TW202113120A - Method of using ALD technology to produce anti-corrosion coating on the inner wall of gas pipeline having a dense coating and uniform film thickness - Google Patents

Method of using ALD technology to produce anti-corrosion coating on the inner wall of gas pipeline having a dense coating and uniform film thickness Download PDF

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TW202113120A
TW202113120A TW109127265A TW109127265A TW202113120A TW 202113120 A TW202113120 A TW 202113120A TW 109127265 A TW109127265 A TW 109127265A TW 109127265 A TW109127265 A TW 109127265A TW 202113120 A TW202113120 A TW 202113120A
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gas
gas pipeline
wall
reaction
pipeline
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朱生華
曹芳成
陳星建
圖強 倪
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大陸商中微半導體設備（上海）股份有限公司
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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
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • 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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
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Abstract

The present invention relates to a method of using ALD technology to produce an anti-corrosion coating on the inner wall of a gas pipeline. The gas pipeline is a gas pipeline of plasma etching equipment or MOCVD equipment. The method includes: step 1: using an atomic layer deposition reactor, introducing the first reaction gas into the gas pipeline to perform the first chemical adsorption, so that the first reaction gas is adsorbed to the inner wall surface of the gas pipeline; step 2: blowing with an inert gas flow to remove the un-adsorbed first reaction gas and/or by-products produced by the first chemical adsorption in the gas pipeline; step 3: introducing the second reaction gas into the atomic layer deposition reactor to perform the second chemical adsorption; step 4: blowing with an inert gas flow to remove the un-adsorbed second reaction gas and/or by-products produced by the second chemical adsorption in the gas pipeline; step 5: repeating steps 1 to 4. The method of the invention is not limited by the shape and structure of the gas pipeline, the coating is dense, and the film thickness is uniform.

Description

採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法Method of using ALD technology to produce anti-corrosion coating on the inner wall of gas pipeline

本發明係關於電漿蝕刻或者MOCVD設備的抗腐蝕技術，具體關於一種採用ALD技術在輸氣管道內壁產生抗腐蝕塗層（corrosion-resistant coating）的方法。The present invention relates to the anti-corrosion technology of plasma etching or MOCVD equipment, and specifically relates to a method for generating a corrosion-resistant coating (corrosion-resistant coating) on the inner wall of a gas pipeline using ALD technology.

原子層沉積(atomiclayer deposition，ALD)技術，是一種基於有序、表面自飽和反應的化學氣相薄膜沉積技術，可以將物質以單原子膜形式一層一層的鍍在基底表面，透過將氣相前驅體交替脈衝通入反應室並在沉積基體表面發生氣固相化學吸附反應形成薄膜。在原子沉積過程中，新一層原子膜的化學反應是直接與之前一層相關聯的，這種方式使每次反應只沉積一層原子。在ALD進行薄膜生長時，將適當的前驅反應氣體以脈衝方式通入反應器中，隨後再通入惰性氣體進行清洗，對隨後的每一沉積層都重複這樣的程序。原子層製程中，透過在一個加熱反應器中的基板上連續引入至少兩種氣相前驅體物質，化學吸附的過程達到表面飽和時自動終止，適當的過程溫度阻礙了分子在表面的物理吸附。一個基本的原子層沉積循環包含4個基本步驟：（1）前驅體A脈衝吸附反應；（2）惰氣吹掃多餘的反應物及副產物；（3）前驅體B脈衝吸附反應；（4）惰氣吹掃多餘的反應物及副產物，然後依次循環從而實現薄膜在基板表面逐層生長。Atomic layer deposition (ALD) technology is a chemical vapor thin film deposition technology based on orderly, surface self-saturation reaction. It can deposit substances layer by layer on the surface of the substrate in the form of monoatomic film. The body is pulsed into the reaction chamber alternately and a gas-solid phase chemical adsorption reaction occurs on the surface of the deposition substrate to form a thin film. In the atomic deposition process, the chemical reaction of the new layer of atomic film is directly related to the previous layer. In this way, only one layer of atoms is deposited per reaction. When ALD is performing thin film growth, an appropriate precursor reaction gas is pulsed into the reactor, and then an inert gas is introduced for cleaning, and this procedure is repeated for each subsequent deposited layer. In the atomic layer manufacturing process, by continuously introducing at least two gas-phase precursor substances on the substrate in a heated reactor, the chemical adsorption process is automatically terminated when the surface is saturated, and the appropriate process temperature hinders the physical adsorption of molecules on the surface. A basic atomic layer deposition cycle consists of 4 basic steps: (1) pulse adsorption reaction of precursor A; (2) inert gas purging excess reactants and by-products; (3) pulse adsorption reaction of precursor B; (4) 1) The inert gas purges the excess reactants and by-products, and then circulates in turn to realize the layer-by-layer growth of the film on the surface of the substrate.

電漿蝕刻設備透過暴露在電子區域的氣體形成電漿，由此產生的電離氣體及釋放高能電子組成的氣體，從而形成了電漿或離子，電離氣體原子通過電場加速時，會釋放足夠的力量與表面驅逐力緊緊粘合材料或蝕刻表面。MOCVD（Metal-organic Chemical Vapor Deposition）是在氣相外延生長(vapor phase epitoxy，VPE)的基礎上發展起來的一種新型氣相外延生長技術，以Ⅲ族、Ⅱ族元素的有機化合物及V、Ⅵ族元素的氫化物等作為晶體生長源材料，以熱分解反應方式在基板上進行氣相外延，生長各種Ⅲ-V族、Ⅱ-Ⅵ族化合物半導體以及它們的多元固溶體的薄層單晶材料。在電漿蝕刻或者MOCVD設備運行過程中，常需要採用深長孔徑的管道以輸送腐蝕性氣體。由於各種腐蝕性氣體流經金屬管道時，會腐蝕輸氣管道（gas line），引起金屬及顆粒污染，污染晶圓。特別是在電漿蝕刻過程中，連接反應腔（chamber）的輸氣管道（gas line）被腐蝕後，需更換輸氣管道（gas line），會提高成本、降低生產效率，而傳統的鍍膜技術難以在管道的內表面（inner wall surface）均勻成膜。The plasma etching equipment forms plasma through the gas exposed to the electron area. The resulting ionized gas and the gas composed of high-energy electrons are released to form plasma or ions. When the ionized gas atoms are accelerated by the electric field, they will release sufficient force. Tightly bond the material or etch the surface with the surface repellent force. MOCVD (Metal-organic Chemical Vapor Deposition) is a new type of vapor phase epitoxy growth technology developed on the basis of vapor phase epitoxy (VPE). The hydrides of group elements are used as crystal growth source materials, and vapor phase epitaxy is carried out on the substrate by thermal decomposition reaction to grow various group III-V, group II-VI compound semiconductors and thin-layer single crystals of their multiple solid solutions material. During the operation of plasma etching or MOCVD equipment, it is often necessary to use deep and long bore pipes to transport corrosive gases. As various corrosive gases flow through the metal pipeline, they will corrode the gas line, causing metal and particle contamination and contaminating wafers. Especially in the plasma etching process, after the gas line connected to the chamber is corroded, the gas line needs to be replaced, which will increase the cost and reduce the production efficiency, while the traditional coating technology It is difficult to form a uniform film on the inner wall surface of the pipe.

本發明的目的是提供一種採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，這種方法可以增強輸氣管道的抗腐蝕性能。The purpose of the present invention is to provide a method for producing an anti-corrosion coating on the inner wall of a gas pipeline by using ALD technology, which can enhance the anti-corrosion performance of the gas pipeline.

為了達到上述目的，本發明提供了一種採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，輸氣管道為電漿蝕刻設備或MOCVD設備的輸氣管道，該方法包含：In order to achieve the above objective, the present invention provides a method for producing an anti-corrosion coating on the inner wall of a gas pipeline by using ALD technology. The gas pipeline is a gas pipeline of plasma etching equipment or MOCVD equipment. The method includes:

步驟1，採用原子層沉積反應器，向輸氣管道內通入第一反應氣體，以進行第一化學吸附，使得第一反應氣體吸附至輸氣管道的內壁表面；Step 1. Using an atomic layer deposition reactor, pass the first reaction gas into the gas pipeline to perform the first chemical adsorption, so that the first reaction gas is adsorbed to the inner wall surface of the gas pipeline;

步驟2，採用惰性氣流吹掃，以除去輸氣管道未吸附的第一反應氣體及/或第一化學吸附產生的副產物；Step 2: Purging with an inert gas flow to remove the unadsorbed first reaction gas and/or by-products generated by the first chemical adsorption in the gas pipeline;

步驟3，向原子層沉積反應器中通入第二反應氣體，以進行第二化學吸附；Step 3. Pass the second reaction gas into the atomic layer deposition reactor to perform the second chemical adsorption;

步驟4，採用惰性氣流吹掃，以除去輸氣管道未吸附的第二反應氣體及/或第二化學吸附產生的副產物；Step 4, purging with an inert gas flow to remove the unadsorbed second reaction gas and/or by-products produced by the second chemical adsorption in the gas pipeline;

步驟5，重複步驟1-4，直到輸氣管道的內壁產生的抗腐蝕塗層符合要求。Step 5, repeat steps 1-4 until the anti-corrosion coating produced on the inner wall of the gas pipeline meets the requirements.

較佳地，抗腐蝕塗層的成分包含Al2 O3 、SiO2 、Y2 O3 、YF3 、YOF、Ta2 O5 及TaN中的至少一種。Preferably, the composition of the anti-corrosion coating includes at least one of Al 2 O 3 , SiO 2 , Y 2 O 3 , YF 3 , YOF, Ta 2 O 5 and TaN.

較佳地，抗腐蝕塗層為Al2 O3 塗層。Preferably, the anti-corrosion coating is an Al 2 O 3 coating.

較佳地，第一反應氣體為Al(CH3 )3 。Preferably, the first reaction gas is Al(CH 3 ) 3 .

較佳地，惰性氣流為氮氣。Preferably, the inert gas stream is nitrogen.

較佳地，第二反應氣體為H2 O。Preferably, the second reaction gas is H 2 O.

較佳地，輸氣管道為工作狀態下，內部流經腐蝕性氣體的金屬管道。Preferably, the gas pipeline is a metal pipeline through which corrosive gas flows in the working state.

較佳地，步驟1中，採用原子層沉積反應器，向輸氣管道內通入第一反應氣體的具體方法為：將輸氣管道置於原子層沉積反應器的反應腔內，向反應腔內通入第一反應氣體，使第一反應氣體進入輸氣管道內。Preferably, in step 1, an atomic layer deposition reactor is used to pass the first reaction gas into the gas pipeline. The specific method is: the gas pipeline is placed in the reaction chamber of the atomic layer deposition reactor and directed to the reaction chamber. The first reaction gas is passed into it, so that the first reaction gas enters the gas pipeline.

較佳地，步驟1中，採用原子層沉積反應器，向輸氣管道內通入第一反應氣體的具體方法為：將輸氣管道的一端堵塞，另一端與原子層沉積反應器的氣路連接，透過氣路將第一反應氣體通入輸氣管道內。Preferably, in step 1, an atomic layer deposition reactor is used to pass the first reaction gas into the gas pipeline. The specific method is: plug one end of the gas pipeline, and the other end is connected to the gas path of the atomic layer deposition reactor. Connect, pass the first reaction gas into the gas pipeline through the gas path.

本發明的有益效果：The beneficial effects of the present invention:

（1）採用原子層沉積技術製備抗腐蝕塗層的方法不受輸氣管道（gas line）形狀及結構的限制，比如可以用於曲面，氣孔(＞Φ1mm)內壁。(1) The method of preparing anti-corrosion coating using atomic layer deposition technology is not limited by the shape and structure of gas line, for example, it can be used on curved surfaces and inner walls of pores (>Φ1mm).

（2）原子層沉積技術具有表面控制性，可以在整個輸氣管道內壁全覆蓋上抗腐蝕塗層。(2) Atomic layer deposition technology has surface control properties, which can cover the entire inner wall of the gas pipeline with an anti-corrosion coating.

（3）原子層沉積技術製備的塗層緻密，膜厚均勻。(3) The coating prepared by atomic layer deposition technology is dense and the film thickness is uniform.

（4）採用本發明抗腐蝕塗層製備方法便於大批量生產。(4) Adopting the anti-corrosion coating preparation method of the present invention is convenient for mass production.

下述將結合附圖對本發明的技術方案進行清楚、完整地描述，顯然，所描述的實施方式是本發明的一部分實施方式，而不是全部的實施方式。基於本發明中的實施方式，所屬技術領域中具有通常知識者在沒有做出創造性勞動前提下所獲得的所有其它實施方式，都屬於本發明保護的範圍。The technical solutions of the present invention will be clearly and completely described in the following with reference to the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by those with ordinary knowledge in the technical field without creative work shall fall within the protection scope of the present invention.

在本發明的描述中，需要說明的是，用語「第一」、「第二」僅用於描述目的，而不能理解為指示或暗示相對重要性。In the description of the present invention, it should be noted that the terms "first" and "second" are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance.

實施例1Example 1

如圖1所示，為現有的一種電漿蝕刻設備，其包含：反應腔1、氣體噴淋頭3、用於通入可能具有腐蝕性的反應氣體的氣體通孔2、複數個輸氣管道4、氣源5及複數個電子開關閥門6。氣源5通過輸氣管道4向反應腔1內通入具有腐蝕性的反應氣體。As shown in Figure 1, it is an existing plasma etching equipment, which includes: a reaction chamber 1, a gas shower head 3, a gas through hole for passing in a potentially corrosive reaction gas 2, a plurality of gas pipelines 4. Air source 5 and multiple electronic switch valves 6. The gas source 5 passes corrosive reaction gas into the reaction chamber 1 through the gas pipeline 4.

在電漿蝕刻設備未組裝前，將輸氣管道4置於原子層沉積反應器的反應腔內，在輸氣管道4內壁沉積氧化鋁薄膜，作為抗腐蝕塗層。輸氣管道4的內徑為2~4mm，長度為1m。Before the plasma etching equipment is assembled, the gas pipeline 4 is placed in the reaction chamber of the atomic layer deposition reactor, and an aluminum oxide film is deposited on the inner wall of the gas pipeline 4 as an anti-corrosion coating. The gas pipeline 4 has an inner diameter of 2~4mm and a length of 1m.

使用超純水作為氧源，三甲基鋁作為鋁源，N2 沖洗氣體。具體步驟如下：Use ultrapure water as the oxygen source, trimethylaluminum as the aluminum source, and N 2 flushing gas. Specific steps are as follows:

步驟1，將輸氣管道4置於原子層沉積反應器的反應腔內，向反應腔內通入第一反應氣體Al(CH3 )3 ，以進行第一化學吸附；第一反應氣體會吸附至輸氣管道4表面，包含輸氣管道4的管道內壁（inner wall surface）表面；Step 1. Place the gas pipeline 4 in the reaction chamber of the atomic layer deposition reactor, and pass the first reaction gas Al(CH 3 ) 3 into the reaction chamber for the first chemical adsorption; the first reaction gas will be adsorbed To the surface of the gas pipeline 4, including the inner wall surface of the gas pipeline 4;

步驟2，採用氮氣流吹掃，以除去輸氣管道4未吸附的第一反應氣體及/或第一化學吸附產生的副產物；Step 2: Purging with a nitrogen stream to remove the unadsorbed first reaction gas and/or by-products produced by the first chemical adsorption in the gas pipeline 4;

步驟3，向原子層沉積反應器中通入第二反應氣體H2 O，以進行第二化學吸附；Step 3. Pass the second reaction gas H 2 O into the atomic layer deposition reactor to perform the second chemical adsorption;

步驟4，採用氮氣流吹掃，以除去輸氣管道4未吸附的第二反應氣體及/或第二化學吸附產生的副產物；Step 4, purging with a nitrogen stream to remove the unadsorbed second reaction gas and/or by-products produced by the second chemical adsorption in the gas pipeline 4;

步驟5，重複步驟1~4，直到輸氣管道4的內壁產生的抗腐蝕塗層符合要求。Step 5, repeat steps 1 to 4 until the anti-corrosion coating produced on the inner wall of the gas pipeline 4 meets the requirements.

上述步驟的總反應式如下：The total reaction formula of the above steps is as follows:

Figure 02_image001
Figure 02_image001

實施例2Example 2

如圖2所述，為現有的一種金屬材質的輸氣管道7，其包含兩個進氣口8、及氣體出口9。該輸氣管道7與電漿蝕刻設備配合使用。電漿蝕刻設備包含反應腔室（chamber）及氣體噴淋頭，輸氣管道7將用於電漿蝕刻的反應氣體透過氣體噴淋頭導入反應腔室中，再向反應腔室施加射頻功率作用於反應氣體產生電漿，對放置於反應腔室中的待加工半導體工件進行電漿處理製程。As shown in FIG. 2, it is an existing gas pipeline 7 made of metal material, which includes two air inlets 8 and a gas outlet 9. The gas pipeline 7 is used in conjunction with plasma etching equipment. The plasma etching equipment includes a reaction chamber (chamber) and a gas shower head. The gas pipeline 7 introduces the reaction gas used for plasma etching into the reaction chamber through the gas shower head, and then applies radio frequency power to the reaction chamber. Plasma is generated from the reaction gas, and the plasma treatment process is performed on the semiconductor workpiece to be processed placed in the reaction chamber.

採用電漿蝕刻設備對半導體材料進行蝕刻，通常採用含有氯、氟等的化學活性物質。這些腐蝕性氣體通過輸氣管道7，會腐蝕輸氣管道7，從而造成污染。本實施例透過原子層沉積技術在輸氣管道7內壁沉積氧化鋁薄膜，作為抗腐蝕塗層。Plasma etching equipment is used to etch semiconductor materials, and chemically active substances containing chlorine and fluorine are usually used. These corrosive gases pass through the gas pipeline 7 and will corrode the gas pipeline 7 and cause pollution. In this embodiment, an aluminum oxide film is deposited on the inner wall of the gas pipeline 7 through atomic layer deposition technology as an anti-corrosion coating.

使用超純水作為氧源，三甲基鋁作為鋁源，N2 沖洗氣體。具體步驟如下：Use ultrapure water as the oxygen source, trimethylaluminum as the aluminum source, and N 2 flushing gas. Specific steps are as follows:

步驟1，將輸氣管道7的兩個進氣口8堵塞，氣體出口9與原子層沉積反應器的氣路連接，使原子層沉積反應器的氣流能夠通入輸氣管道7；密封原子層沉積反應器的反應腔，向反應腔內通入氮氣並抽真空後，向反應腔內通入第一反應氣體Al (CH3 )3 ，第一反應氣體Al (CH3 )3 透過氣路進入輸氣管道7內，以進行第一化學吸附：第一反應氣體會吸附至輸氣管道7的內壁表面；Step 1. Block the two gas inlets 8 of the gas pipeline 7 and connect the gas outlet 9 with the gas path of the atomic layer deposition reactor so that the gas flow from the atomic layer deposition reactor can pass into the gas pipeline 7; seal the atomic layer after the reaction chamber of the deposition reactor, sparged with nitrogen and evacuated reaction chamber, a first reaction gas into a l (CH 3) 3 to a reaction chamber, a first reactive gas a l (CH 3) 3 gas permeable Enter the gas pipeline 7 for the first chemical adsorption: the first reaction gas will be adsorbed to the inner wall surface of the gas pipeline 7;

步驟2，採用氮氣流吹掃，以除去輸氣管道7未吸附的第一反應氣體及/或第一化學吸附產生的副產物；Step 2: Purging with a nitrogen stream to remove the unadsorbed first reaction gas and/or by-products produced by the first chemical adsorption in the gas pipeline 7;

步驟3，向原子層沉積反應器中通入第二反應氣體H2 O，以進行第二化學吸附；Step 3. Pass the second reaction gas H 2 O into the atomic layer deposition reactor to perform the second chemical adsorption;

步驟4，採用氮氣流吹掃，以除去輸氣管道7未吸附的第二反應氣體及/或第二化學吸附產生的副產物；Step 4, purging with a nitrogen stream to remove the unadsorbed second reaction gas and/or by-products produced by the second chemical adsorption in the gas pipeline 7;

步驟5，重複步驟1~4，直到輸氣管道7的內壁產生的抗腐蝕塗層符合要求。Step 5. Repeat steps 1 to 4 until the anti-corrosion coating produced on the inner wall of the gas pipeline 7 meets the requirements.

採用原子層沉積(atomiclayer deposition，ALD)技術，得到的薄膜純度高，均勻及保形性好，還能精確地控制薄膜厚度。本發明塗層採用ALD技術能夠有效增強輸氣管道耐腐蝕性能。本發明採用ALD技術在輸氣管道內壁產生抗腐蝕塗層，包含但不限於Al2 O3 、SiO2 、Y2 O3 、YF3 、YOF、Ta2 O5 、TaN等。其中，Al2 O3 薄膜硬度高，耐磨性好，耐高溫，並且具有優良的電絕緣性及耐腐蝕性。Using atomic layer deposition (ALD) technology, the obtained film has high purity, uniformity and good shape retention, and the film thickness can be precisely controlled. The coating of the invention adopts the ALD technology to effectively enhance the corrosion resistance of the gas pipeline. The present invention adopts ALD technology to produce an anti-corrosion coating on the inner wall of a gas pipeline, including but not limited to Al 2 O 3 , SiO 2 , Y 2 O 3 , YF 3 , YOF, Ta 2 O 5 , TaN and the like. Among them, the Al 2 O 3 film has high hardness, good wear resistance, high temperature resistance, and has excellent electrical insulation and corrosion resistance.

實施例3Example 3

利用SEM-EDS對部分金屬輸氣管道樣品的內壁沉積的氧化鋁薄膜的形貌及能譜進行觀察。輸氣管道樣品的材質為不銹鋼。儀器為場發射掃描電鏡（TESCAN MIRA），並透過能譜儀（EDS）進行樣品成分元素種類與含量分析。SEM-EDS was used to observe the morphology and energy spectrum of the aluminum oxide film deposited on the inner wall of some metal gas pipeline samples. The material of the gas pipeline sample is stainless steel. The instrument is a field emission scanning electron microscope (TESCAN MIRA), and an energy spectrometer (EDS) is used to analyze the types and contents of the components of the sample.

將輸氣管道沿其長軸橫剖，結果如圖3A所示，作為抗腐蝕塗層的氧化鋁薄膜已完全覆蓋管道內壁。圖3B至圖3E為管道內壁在不同放大倍數下的顯微圖，經ALD技術產生氧化鋁膜後的管道內壁薄厚均勻，塗層緻密。The gas pipeline is cross-sectioned along its long axis. As shown in Figure 3A, the aluminum oxide film as an anti-corrosion coating has completely covered the inner wall of the pipeline. Figures 3B to 3E are micrographs of the inner wall of the pipeline under different magnifications. The inner wall of the pipeline after the aluminum oxide film is produced by the ALD technology has a uniform thickness and a dense coating.

如圖4所示，輸氣管道樣品內壁的抗腐蝕塗層主要成分為C、O、Al，未檢測到其它金屬，說明抗腐蝕塗層的純度高、完整、緻密，已將管道內壁完全覆蓋。As shown in Figure 4, the main components of the anti-corrosion coating on the inner wall of the gas pipeline sample are C, O, Al, and no other metals are detected, indicating that the anti-corrosion coating is of high purity, integrity, and compactness. Fully covered.

綜上所述，採用原子層沉積技術製備抗腐蝕塗層的方法不受輸氣管道形狀及結構的限制，可以在整個輸氣管道內壁全覆蓋上抗腐蝕塗層，塗層緻密，膜厚均勻，便於大批量生產。In summary, the method of preparing anti-corrosion coatings by atomic layer deposition technology is not limited by the shape and structure of gas pipelines, and the entire gas pipeline inner wall can be covered with anti-corrosion coatings. The coating is dense and the film is thick. Uniform, convenient for mass production.

儘管本發明的內容已經透過上述較佳實施例作了詳細介紹，但應當認識到上述的描述不應被認為是對本發明的限制。在所屬技術領域中具有通常知識者閱讀了上述內容後，對於本發明的多種修改及替代都將是顯而易見的。因此，本發明的保護範圍應由所附之申請專利範圍來定義。Although the content of the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description should not be considered as limiting the present invention. Various modifications and alternatives to the present invention will be obvious to those with ordinary knowledge in the technical field after reading the above content. Therefore, the scope of protection of the present invention should be defined by the scope of the attached patent application.

1:反應腔 2:氣體通孔 3:氣體噴淋頭 4:輸氣管道 5:氣源 6:電子開關閥門 7:輸氣管道 8:進氣口 9:氣體出口1: Reaction chamber 2: Gas through hole 3: Gas shower head 4: Gas pipeline 5: Air source 6: Electronic switch valve 7: Gas pipeline 8: Air inlet 9: Gas outlet

圖1係為現有的一種電漿蝕刻設備的結構示意圖。 圖2係為現有的一種輸氣管道的結構示意圖。 圖3A係為實施例3的輸氣管道的橫剖面的掃描電鏡顯微圖。 圖3B、圖3C、圖3D、圖3E係分別為實施例3的輸氣管道在不同放大倍數下的掃描電鏡顯微圖。 圖4係為能譜儀對實施例3的輸氣管道的成分元素種類與含量的分析結果。FIG. 1 is a schematic diagram of the structure of a conventional plasma etching equipment. Figure 2 is a schematic structural diagram of an existing gas pipeline. FIG. 3A is a scanning electron microscope micrograph of the cross section of the gas pipeline of Example 3. FIG. Fig. 3B, Fig. 3C, Fig. 3D, and Fig. 3E are respectively scanning electron microscope micrographs of the gas pipeline of Example 3 under different magnifications. Figure 4 is the analysis result of the type and content of the component elements of the gas pipeline of Example 3 by the energy spectrometer.

Claims (9)

一種採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中該輸氣管道為電漿蝕刻設備或MOCVD設備的輸氣管道，該方法包含： 步驟1，採用一原子層沉積反應器，向該輸氣管道內通入一第一反應氣體，以進行一第一化學吸附，使得該第一反應氣體吸附至該輸氣管道的內壁表面； 步驟2，採用一惰性氣流吹掃，以除去該輸氣管道未吸附的該第一反應氣體及/或該第一化學吸附產生的副產物； 步驟3，向該原子層沉積反應器中通入一第二反應氣體，以進行一第二化學吸附； 步驟4，採用該惰性氣流吹掃，以除去該輸氣管道未吸附的該第二反應氣體及/或該第二化學吸附產生的副產物； 步驟5，重複步驟1-4，直到該輸氣管道的內壁產生的抗腐蝕塗層符合要求。A method of using ALD technology to produce an anti-corrosion coating on the inner wall of a gas pipeline, wherein the gas pipeline is a gas pipeline of plasma etching equipment or MOCVD equipment, and the method includes: Step 1. Using an atomic layer deposition reactor, pass a first reaction gas into the gas pipeline to perform a first chemical adsorption, so that the first reaction gas is adsorbed to the inner wall surface of the gas pipeline; Step 2: Purging with an inert gas stream to remove the first reaction gas and/or the by-products generated by the first chemical adsorption that are not adsorbed by the gas pipeline; Step 3. Pass a second reaction gas into the atomic layer deposition reactor to perform a second chemical adsorption; Step 4, purging with the inert gas flow to remove the second reaction gas and/or the by-products generated by the second chemical adsorption that are not adsorbed by the gas pipeline; Step 5: Repeat steps 1-4 until the anti-corrosion coating produced on the inner wall of the gas pipeline meets the requirements. 如請求項1所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中該抗腐蝕塗層的成分包含Al2 O3 、SiO2 、Y2 O3 、YF3 、YOF、Ta2 O5 及TaN中的至少一種。The method of using ALD technology to produce an anti-corrosion coating on the inner wall of a gas pipeline as described in claim 1, wherein the composition of the anti-corrosion coating includes Al 2 O 3 , SiO 2 , Y 2 O 3 , YF 3 , YOF , At least one of Ta 2 O 5 and TaN. 如請求項2所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中該抗腐蝕塗層為Al2 O3 塗層。The method for producing an anti-corrosion coating on the inner wall of a gas pipeline using ALD technology as described in claim 2, wherein the anti-corrosion coating is an Al 2 O 3 coating. 如請求項1所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中該第一反應氣體為Al (CH3 )3 。The requested item 1 of the method of producing anti-corrosion coating ALD technique in gas pipeline inside wall, wherein the first reactive gas is A l (CH 3) 3. 如請求項1所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中該惰性氣流為氮氣。The method for producing an anti-corrosion coating on the inner wall of a gas pipeline using ALD technology as described in claim 1, wherein the inert gas stream is nitrogen. 如請求項1所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中該第二反應氣體為H2 O。The method for producing an anti-corrosion coating on the inner wall of a gas pipeline using ALD technology as described in claim 1, wherein the second reaction gas is H 2 O. 如請求項1所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中該輸氣管道為工作狀態下，內部流經腐蝕性氣體的金屬管道。The method for producing an anti-corrosion coating on the inner wall of a gas pipeline using ALD technology as described in claim 1, wherein the gas pipeline is a metal pipeline through which corrosive gas flows through the gas pipeline under working conditions. 如請求項1所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中在步驟1中，採用該原子層沉積反應器，向該輸氣管道內通入該第一反應氣體的具體方法為：將該輸氣管道置於該原子層沉積反應器的一反應腔內，向該反應腔內通入該第一反應氣體，使該第一反應氣體進入該輸氣管道內。The method for producing an anti-corrosion coating on the inner wall of a gas pipeline using ALD technology as described in claim 1, wherein in step 1, the atomic layer deposition reactor is used to pass the first reaction into the gas pipeline The specific method of gas is: placing the gas pipeline in a reaction chamber of the atomic layer deposition reactor, passing the first reaction gas into the reaction chamber, and allowing the first reaction gas to enter the gas pipeline . 如請求項1所述之採用ALD技術在輸氣管道內壁產生抗腐蝕塗層的方法，其中步驟1中，採用該原子層沉積反應器，向該輸氣管道內通入該第一反應氣體的具體方法為：將該輸氣管道的一端堵塞，另一端與該原子層沉積反應器的氣路連接，透過氣路將該第一反應氣體通入該輸氣管道內。The method for producing an anti-corrosion coating on the inner wall of a gas pipeline using ALD technology as described in claim 1, wherein in step 1, the atomic layer deposition reactor is used to pass the first reaction gas into the gas pipeline The specific method is as follows: one end of the gas pipeline is blocked, the other end is connected with the gas path of the atomic layer deposition reactor, and the first reaction gas is passed into the gas pipeline through the gas path.
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