JPH08144089A - Vacuum chamber member made of aluminum or aluminum alloy - Google Patents
Vacuum chamber member made of aluminum or aluminum alloyInfo
- Publication number
- JPH08144089A JPH08144089A JP28231294A JP28231294A JPH08144089A JP H08144089 A JPH08144089 A JP H08144089A JP 28231294 A JP28231294 A JP 28231294A JP 28231294 A JP28231294 A JP 28231294A JP H08144089 A JPH08144089 A JP H08144089A
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- Prior art keywords
- vacuum chamber
- alloy
- chamber member
- member made
- oxide film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Chemical Vapour Deposition (AREA)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＣＶＤ装置，ＰＶＤ装
置，ドライエッチング装置などに用いられるＡｌまたは
Ａｌ合金製真空チャンバ部材であって、真空チャンバ内
に導入される腐食性のガスやプラズマに対して優れた耐
食性を発揮するＡｌまたはＡｌ合金製真空チャンバ部材
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vacuum chamber member made of Al or Al alloy used in a CVD apparatus, a PVD apparatus, a dry etching apparatus, etc., and is suitable for corrosive gas or plasma introduced into the vacuum chamber. On the other hand, the present invention relates to a vacuum chamber member made of Al or Al alloy that exhibits excellent corrosion resistance.
【０００２】[0002]
【従来の技術】ＣＶＤ装置，ＰＶＤ装置，ドライエッチ
ング装置などに用いられる真空チャンバの内部には、反
応ガスやエッチングガスとしてＣｌやＦ等のハロゲン元
素を含む腐食性のガスが導入されることから、腐食性ガ
スに対する耐食性（以下、耐ガス性ということがある）
が要求されている。また熱プラズマＣＶＤ装置等の場合
には、上記腐食性ガスに加えて、ハロゲン系のプラズマ
も発生するので、プラズマに対する耐食性（以下、耐プ
ラズマ性ということがある）も重要である。2. Description of the Related Art Since a corrosive gas containing a halogen element such as Cl or F is introduced as a reaction gas or an etching gas into a vacuum chamber used in a CVD apparatus, a PVD apparatus, a dry etching apparatus or the like. , Corrosion resistance to corrosive gas (hereinafter sometimes referred to as gas resistance)
Is required. Further, in the case of a thermal plasma CVD apparatus or the like, halogen-based plasma is also generated in addition to the above corrosive gas, so that the corrosion resistance to plasma (hereinafter sometimes referred to as plasma resistance) is also important.
【０００３】その為、上記真空チャンバ用材料としては
従来主にステンレス鋼材が用いられていた。しかしなが
ら、ステンレス鋼製の真空チャンバは重量が大きく土台
に大掛かりな工事が必要であり、また熱伝導性が十分で
なく作動時のベーキングに時間がかかるという問題があ
った。更に、ステンレス鋼の成分であるＣｒなどの重金
属が、何らかの要因でプロセス中に放出されて汚染源と
なることもあった。そこで、ステンレス鋼より軽量で、
熱伝導性に優れ、しかも重金属汚染のおそれのないＡｌ
またはＡｌ合金製の真空チャンバの開発が検討されてい
る。Therefore, stainless steel has been mainly used as the material for the vacuum chamber. However, the vacuum chamber made of stainless steel has a problem that it is heavy and requires a large amount of work on the base, and the thermal conductivity is not sufficient, and it takes a long time to bake at the time of operation. Further, heavy metals such as Cr, which is a component of stainless steel, may be released into the process during some reason and become a pollution source. So it's lighter than stainless steel,
Al with excellent thermal conductivity and without fear of heavy metal contamination
Alternatively, development of a vacuum chamber made of Al alloy is under consideration.
【０００４】しかしながら、ＡｌまたはＡｌ合金の地金
表面は耐プラズマ性が必ずしも良い訳ではなく、何らか
の表面処理を施すことが必要と考えられ、種々検討され
ている。例えば、特公平５−５３８７０号公報には、Ａ
ｌまたはＡｌ合金製真空チャンバ部材の表面に陽極酸化
処理を施し、陽極酸化皮膜を形成することによりＡｌま
たはＡｌ合金の耐ガス性を向上させて真空チャンバとす
る発明が開示されている。但し上記陽極酸化皮膜は、前
記腐食性ガスやプラズマとの反応を全く起こさないとい
うものではなく、使用中に腐食されると反応生成物が微
粒子として発生し、例えば半導体製造に用いられると不
良品の原因となることがあり、改善が望まれていた。However, the surface of a bare metal of Al or an Al alloy does not necessarily have good plasma resistance, and it is considered necessary to perform some kind of surface treatment, and various studies have been conducted. For example, in Japanese Examined Patent Publication No. 5-53870, A
An invention has been disclosed in which the surface of a vacuum chamber member made of l or Al alloy is anodized to form an anodic oxide film to improve the gas resistance of Al or Al alloy to form a vacuum chamber. However, the above anodic oxide film does not cause any reaction with the corrosive gas or plasma at all, and reaction products are generated as fine particles when corroded during use, for example, defective products when used in semiconductor manufacturing. There is a possibility that it may cause a problem, and improvement has been desired.
【０００５】また特公平５−５３８７１号公報には、イ
オンプレーティング法を採用しＡｌまたはＡｌ合金製真
空チャンバ部材の表面に、耐食性に優れた皮膜（例え
ば、ＴｉＮ，ＴｉＣ等）を形成する技術が開示されてい
る。但し、上記皮膜をイオンプレーティング等の気相合
成法により作成すると、かなりの処理コストがかかると
いう問題がある。Japanese Patent Publication No. 5-53871 discloses a technique for forming a film (for example, TiN, TiC, etc.) having excellent corrosion resistance on the surface of a vacuum chamber member made of Al or Al alloy by adopting an ion plating method. Is disclosed. However, if the above-mentioned film is formed by a vapor phase synthesis method such as ion plating, there is a problem that a considerable processing cost is required.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記事情に着
目してなされたものであって、コスト的に有利な陽極酸
化処理法を採用することを前提として、耐ガス性及び耐
プラズマ性に優れたＡｌまたはＡｌ合金製真空チャンバ
部材を提供しようとするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is based on the premise that a cost-effective anodizing treatment method is adopted, and gas resistance and plasma resistance are improved. It is intended to provide an excellent Al or Al alloy vacuum chamber member.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成した本発
明のＡｌまたはＡｌ合金製真空チャンバ部材とは、硫酸
イオンを含む溶液中で陽極酸化処理されて多孔質な酸化
皮膜が形成されてなるＡｌまたはＡｌ合金製真空チャン
バ部材であって、上記酸化皮膜の表面に形成された凹部
の全表面積をａ、該凹部を除いた外表面の面積をｂとし
たとき、（ａ＋ｂ）／ｂの値が３０００以下であること
を要旨とするものである。The vacuum chamber member made of Al or Al alloy of the present invention, which has achieved the above object, is formed by anodizing in a solution containing sulfate ions to form a porous oxide film. A vacuum chamber member made of Al or Al alloy, where the total surface area of the recesses formed on the surface of the oxide film is a and the area of the outer surface excluding the recesses is b, the value of (a + b) / b Is 3,000 or less.
【０００８】また上記硫酸イオンに代えてりん酸イオン
を含む溶液中で陽極酸化処理されて多孔質な酸化皮膜が
形成されてなるＡｌまたはＡｌ合金製真空チャンバ部材
であってもよく、その場合には上記（ａ＋ｂ）／ｂの値
は、７００以下とすることが好ましい。Further, it may be an Al or Al alloy vacuum chamber member formed by anodizing in a solution containing phosphate ions instead of the above-mentioned sulfate ions to form a porous oxide film, in which case It is preferable that the value of (a + b) / b is 700 or less.
【０００９】更に、りん酸イオンを含む溶液中で陽極酸
化処理された上記真空チャンバ部材の場合には、上記酸
化皮膜の表面に形成された凹部の中で、相隣接する２つ
の凹部の平面視の中心点を結ぶ距離が０．００５〜０．
５μｍであり、上記酸化皮膜中のＰ濃度が０．０１重量
％以上であることが推奨される。Further, in the case of the vacuum chamber member anodized in a solution containing phosphate ions, two recesses adjacent to each other among the recesses formed on the surface of the oxide film are viewed in plan view. Is 0.005 to 0.
It is 5 μm, and it is recommended that the P concentration in the oxide film is 0.01% by weight or more.
【００１０】尚、本発明において、ＡｌまたはＡｌ合金
製真空チャンバ部材とは、ＡｌまたはＡｌ合金製真空チ
ャンバの構造材だけではなく、該真空チャンバ内に配設
されるクランパー，シャワーヘッド，サセプターなどの
部材であって、ＡｌまたはＡｌ合金で製作されるものは
全て適用可能であり、以下の説明では、これらの部材を
すべて包含してＡｌまたはＡｌ合金製真空チャンバ部材
と総称する。In the present invention, the vacuum chamber member made of Al or Al alloy is not only the structural material of the vacuum chamber made of Al or Al alloy, but also a clamper, a shower head, a susceptor, etc. arranged in the vacuum chamber. All the members manufactured by Al or Al alloy are applicable, and in the following description, these members are collectively referred to as an Al or Al alloy vacuum chamber member.
【００１１】[0011]
【作用】本発明者らは、ＡｌまたはＡｌ合金について、
前述の腐食性ガスやプラズマに対する耐食性が悪いので
これを改善すべく、陽極酸化処理について種々の実験を
重ねてきた。その結果、特定の形態を有する陽極酸化皮
膜であれば、非常に優れた耐ガス性及び耐プラズマ性を
発揮することを見出した。The present inventors have found that Al or Al alloy
Since the above-mentioned corrosion resistance to the corrosive gas and plasma is poor, various experiments have been conducted on the anodizing treatment in order to improve this. As a result, they have found that an anodic oxide film having a specific form exhibits extremely excellent gas resistance and plasma resistance.
【００１２】尚、従来のＡｌまたはＡｌ合金製真空チャ
ンバ部材では、陽極酸化処理を行うに際して陽極酸化処
理皮膜の膜厚を制御する技術（例えば、上記特公平５ー
５３８７０号公報）は知られていた。しかしながら、腐
食性ガスやプラズマとの腐食反応を抑制するために、陽
極酸化皮膜の形態を制御するという試みは行われておら
ず、またこの観点から検討を行った事例の報告はない。Incidentally, in the conventional vacuum chamber member made of Al or Al alloy, there is known a technique for controlling the film thickness of the anodizing film when the anodizing process is carried out (for example, Japanese Patent Publication No. 53870/1993). It was However, no attempt has been made to control the morphology of the anodized film in order to suppress the corrosive reaction with corrosive gas or plasma, and there are no reports of cases examined from this viewpoint.
【００１３】即ち、本発明に係るＡｌまたはＡｌ合金製
真空チャンバ部材では、陽極酸化皮膜の形態が、ある特
定の条件を満足する場合にのみ、優れた耐ガス性と耐プ
ラズマ性を発揮する。その特定の条件とは、下記〜
のいずれかの条件である。尚、図１は代表的な陽極酸化
皮膜の概略構造を示す一部断面説明図である。図１にお
いて、１はＡｌまたはＡｌ合金製の基材であり、２は陽
極酸化皮膜、３は凹部である。That is, in the vacuum chamber member made of Al or Al alloy according to the present invention, excellent gas resistance and plasma resistance are exhibited only when the morphology of the anodized film satisfies certain specific conditions. The specific conditions are as follows:
Is one of the conditions. Incidentally, FIG. 1 is a partial cross-sectional explanatory view showing a schematic structure of a typical anodized film. In FIG. 1, 1 is a base material made of Al or Al alloy, 2 is an anodized film, and 3 is a recess.
【００１４】 硫酸イオンを含む溶液中で陽極酸化処
理されて形成された酸化皮膜においては、凹部の全表面
積をａ、該凹部を除いた外表面の面積をｂとしたとき、
（ａ＋ｂ）／ｂの値が３０００以下であること。 りん酸イオンを含む溶液中で陽極酸化処理されて形
成された酸化皮膜においては、上記（ａ＋ｂ）／ｂの値
が７００以下であること。 りん酸イオンを含む溶液中で陽極酸化処理されて形
成された酸化皮膜においては、該酸化皮膜の表面に形成
された凹部の中で、相隣接する２つの凹部の平面視の中
心点を結ぶ距離が０．００５〜０．５μｍであり、上記
酸化皮膜中のＰ濃度が０．０１重量％以上であること。In the oxide film formed by anodizing in a solution containing sulfate ions, when the total surface area of the recesses is a and the outer surface area excluding the recesses is b,
The value of (a + b) / b should be 3000 or less. The value of (a + b) / b is 700 or less in the oxide film formed by anodizing in a solution containing phosphate ions. In an oxide film formed by anodizing in a solution containing phosphate ions, the distance between the center points of two adjacent recesses in plan view among the recesses formed on the surface of the oxide film. Is 0.005 to 0.5 μm, and the P concentration in the oxide film is 0.01% by weight or more.
【００１５】上記〜の条件のいずれかを満足する酸
化皮膜を形成することにより、優れた耐食性が得られる
理由については十分解明された訳ではないが、以下のよ
うに考えられる。即ち、陽極酸化皮膜を上記形態に制御
することによって、腐食性ガスに対しては、酸化皮膜表
面での滞留時間を可及的に小さくでき、局部的に発生し
易い腐食性ガスの濃化現象にもとづく腐食発生を低減
し、一方プラズマに曝された場合には、上記酸化皮膜表
面におけるプラズマの局部的な集中が抑制されるものと
考えられる。The reason why excellent corrosion resistance can be obtained by forming an oxide film satisfying any of the above conditions (1) to (4) has not been fully clarified, but it is considered as follows. That is, by controlling the anodized film in the above-described form, the residence time on the surface of the oxide film can be made as short as possible with respect to the corrosive gas, and the concentration phenomenon of the corrosive gas that is likely to occur locally It is considered that the occurrence of corrosion based on the above is reduced, and when exposed to plasma, local concentration of plasma on the surface of the oxide film is suppressed.
【００１６】上記条件において、凹部を含まない外表
面の面積（ａ）および凹部の表面積（ｂ）は、ＳＥＭ観
察により算出すればよく、（ａ＋ｂ）／ｂの値が３００
０以下であれば優れた耐食性を発揮する。望ましくは、
２５００以下であり、１５００以下であるとより望まし
い。Under the above conditions, the area (a) of the outer surface not including the recess and the surface area (b) of the recess may be calculated by SEM observation, and the value of (a + b) / b is 300.
If it is 0 or less, excellent corrosion resistance is exhibited. Preferably,
It is 2500 or less, and more preferably 1500 or less.
【００１７】また上記条件、即ち条件の硫酸イオン
をりん酸イオンに代えて陽極酸化皮膜を形成した場合
は、上記（ａ＋ｂ）／ｂの値が、７００以下であれば優
れた耐食性を発揮する。望ましくは、５００以下であ
り、３００以下であるとより望ましい。なお、りん酸を
含む溶液中で陽極酸化処理することが好ましい理由とし
ては、上記溶液の成分または溶液成分とＡｌの化合物
［例えばＡｌＰＯ4 やＡｌ（Ｈ2 ＰＯ4 ）3 等］が、耐
食性の向上に寄与しているものと考えられる。Further, when the anodic oxide film is formed under the above conditions, that is, the sulfate ions are replaced by the phosphate ions, excellent corrosion resistance is exhibited when the value of (a + b) / b is 700 or less. It is preferably 500 or less, and more preferably 300 or less. The reason why it is preferable to carry out the anodizing treatment in a solution containing phosphoric acid is that the components of the solution or the compound of the solution and Al [for example, AlPO 4 or Al (H 2 PO 4 ) 3 ] have high corrosion resistance. It is considered that it contributes to the improvement.
【００１８】さらに上記条件において、酸化皮膜中に
Ｐを含有させることによって耐食性が向上される理由し
ては、Ｐがりん酸塩またはＰ化合物として酸化皮膜中に
存在することにより、該酸化皮膜の化学的安定性を向上
するからであると考えられる。尚、Ｐの添加効果を発揮
させるには、少なくとも０．０１重量％以上含有させる
ことが必要であり、０．１重量％以上が好ましく、０．
５重量％以上であればより好ましい。本発明はＰ含有量
の上限を設定するものではなく、溶液組成と陽極酸化処
理条件によって適宜設定すればよい。Further, the reason why the corrosion resistance is improved by including P in the oxide film under the above-mentioned conditions is that P is present in the oxide film as a phosphate or a P compound, so that It is considered that this is because the chemical stability is improved. In order to exert the effect of adding P, it is necessary to contain at least 0.01 wt% or more, preferably 0.1 wt% or more, and 0.1.
More preferably, it is 5% by weight or more. In the present invention, the upper limit of the P content is not set, but may be set appropriately depending on the solution composition and the anodizing condition.
【００１９】また、上記酸化皮膜の表面に形成された凹
部の中で、相隣接する２つの凹部の平面視の中心点を結
ぶ距離が０．００５〜０．５μｍの範囲内であることが
望ましく、上記距離がこの範囲外では優れた耐食性が期
待できない。より好ましい範囲は、０．０２〜０．３μ
ｍである。Further, among the recesses formed on the surface of the oxide film, the distance connecting the center points of two adjacent recesses in plan view is preferably in the range of 0.005 to 0.5 μm. However, if the above distance is outside this range, excellent corrosion resistance cannot be expected. A more preferable range is 0.02-0.3μ
m.
【００２０】本発明は、陽極酸化皮膜の厚さを特に限定
するものではないが、優れた耐食性を発揮するには、
０．１μｍ以上形成することが好ましく、０．５μｍ以
上がより好ましい。但し、皮膜厚さが厚過ぎると、内部
応力等の影響により割れを生じて表面の被覆が不充分に
なったり、更には皮膜の剥離を起こすので４０μｍ以下
とすることが望ましい。The present invention does not particularly limit the thickness of the anodic oxide film, but in order to exhibit excellent corrosion resistance,
The thickness is preferably 0.1 μm or more, more preferably 0.5 μm or more. However, if the coating thickness is too thick, cracking occurs due to the influence of internal stress and the like, the surface coating becomes insufficient, or the coating peels off.
【００２１】尚、本発明は陽極酸化皮膜の膜質により限
定されるものではないが、Ｘ線回折を行ったところ、皮
膜の主体が非晶質であるときに特に優れた耐食性を発揮
することを見出した。皮膜中の結晶質酸化物の含有率
は、３０％以下が好ましく、１０％以下であればより好
ましい。The present invention is not limited by the film quality of the anodized film, but X-ray diffraction shows that it exhibits particularly excellent corrosion resistance when the film is mainly amorphous. I found it. The content of the crystalline oxide in the film is preferably 30% or less, more preferably 10% or less.
【００２２】本発明は、陽極酸化皮膜を形成する方法を
限定するものではなく、前記〜の条件のいずれかを
満足する様に適宜陽極酸化処理条件を設定すればよい。
尚、陽極酸化処理条件としては、溶液の組成、溶液温
度、電解条件（電圧、電流密度、電流−電圧波形）等が
挙げられる。The present invention does not limit the method for forming the anodized film, and the anodizing conditions may be set appropriately so as to satisfy any one of the above conditions (1) to (4).
The conditions of the anodizing treatment include the composition of the solution, the solution temperature, the electrolysis conditions (voltage, current density, current-voltage waveform) and the like.
【００２３】陽極酸化皮膜の凹部の全表面積ａを決定す
る因子としては、膜厚、凹部内径、凹部密度が挙げら
れ、いずれの因子も夫々の値が小さい程、凹部の全表面
積ａは小さくなる。また上記の因子の中で膜厚は積算電
気量（［電流密度］×［陽極酸化処理時間］）を調整す
ることにより、制御することができる。The factors that determine the total surface area a of the recesses of the anodized film include the film thickness, the inner diameter of the recesses, and the density of the recesses. The smaller the respective values of any of these factors, the smaller the total surface area a of the recesses. . Further, among the above factors, the film thickness can be controlled by adjusting the cumulative amount of electricity ([current density] × [anodizing time]).
【００２４】電流密度は主として電圧、溶液組成、溶液
温度により決定されるが、例えば、１０℃、１０重量％
のＨ2 ＳＯ4 の場合、電流密度ｉは電圧Ｖの変数として
下記（１）式で求めることができる。 ｌｏｇe （ｉ）＝０．１２Ｖ−１．１７ …（１）The current density is mainly determined by the voltage, the solution composition, and the solution temperature, and is, for example, 10 ° C. and 10% by weight.
In case of H 2 SO 4 , the current density i can be obtained by the following equation (1) as a variable of the voltage V. log e (i) = 0.12V-1.17 (1)
【００２５】尚、電流密度が約１００ｍＡ／ｃｍ2 以上
になると皮膜の溶解が激しく、皮膜が生成しないので注
意が必要である。好ましい電流密度の範囲は、０．１〜
８０ｍＡ／ｃｍ2 である。It should be noted that when the current density is about 100 mA / cm 2 or more, the film is so much dissolved that no film is formed. The preferred current density range is 0.1 to
It is 80 mA / cm 2 .
【００２６】電圧は２〜４０Ｖが好ましく、１０〜３０
Ｖがより好ましい。これは電圧が低過ぎると皮膜が成長
せず、一方電圧が高過ぎると他の条件を制御しても電流
密度を適正範囲内に制御することが困難となり、電流密
度が大きくなって皮膜が溶解してしまうからである。The voltage is preferably 2 to 40 V, and 10 to 30
V is more preferred. If the voltage is too low, the film will not grow, while if the voltage is too high, it will be difficult to control the current density within the proper range even if other conditions are controlled, and the current density will increase and the film will melt. Because I will do it.
【００２７】また、電流密度は電圧に比例する他、溶液
濃度や溶液温度によっても変動する。溶液濃度が薄いほ
ど電流密度は小さく、溶液温度は低い程電流密度は小さ
い。例えば、硫酸アルマイト処理を行うにあたっては、
硫酸濃度が４〜４０重量％であることが好ましく、１０
〜３０重量％であればより好ましい。これは、硫酸濃度
が希薄過ぎると、皮膜が不均一に形成され易く、濃厚過
ぎると皮膜の溶解が激しく、皮膜が生成しないからであ
る。The current density is proportional to the voltage and also changes depending on the solution concentration and the solution temperature. The lower the solution concentration, the smaller the current density, and the lower the solution temperature, the smaller the current density. For example, when performing the sulfuric acid alumite treatment,
The sulfuric acid concentration is preferably 4 to 40% by weight, and 10
More preferably, it is ˜30 wt%. This is because if the concentration of sulfuric acid is too dilute, the film is likely to be formed unevenly, and if it is too thick, the film is severely dissolved and the film is not formed.
【００２８】溶液温度は、−１０〜４０℃が好ましく、
−５〜３５℃がより好ましい。これは、溶液温度が低過
ぎると溶液が凝固してしまい、一方溶液温度が高過ぎる
と他の条件を制御しても電流密度を適正範囲内に制御す
ることが困難となり、電流密度が大きくなって皮膜が溶
解してしまうからである。The solution temperature is preferably -10 to 40 ° C,
-5-35 degreeC is more preferable. This is because if the solution temperature is too low, the solution will solidify, while if the solution temperature is too high, it will be difficult to control the current density within an appropriate range even if other conditions are controlled, and the current density will increase. The film will dissolve.
【００２９】尚、例えば１０℃、１０重量％のＨ2 ＳＯ
4 を電解液として１５Ｖで電解を行った場合の膜厚は、
下記（２）式で求めることができる。 ０．３μｍ／Ｃ／ｃｍ2 （１Ｃ＝１Ａ×１ｓｅｃ．）…（２） 前記の因子の中で凹部内径および凹部密度は電圧と相関
があり、電圧が大きい程、凹部内径は大きくなり、凹部
密度は小さくなるが、凹部内径と凹部密度の兼ね合いで
電圧が大きい程、凹部の全表面積ａは小さくなる。Incidentally, for example, 10 ° C., 10% by weight of H 2 SO
The film thickness when electrolysis is performed at 15 V using 4 as the electrolytic solution is
It can be calculated by the following equation (2). 0.3 μm / C / cm 2 (1 C = 1 A × 1 sec.) (2) Among the above-mentioned factors, the inner diameter of the recess and the density of the recess are correlated with the voltage. Although the density becomes smaller, the total surface area a of the recess becomes smaller as the voltage increases due to the balance between the inner diameter of the recess and the density of the recess.
【００３０】更に本発明に係るＡｌまたはＡｌ合金製真
空チャンバを製造するにあたって、前記の因子を一定に
して陽極酸化処理を行う方法に限定されず、例えば、電
圧等を変化させることによって、凹部内径を段階的に又
は連続的に変化させてもよい。Further, in manufacturing the vacuum chamber made of Al or Al alloy according to the present invention, it is not limited to the method of performing the anodizing treatment while keeping the above-mentioned factors constant, and for example, by changing the voltage or the like, the inner diameter of the recess can be changed. May be changed stepwise or continuously.
【００３１】本発明は陽極酸化処理を施すＡｌ合金の種
類についても限定するものではなく、従来のＡｌ−Ｍｇ
−Ｓｉ系合金（＃６０００系）はもとより、純Ａｌ（＃
１０００系），Ａｌ−Ｃｕ系合金（＃２０００系），Ａ
ｌ−Ｍｎ系合金（＃５０００系），Ａｌ−Ｚｎ−Ｍｇ系
合金（＃７０００系）についても、前記条件〜のい
ずれかを満足する陽極酸化皮膜を形成しさえすれば、優
れた耐ガス性及び耐プラズマ性を得ることができる。The present invention is not limited to the type of Al alloy to be anodized, and the conventional Al--Mg is used.
-Si-based alloys (# 6000 series) as well as pure Al (# 6000)
1000 series), Al-Cu series alloy (# 2000 series), A
With respect to the 1-Mn-based alloy (# 5000 series) and the Al-Zn-Mg-based alloy (# 7000 series), as long as an anodic oxide film satisfying any of the above conditions (1) to (4) is formed, excellent gas resistance is obtained. And plasma resistance can be obtained.
【００３２】[0032]
【実施例】実施例１ ＃６０００系Ａｌ合金板を用いて、１３％Ｈ2 ＳＯ4 溶
液（液温１０℃）の電解液に浸漬し、電圧５Ｖ，電流密
度０．１Ａ／ｄｍ2 の直流電解により７０分間の陽極酸
化処理を施して厚さ１．２μｍの硫酸陽極酸化皮膜を形
成した（表１中実施例Ｎｏ．５）。同様にして表１に示
す各種Ａｌ合金板を用いて、表１に併記する厚さおよび
（ａ＋ｂ）／ｂの各種硫酸陽極酸化皮膜を形成した。 Example 1 A # 6000 series Al alloy plate was used to immerse in a 13% H 2 SO 4 solution (solution temperature 10 ° C.) electrolyte solution, and a DC voltage of 5 V and a current density of 0.1 A / dm 2 was applied. The solution was subjected to anodizing treatment for 70 minutes to form a sulfuric acid anodized film having a thickness of 1.2 μm (Example No. 5 in Table 1). Similarly, various Al alloy plates shown in Table 1 were used to form various sulfuric acid anodized films having the thickness and (a + b) / b shown in Table 1.
【００３３】尚、比較例Ｎｏ．１０は、従来技術（特公
平５−５３８７０号公報）に従い陽極酸化処理を行った
ものであり、＃６０００系Ａｌ合金板を用いて、１５％
Ｈ2ＳＯ4 溶液（液温２０℃）の電解液に浸漬し、電圧
１５Ｖ，電流密度１．３Ａ／ｄｍ2 の直流電解により２
５分間の陽極酸化処理を施して厚さ９μｍの硫酸陽極酸
化皮膜を形成した。Comparative Example No. No. 10 was anodized according to the prior art (Japanese Patent Publication No. 53870/1993), and was 15% using # 6000 series Al alloy plate.
H 2 SO 4 solution was immersed in an electrolytic solution of (solution temperature 20 ° C.), voltages 15V, the DC electrolysis current density 1.3A / dm 2 2
Anodizing treatment was performed for 5 minutes to form a sulfuric acid anodized film having a thickness of 9 μm.
【００３４】上記試験片のハロゲン系ガスに対する耐食
性を評価することを目的として、５％Ｃｌ−Ａｒ混合ガ
スにより、３３０℃で６時間のガス腐食試験を行い、試
験後の外観を調べて以下の基準で評価した。結果は表１
に示す。 ◎： 腐食発生なし ○： 腐食発生面積率 １％未満 △： 腐食発生面積率 １％以上３％未満 △×： 腐食発生面積率 ３％以上５％未満 ×： 腐食発生面積率 ５％以上For the purpose of evaluating the corrosion resistance of the above-mentioned test piece to halogen-based gas, a gas corrosion test was carried out with a 5% Cl-Ar mixed gas at 330 ° C. for 6 hours, and the appearance after the test was examined to obtain the following. It was evaluated according to the standard. The results are shown in Table 1.
Shown in ◎: No corrosion occurred ○: Corrosion occurrence area ratio less than 1% △: Corrosion occurrence area ratio 1% or more and less than 3% △ ×: Corrosion occurrence area ratio 3% or more and less than 5% ×: Corrosion occurrence area ratio 5% or more
【００３５】[0035]
【表１】 [Table 1]
【００３６】表１の結果から明らかな様に、本発明に係
る条件を満足するＮｏ．１〜６は、優れた耐ガス性を示
した。一方Ｎｏ．７〜１２は、本発明に係る条件のいず
れかを満足しない比較例であり、耐ガス性が不充分であ
る。As is clear from the results shown in Table 1, No. 1 which satisfies the conditions according to the present invention. Nos. 1 to 6 showed excellent gas resistance. On the other hand, No. Nos. 7 to 12 are comparative examples that do not satisfy any of the conditions according to the present invention, and the gas resistance is insufficient.
【００３７】実施例２ ＃６０００系Ａｌ合金板を用いて、１３％Ｈ2 ＳＯ4 溶
液（液温１０℃）の電解液に浸漬し、電圧２０Ｖ，電流
密度１．３Ａ／ｄｍ2 の直流電解により５分間の陽極酸
化処理を施して厚さ１．８μｍの硫酸陽極酸化皮膜を形
成した（表２中実施例Ｎｏ．１７）。同様にして表２に
示す各種Ａｌ合金板を用いて、表２に併記する厚さおよ
び（ａ＋ｂ）／ｂの各種硫酸陽極酸化皮膜を形成した。
尚、比較例Ｎｏ．２２は、前記比較例１０と同様にして
陽極酸化処理を行ったものである。 Example 2 Using a # 6000 series Al alloy plate, it was immersed in an electrolytic solution of a 13% H 2 SO 4 solution (solution temperature 10 ° C.), and DC electrolysis with a voltage of 20 V and a current density of 1.3 A / dm 2 . Was applied for 5 minutes to form a sulfuric acid anodized film having a thickness of 1.8 μm (Example No. 17 in Table 2). Similarly, various Al alloy plates shown in Table 2 were used to form various sulfuric acid anodized films having the thickness and (a + b) / b shown in Table 2.
Comparative example No. No. 22 was anodized in the same manner as in Comparative Example 10.
【００３８】ハロゲン系プラズマに対する耐食性を評価
することを目的として、上記試験片を用いて４時間の塩
素プラズマ照射試験を行い、試験後の外観を調べて以下
の基準で評価した。結果は表２に示す。 ◎： 腐食発生なし ○： 腐食発生面積率 １％未満 △： 腐食発生面積率 １％以上３％未満 △×： 腐食発生面積率 ３％以上５％未満 ×： 腐食発生面積率 ５％以上For the purpose of evaluating the corrosion resistance to halogen-based plasma, a chlorine plasma irradiation test was conducted for 4 hours using the above test piece, and the appearance after the test was examined and evaluated according to the following criteria. The results are shown in Table 2. ◎: No corrosion occurred ○: Corrosion occurrence area ratio less than 1% △: Corrosion occurrence area ratio 1% or more and less than 3% △ ×: Corrosion occurrence area ratio 3% or more and less than 5% ×: Corrosion occurrence area ratio 5% or more
【００３９】[0039]
【表２】 [Table 2]
【００４０】表２の結果から明らかな様に、本発明に係
る条件を満足するＮｏ．１３〜１８は、優れた耐ガス性
を示した。一方Ｎｏ．１９〜２４は、本発明に係る条件
のいずれかを満足しない比較例であり、耐プラズマ性が
不充分である。As is clear from the results shown in Table 2, No. 1 satisfying the conditions according to the present invention. Nos. 13 to 18 showed excellent gas resistance. On the other hand, No. 19 to 24 are comparative examples that do not satisfy any of the conditions according to the present invention, and the plasma resistance is insufficient.
【００４１】実施例３ ＃６０００系Ａｌ合金板を用いて、３．３５％Ｈ3 ＰＯ
4 溶液（液温１０℃）の電解液に浸漬し、電圧１５Ｖ，
電流密度０．０５Ａ／ｄｍ2 の直流電解により４０分間
の陽極酸化処理を施して厚さ０．９μｍのりん酸陽極酸
化皮膜を形成した（表３中実施例Ｎｏ．２８）。同様に
して表３に示す各種Ａｌ合金板を用いて、表３に併記す
る厚さおよび（ａ＋ｂ）／ｂの各種りん酸陽極酸化皮膜
を形成した。上記試験片を用いて実施例１と同様にして
耐ガス性を調べた。結果は表３に示す。 Example 3 Using a # 6000 series Al alloy plate, 3.35% H 3 PO
Immerse 4 solutions (liquid temperature 10 ℃) in electrolyte, voltage 15V,
Anodizing treatment was performed for 40 minutes by direct current electrolysis with a current density of 0.05 A / dm 2 to form a phosphoric acid anodized film having a thickness of 0.9 μm (Example No. 28 in Table 3). Similarly, various Al alloy plates shown in Table 3 were used to form various phosphoric acid anodic oxide coatings having the thickness and (a + b) / b shown in Table 3 together. Using the above test piece, gas resistance was examined in the same manner as in Example 1. The results are shown in Table 3.
【００４２】[0042]
【表３】 [Table 3]
【００４３】表３の結果から明らかな様に、本発明に係
る条件を満足するＮｏ．２５〜３０は、優れた耐ガス性
を示した。一方Ｎｏ．３１〜３５は、本発明に係る条件
のいずれかを満足しない比較例であり、耐ガス性が不充
分である。As is clear from the results shown in Table 3, No. 1 which satisfies the conditions according to the present invention. 25 to 30 showed excellent gas resistance. On the other hand, No. Nos. 31 to 35 are comparative examples that do not satisfy any of the conditions according to the present invention, and have insufficient gas resistance.
【００４４】実施例４ ＃６０００系Ａｌ合金板を用いて、３．３５％Ｈ3 ＰＯ
4 溶液（液温１０℃）の電解液に浸漬し、電圧１２０
Ｖ，電流密度０．１８Ａ／ｄｍ2 の直流電解により１０
分間の陽極酸化処理を施して厚さ１．４μｍのりん酸陽
極酸化皮膜を形成した（表４中実施例Ｎｏ．３９）。同
様にして表４に示す各種Ａｌ合金板を用いて、表４に併
記する厚さおよび（ａ＋ｂ）／ｂの各種りん酸陽極酸化
皮膜を形成した。上記試験片を用いて実施例２と同様に
して耐プラズマ性を調べた。結果は表４に示す。 Example 4 Using a # 6000 series Al alloy plate, 3.35% H 3 PO
Immerse in 4 solutions (liquid temperature 10 ℃) of electrolyte, voltage 120
10 by DC electrolysis with V and current density of 0.18 A / dm 2.
A anodic oxidation treatment was performed for 1 minute to form a phosphoric acid anodic oxide film having a thickness of 1.4 μm (Example No. 39 in Table 4). Similarly, various Al alloy plates shown in Table 4 were used to form various phosphoric acid anodic oxide coatings having the thickness and (a + b) / b shown in Table 4. Plasma resistance was examined in the same manner as in Example 2 using the above test piece. The results are shown in Table 4.
【００４５】[0045]
【表４】 [Table 4]
【００４６】表４の結果から明らかな様に、本発明に係
る条件を満足するＮｏ．３６〜４２は、優れた耐プラズ
マ性を示した。一方Ｎｏ．４３〜４６は、本発明に係る
条件のいずれかを満足しない比較例であり、耐プラズマ
性が不充分である。As is clear from the results shown in Table 4, No. 1 satisfying the conditions according to the present invention. 36 to 42 showed excellent plasma resistance. On the other hand, No. Nos. 43 to 46 are comparative examples that do not satisfy any of the conditions according to the present invention, and the plasma resistance is insufficient.
【００４７】実施例５ 表５に記載のＡｌ合金板に種々の陽極酸化処理を行い、
表５に併記する形態の酸化皮膜を形成して試験片とし
た。尚、Ｎｏ．５２の試験片に関しては、まずりん酸イ
オンを含まない溶液中で陽極酸化処理を行った後、イオ
ン注入を施すことによって皮膜表面近傍（表面から約
０．１μｍの範囲）におけるＰ含有量を所定の値にし
た。また、Ｎｏ．５３の試験片に関しては、陽極酸化処
理を行った後、沸騰水中に３分間浸漬する熱水処理を施
すことによって所定の凹部間距離にした。上記試験片を
用いて実施例１と同様にして耐ガス性を調べた。結果は
表５に示す。 Example 5 The Al alloy plates shown in Table 5 were subjected to various anodic oxidation treatments,
An oxide film having the form described in Table 5 was formed to obtain a test piece. Incidentally, No. With respect to the test piece No. 52, first, an anodizing treatment was performed in a solution containing no phosphate ion, and then ion implantation was performed to determine the P content in the vicinity of the coating surface (in the range of about 0.1 μm from the surface). The value of In addition, No. The test piece of No. 53 was subjected to anodizing treatment and then subjected to hot water treatment of being immersed in boiling water for 3 minutes so that a predetermined distance between recesses was obtained. Using the above test piece, gas resistance was examined in the same manner as in Example 1. The results are shown in Table 5.
【００４８】[0048]
【表５】 [Table 5]
【００４９】表５の結果から明らかな様に、本発明に係
る条件を満足するＮｏ．４７〜５３は、優れた耐ガス性
を示した。一方Ｎｏ．５４〜５７は、本発明に係る条件
のいずれかを満足しない比較例であり、耐ガス性が不充
分である。As is clear from the results shown in Table 5, No. 1 satisfying the conditions according to the present invention. 47-53 showed the outstanding gas resistance. On the other hand, No. Nos. 54 to 57 are comparative examples that do not satisfy any of the conditions according to the present invention, and the gas resistance is insufficient.
【００５０】[0050]
【発明の効果】本発明は以上の様に構成されているの
で、耐ガス性および耐プラズマ性に優れたＡｌまたはＡ
ｌ合金製真空チャンバ部材が提供できることとなった。Since the present invention is constituted as described above, Al or A having excellent gas resistance and plasma resistance.
It is now possible to provide a vacuum chamber member made of an alloy.
【図１】陽極酸化皮膜の概略構造を示す一部断面説明図
である。FIG. 1 is a partial cross-sectional explanatory view showing a schematic structure of an anodized film.
Claims (3)
されて多孔質な酸化皮膜が形成されてなるＡｌまたはＡ
ｌ合金製真空チャンバ部材であって、 上記酸化皮膜の表面に形成された凹部の全表面積をａ、
該凹部を除いた外表面の面積をｂとしたとき、（ａ＋
ｂ）／ｂの値が３０００以下であることを特徴とするＡ
ｌまたはＡｌ合金製真空チャンバ部材。1. Al or A obtained by anodizing in a solution containing sulfate ions to form a porous oxide film.
1 is a vacuum chamber member made of an alloy, the total surface area of the concave portion formed on the surface of the oxide film is a,
When the area of the outer surface excluding the concave portion is b, (a +
A) characterized in that the value of b) / b is 3000 or less
1 or Al alloy vacuum chamber member.
理が施され多孔質な酸化皮膜が形成されてなるＡｌまた
はＡｌ合金製真空チャンバ部材であって、 上記酸化皮膜の表面に形成された凹部の全表面積をａ、
該凹部を除いた外表面の面積をｂとしたとき、（ａ＋
ｂ）／ｂの値が７００以下であることを特徴とするＡｌ
またはＡｌ合金製真空チャンバ部材。2. A vacuum chamber member made of Al or Al alloy which is anodized in a solution containing phosphate ions to form a porous oxide film, which is formed on the surface of the oxide film. The total surface area of the recess is a,
When the area of the outer surface excluding the concave portion is b, (a +
Al) characterized in that the value of b) / b is 700 or less
Or a vacuum chamber member made of Al alloy.
理が施され多孔質な酸化皮膜が形成されてなるＡｌまた
はＡｌ合金製真空チャンバ部材であって、 上記酸化皮膜の表面に形成された凹部の中で、相隣接す
る２つの凹部の平面視の中心点を結ぶ距離が０．００５
〜０．５μｍであり、 上記酸化皮膜中のＰ濃度が０．０１重量％以上であるこ
とを特徴とするＡｌまたはＡｌ合金製真空チャンバ部
材。3. A vacuum chamber member made of Al or Al alloy that is anodized in a solution containing phosphate ions to form a porous oxide film, the vacuum chamber member being formed on the surface of the oxide film. Among the recesses, the distance connecting the center points of two adjacent recesses in plan view is 0.005.
The vacuum chamber member made of Al or Al alloy is characterized in that the P concentration in the oxide film is 0.01% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28231294A JPH08144089A (en) | 1994-11-16 | 1994-11-16 | Vacuum chamber member made of aluminum or aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28231294A JPH08144089A (en) | 1994-11-16 | 1994-11-16 | Vacuum chamber member made of aluminum or aluminum alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08144089A true JPH08144089A (en) | 1996-06-04 |
Family
ID=17650784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28231294A Withdrawn JPH08144089A (en) | 1994-11-16 | 1994-11-16 | Vacuum chamber member made of aluminum or aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08144089A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6066392A (en) * | 1997-11-14 | 2000-05-23 | Kabushiki Kaisha Kobe Seiko Sho | Al material excellent in thermal crack resistance and corrosion resistance |
| JP2000192293A (en) * | 1998-12-24 | 2000-07-11 | Aisin Seiki Co Ltd | Anodized aluminum coating |
| US6444304B1 (en) | 1998-10-09 | 2002-09-03 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Anodic oxide layer and ceramic coating for aluminum alloy excellent in resistance to gas and plasma corrosion |
| US6521046B2 (en) | 2000-02-04 | 2003-02-18 | Kabushiki Kaisha Kobe Seiko Sho | Chamber material made of Al alloy and heater block |
| KR100397860B1 (en) * | 1997-09-22 | 2003-12-18 | 카가쿠기쥬쯔죠 킨조쿠자이료 기쥬쯔켄큐죠 | Reactive ion-etching method and an appartus thereof |
| US6686053B2 (en) | 2001-07-25 | 2004-02-03 | Kabushiki Kaisha Kobe Seiko Sho | AL alloy member having excellent corrosion resistance |
| JP2010133003A (en) * | 2008-10-30 | 2010-06-17 | Kobe Steel Ltd | Aluminum alloy member superior in cracking resistance and corrosion resistance, method for confirming cracking resistance and corrosion resistance of porous-type anodic oxide coating, and method for setting condition of forming porous-type anodic oxide coating superior in cracking resistance and corrosion resistance |
| JP2010209367A (en) * | 2009-03-06 | 2010-09-24 | Kobe Steel Ltd | Aluminum alloy member having excellent low staining property |
| JP2015098627A (en) * | 2013-11-19 | 2015-05-28 | 株式会社神戸製鋼所 | Anodic oxidation treated aluminum alloy member excellent in insulation property |
-
1994
- 1994-11-16 JP JP28231294A patent/JPH08144089A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100397860B1 (en) * | 1997-09-22 | 2003-12-18 | 카가쿠기쥬쯔죠 킨조쿠자이료 기쥬쯔켄큐죠 | Reactive ion-etching method and an appartus thereof |
| US6066392A (en) * | 1997-11-14 | 2000-05-23 | Kabushiki Kaisha Kobe Seiko Sho | Al material excellent in thermal crack resistance and corrosion resistance |
| US6444304B1 (en) | 1998-10-09 | 2002-09-03 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Anodic oxide layer and ceramic coating for aluminum alloy excellent in resistance to gas and plasma corrosion |
| JP2000192293A (en) * | 1998-12-24 | 2000-07-11 | Aisin Seiki Co Ltd | Anodized aluminum coating |
| US6521046B2 (en) | 2000-02-04 | 2003-02-18 | Kabushiki Kaisha Kobe Seiko Sho | Chamber material made of Al alloy and heater block |
| US6686053B2 (en) | 2001-07-25 | 2004-02-03 | Kabushiki Kaisha Kobe Seiko Sho | AL alloy member having excellent corrosion resistance |
| JP2010133003A (en) * | 2008-10-30 | 2010-06-17 | Kobe Steel Ltd | Aluminum alloy member superior in cracking resistance and corrosion resistance, method for confirming cracking resistance and corrosion resistance of porous-type anodic oxide coating, and method for setting condition of forming porous-type anodic oxide coating superior in cracking resistance and corrosion resistance |
| JP2010209367A (en) * | 2009-03-06 | 2010-09-24 | Kobe Steel Ltd | Aluminum alloy member having excellent low staining property |
| JP2015098627A (en) * | 2013-11-19 | 2015-05-28 | 株式会社神戸製鋼所 | Anodic oxidation treated aluminum alloy member excellent in insulation property |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20020205 |