泥廢料來製造一氧化矽沉積物,可以同時降低一氧化矽沉積物的製造成本以及提升矽泥廢料回收的價值,甚至可以免除將矽泥廢料運出矽晶圓製造廠可能造成的汙染。 Compared with the prior art, the method according to the present invention uses silica sludge waste to produce silicon monoxide deposits, which can simultaneously reduce the manufacturing cost of silicon monoxide deposits and increase the value of silicon sludge waste recycling. It can even eliminate the need for silica sludge waste. Pollution that may be caused by shipping out of the silicon wafer manufacturing plant.

藉由以上較佳具體實施例之詳述,係希望能更加清楚描述本發明之特徵與精神,而並非以上述所揭露的較佳具體實施例來對本發明之面向加以限制。相反地,其目的是希望能涵蓋各種改變及具相等性的安排於本發明所欲申請之專利範圍的面向內。因此,本發明所申請之專利範圍的面向應該根據上述的說明作最寬廣的解釋,以致使其涵蓋所有可能的改變以及具相等性的安排。 Based on the above detailed description of the preferred embodiments, it is hoped that the characteristics and spirit of the present invention can be described more clearly, instead of limiting the aspect of the present invention by the preferred embodiments disclosed above. On the contrary, its purpose is to cover various changes and equivalent arrangements within the scope of the patent for which the present invention is intended. Therefore, the aspect of the patent scope applied for by the present invention should be interpreted in the broadest way based on the above description, so as to cover all possible changes and equivalent arrangements.

1‧‧‧製造方法 1‧‧‧Manufacturing method

S10~S19‧‧‧流程步驟 S10~S19‧‧‧Process steps

Claims (7)

一種以一矽泥廢料製造一一氧化矽沉積物之方法,包含下列步驟:(a)加入一鹼液至基於該矽泥廢料之一初始漿料內,其中該初始漿料包含多顆第一矽粉體,該鹼液的pH值係控制讓該多顆第一矽粉體之一反應部份與該鹼液反應成一矽酸鹽;(b)當該多顆第一矽粉體之一剩餘部份與該矽酸鹽之一Si/SiO4 2+比例達一預定值時,加入一酸液以中止該多顆第一矽粉體之該反應部份繼續與該鹼液反應成該矽酸鹽,並且控制該酸液的pH值讓該矽酸鹽與該酸液反應成多顆二氧化矽粉體;(c)倒出步驟(b)所產生之一液體,以保留該多顆第一矽粉體之該剩餘部份以及該多顆二氧化矽粉體;(d)以一洗滌劑清洗並乾燥該多顆第一矽粉體之該剩餘部份以及該多顆二氧化矽粉體;(e)將該多顆第一矽粉體之該剩餘部份以及該多顆二氧化矽粉體置於一真空環境或一鈍態氣氛中且加熱致使該多顆第一矽粉體之該剩餘部份以及該多顆二氧化矽粉體反應成一氧化矽且昇華成一一氧化矽蒸氣;以及(f)收集且冷卻該一氧化矽蒸氣,即獲得該一氧化矽沉積物。 A method for producing a silicon monoxide deposit from a silicon mud waste material, comprising the following steps: (a) adding a lye to an initial slurry based on the silicon mud waste material, wherein the initial slurry contains a plurality of first Silicon powder, the pH value of the lye is controlled so that a reactive part of the plurality of first silicon powders reacts with the lye to form a silicate; (b) when one of the plurality of first silicon powders When the ratio between the remaining part and one of the silicate Si/SiO 4 2+ reaches a predetermined value, an acid solution is added to stop the reaction part of the plurality of first silicon powders and continue to react with the alkali solution to form the Silicate, and control the pH of the acid solution to allow the silicate to react with the acid solution to form a plurality of silica powders; (c) pour out one of the liquids produced in step (b) to retain the The remaining part of the first silicon powder and the plurality of silicon dioxide powders; (d) washing and drying the remaining part of the first silicon powder and the plurality of silicon dioxide with a detergent Silicon powder; (e) placing the remaining part of the plurality of first silicon powders and the plurality of silicon dioxide powders in a vacuum environment or a passive atmosphere and heating to cause the plurality of first silicon The remaining part of the powder and the plurality of silicon dioxide powders react to form silicon monoxide and sublimate into silicon monoxide vapor; and (f) collecting and cooling the silicon monoxide vapor to obtain the silicon monoxide deposit . 如請求項1所述之方法,其中該酸液係選自由H2SO4、HCl、HNO3以及H3PO4所組成之群組中之其一。 The method according to claim 1, wherein the acid solution is selected from one of the group consisting of H 2 SO 4 , HCl, HNO 3 and H 3 PO 4 . 如請求項2所述之方法,其中該酸液的pH值係控制在等於或小於5。 The method according to claim 2, wherein the pH value of the acid solution is controlled to be 5 or less. 如請求項1所述之方法,其中該鹼液係選自由KOH、NaOH以及NH4OH所組成之群組中之其一。 The method according to claim 1, wherein the lye is selected from one of the group consisting of KOH, NaOH, and NH 4 OH. 如請求項4所述之方法,其中該鹼液的pH值係控制在等於或大於7。 The method according to claim 4, wherein the pH value of the lye is controlled to be equal to or greater than 7. 如請求項1所述之方法,其中該預定值係介於0.8至1.2。 The method according to claim 1, wherein the predetermined value is between 0.8 and 1.2. 如請求項1所述之方法,其中於步驟(e)中,加入將另一矽泥廢料沉降所得多顆第二矽粉體,將該多顆第一矽粉體之該剩餘部份、該多顆第二矽粉體以及該多顆二氧化矽粉體置於該真空環境或該鈍態氣氛中且加熱致使該多顆第一矽粉體之該剩餘部份、該多顆第二矽粉體以及該多顆二氧化矽粉體反應成一氧化矽且昇華成該一氧化矽蒸氣。 The method according to claim 1, wherein in step (e), a plurality of second silicon powder bodies obtained by sedimentation of another silicon mud waste material are added, and the remaining part of the plurality of first silicon powder bodies, the The plurality of second silicon powder bodies and the plurality of silicon dioxide powder bodies are placed in the vacuum environment or the passive atmosphere and heated so that the remaining part of the plurality of first silicon powder bodies, the plurality of second silicon powder bodies The powder and the plurality of silicon dioxide powders react to form silicon monoxide and sublimate into the silicon monoxide vapor.
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