JPH0995784A - Formation of carbon film - Google Patents
Formation of carbon filmInfo
- Publication number
- JPH0995784A JPH0995784A JP7254949A JP25494995A JPH0995784A JP H0995784 A JPH0995784 A JP H0995784A JP 7254949 A JP7254949 A JP 7254949A JP 25494995 A JP25494995 A JP 25494995A JP H0995784 A JPH0995784 A JP H0995784A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- film
- gas
- plasma
- carbon 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機材料からなる
被成膜基体上にＤＬＣ(Diamond Like Carbon) 膜等の炭
素膜を形成する方法に関する。TECHNICAL FIELD The present invention relates to a method for forming a carbon film such as a DLC (Diamond Like Carbon) film on a film formation substrate made of an organic material.
【０００２】[0002]
【従来の技術】炭素膜の中でもＤＬＣ膜は、耐摩耗性、
摺動性、絶縁性等に優れていることから、物品の潤滑性
等を向上させる目的で幅広い用途が開拓されている。ま
た、ＤＬＣ膜は比較的低温で形成できるため、比較的耐
熱性が劣る樹脂等の有機材料からなる物品上へも形成す
ることができる。2. Description of the Related Art Among carbon films, a DLC film has abrasion resistance,
Due to its excellent slidability and insulating properties, a wide range of applications have been developed for the purpose of improving the lubricity of articles. Further, since the DLC film can be formed at a relatively low temperature, it can be formed on an article made of an organic material such as resin having a relatively poor heat resistance.
【０００３】従来、ＤＬＣ膜等の炭素膜の形成にはプラ
ズマＣＶＤ法が多用されている。しかし、通常のプラズ
マＣＶＤ法によっては、ＤＬＣ膜等の炭素膜を基体上に
密着性良好に形成することは困難である。そこで、基体
が金属等の導電性材料からなる場合は、炭素膜と基体と
の密着性を向上させるために、例えば図２又は図３に示
すプラズマＣＶＤ装置を用いて成膜している。Conventionally, a plasma CVD method is often used for forming a carbon film such as a DLC film. However, it is difficult to form a carbon film such as a DLC film on a substrate with good adhesion by a usual plasma CVD method. Therefore, in the case where the substrate is made of a conductive material such as metal, in order to improve the adhesion between the carbon film and the substrate, the film is formed by using, for example, the plasma CVD apparatus shown in FIG. 2 or FIG.
【０００４】図２の装置は、排気装置１１が付設された
真空チャンバ１を有し、チャンバ１内には基体ホルダを
兼ねる電極２及びこれに対向する位置に高周波電極３１
が設置されている。電極２には直流電源２１が接続さ
れ、高周波電極３１にはマッチングボックス３２を介し
て高周波電源３３が接続されている。また、電極２には
ヒータ２０が付設されており、電極２に支持される被成
膜基体Ｓ１を所定の成膜温度に加熱することができる。
また、チャンバ１にはガス供給部４が付設されて、内部
にプラズマ原料ガスを導入できるようになっている。ガ
ス供給部４には、マスフローコントローラ４１１、４１
２・・・及び弁４２１、４２２・・・を介して接続され
た１又は２以上のプラズマ原料ガスのガス源４３１、４
３２・・・が含まれる。The apparatus shown in FIG. 2 has a vacuum chamber 1 to which an exhaust device 11 is attached. Inside the chamber 1, an electrode 2 also serving as a substrate holder and a high frequency electrode 31 at a position facing the electrode 2 are provided.
Is installed. A DC power supply 21 is connected to the electrode 2, and a high frequency power supply 33 is connected to the high frequency electrode 31 via a matching box 32. A heater 20 is attached to the electrode 2 so that the film formation substrate S1 supported by the electrode 2 can be heated to a predetermined film formation temperature.
Further, the chamber 1 is provided with a gas supply unit 4 so that a plasma source gas can be introduced therein. The gas supply unit 4 includes mass flow controllers 411 and 41
.. And one or more plasma source gases 431, 4 connected via valves 421, 422,.
32 ... are included.
【０００５】この装置を用いて金属材料からなる被成膜
基体Ｓ１上に炭素膜を形成するにあたっては、基体Ｓ１
をチャンバ１内に搬入し、ホルダ２に支持させた後、排
気装置１１の運転にてチャンバ１内を所定の真空度とす
る。次いで、ガス供給部４からチャンバ１内にプラズマ
原料ガスとして炭化水素化合物ガスを導入するととも
に、高周波電源３３からマッチングボックス３２を介し
て電極３１に高周波電圧を印加して前記導入したプラズ
マ原料ガスをプラズマ化し、該プラズマの下で基体Ｓ１
上に炭素膜を形成する。この間、電源２１から電極２に
数ｋＶ程度の負バイアスを印加することで、プラズマ中
の炭素イオンを引きつけ、基体Ｓ１に打ち込みながら成
膜を行う。これにより、形成される炭素膜と基体Ｓ１と
の密着性を向上させることができる。When forming a carbon film on a film-forming substrate S1 made of a metal material by using this apparatus, the substrate S1 is used.
After being loaded into the chamber 1 and supported by the holder 2, the exhaust device 11 is operated to bring the inside of the chamber 1 to a predetermined vacuum degree. Next, a hydrocarbon compound gas is introduced as a plasma raw material gas into the chamber 1 from the gas supply unit 4, and a high frequency voltage is applied from the high frequency power source 33 to the electrode 31 via the matching box 32 to remove the introduced plasma raw material gas. It is made into plasma and the substrate S1 is placed under the plasma.
A carbon film is formed on top. During this period, a negative bias of about several kV is applied from the power source 21 to the electrode 2 to attract the carbon ions in the plasma and form the film while implanting it into the substrate S1. Thereby, the adhesiveness between the formed carbon film and the substrate S1 can be improved.
【０００６】また、図３の装置は、図２の装置におい
て、高周波電極３１とこれに接続されたマッチングボッ
クス３２及び高周波電源３３に代えて、接地電極５を備
えたものである。その他の構成は図２の装置と同様であ
り、実質上同じ部品は同じ符号を付してある。この装置
を用いて金属材料からなる被成膜基体Ｓ１上に炭素膜を
形成するにあたっては、基体Ｓ１をチャンバ１内に搬入
し、ホルダ２に支持させた後、排気装置１１の運転にて
チャンバ１内を所定の真空度とする。次いで、ガス供給
部４からチャンバ１内にプラズマ原料ガスとして炭化水
素化合物ガスを導入するとともに、直流電源２１から電
極２に負電圧を印加して前記導入したガスをプラズマ化
し、該プラズマの下で基体Ｓ１上に炭素膜を形成する。
この間、負バイアスが印加される電極２１にプラズマ中
の炭素イオンが引きつけられることで、該イオンが基体
Ｓ１に打ち込まれ、これにより形成される炭素膜と基体
Ｓ１との密着性を向上させることができる。The apparatus shown in FIG. 3 is different from the apparatus shown in FIG. 2 in that the high-frequency electrode 31, the matching box 32 and the high-frequency power source 33 connected to the high-frequency electrode 31 are replaced with a ground electrode 5. The other structure is the same as that of the apparatus of FIG. 2, and the substantially same parts are denoted by the same reference numerals. When forming a carbon film on a film-forming substrate S1 made of a metal material by using this apparatus, the substrate S1 is carried into the chamber 1 and supported by the holder 2, and then the exhaust device 11 is operated to operate the chamber. The inside of 1 is set to a predetermined vacuum degree. Next, while introducing a hydrocarbon compound gas as a plasma raw material gas into the chamber 1 from the gas supply unit 4 and applying a negative voltage from the DC power source 21 to the electrode 2, the introduced gas is made into plasma, and under the plasma, A carbon film is formed on the substrate S1.
During this time, the carbon ions in the plasma are attracted to the electrode 21 to which the negative bias is applied, so that the ions are implanted into the substrate S1 and the adhesion between the carbon film formed thereby and the substrate S1 can be improved. it can.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、被成膜
基体が樹脂、ゴム等の有機材料からなる場合、該材料は
電気絶縁性を示すため、プラズマＣＶＤにおいてこのよ
うに基体側電極に直流バイアスを印加すると、該基体が
帯電し、絶縁破壊を起こし易い。このように有機材料か
らなる被成膜基体上に炭素膜を密着性良好に形成する方
法は得られていないのが現状である。However, when the film-forming substrate is made of an organic material such as resin or rubber, the material exhibits electrical insulation, so that a direct current bias is applied to the substrate-side electrode in plasma CVD in this way. When applied, the substrate is likely to be charged and dielectric breakdown is likely to occur. Under the present circumstances, a method for forming a carbon film on a film-forming substrate made of an organic material with good adhesion has not been obtained.
【０００８】そこで本発明は、有機材料からなる被成膜
基体上に炭素膜を密着性良好に形成できる炭素膜の形成
方法を提供することを課題とする。Therefore, it is an object of the present invention to provide a method for forming a carbon film, which can form a carbon film on a film-forming substrate made of an organic material with good adhesion.
【０００９】[0009]
【課題を解決するための手段】前記課題を解決する本発
明の炭素膜の形成方法は、有機材料からなる被成膜基体
をフッ素（Ｆ）含有ガス、水素（Ｈ2 ）ガス及び酸素ガ
ス（Ｏ2 ）ガスから選ばれた少なくとも１種のガスのプ
ラズマに曝した後、該基体上に炭素膜を形成することを
特徴とする。According to the method of forming a carbon film of the present invention for solving the above-mentioned problems, a film-forming substrate made of an organic material is provided with a fluorine (F) -containing gas, a hydrogen (H 2 ) gas and an oxygen gas ( A carbon film is formed on the substrate after being exposed to plasma of at least one gas selected from O 2 ) gas.
【００１０】本発明方法における被成膜基体の材質であ
る有機材料としては、各種の樹脂、ゴム等を挙げること
ができるが、特に限定されない。また、前記基体の形状
も膜被覆基体の用途により異なり、ブロック状、プレー
ト状、チューブ状、袋状、フィルム状、繊維状等種々考
えられるが、特に限定されない。また、本発明方法にお
けるフッ素含有ガスとしては、フッ素（Ｆ2 ）ガス、３
フッ化窒素（ＮＦ3 ）ガス、６フッ化硫黄（ＳＦ6 ）ガ
ス、４フッ化炭素（ＣＦ 4 ）ガス、４フッ化ケイ素（Ｓ
ｉＦ4 ）ガス、６フッ化２ケイ素（Ｓｉ2 Ｆ6 ）ガス、
３フッ化塩素（ＣｌＦ3 ）ガス、フッ化水素（ＨＦ）ガ
ス等を挙げることができる。The material of the film-forming substrate in the method of the present invention
Examples of organic materials include various resins and rubbers.
However, it is not particularly limited. Also, the shape of the base
Also depends on the application of the film-coated substrate, and can
Various considerations such as sheet shape, tube shape, bag shape, film shape, fiber shape
Yes, but it is not particularly limited. In addition, the method of the present invention
As the fluorine-containing gas, fluorine (F2) Gas, 3
Nitrogen fluoride (NFThree) Gas, sulfur hexafluoride (SF6) Moth
Carbon tetrafluoride (CF Four) Gas, silicon tetrafluoride (S
iFFour) Gas, disilicon hexafluoride (Si2F6)gas,
Chlorine trifluoride (ClFThree) Gas, hydrogen fluoride (HF) gas
Can be mentioned.
【００１１】また、本発明方法における炭素膜形成方法
としては、プラズマＣＶＤ法、スパッタリング法、イオ
ンプレーティング法等を挙げることができるが、特にプ
ラズマＣＶＤ法を用いる場合は、被成膜基体のプラズマ
による前処理と炭素膜形成とを同一の装置で行うことが
できる。また、本発明方法により形成する炭素膜は、被
成膜基体に熱的損傷を与えない温度範囲で形成できるも
のであればよいが、代表的には用途の広いＤＬＣ膜を挙
げることができる。As the carbon film forming method in the method of the present invention, a plasma CVD method, a sputtering method, an ion plating method and the like can be mentioned. Particularly when the plasma CVD method is used, the plasma of the substrate to be formed is The pretreatment by and the carbon film formation can be performed in the same apparatus. Further, the carbon film formed by the method of the present invention may be any one that can be formed in a temperature range that does not cause thermal damage to the film-forming substrate, but a typical example is a DLC film having a wide range of uses.
【００１２】プラズマＣＶＤ法により炭素膜を形成する
場合のプラズマ原料ガスとしては、炭素膜形成に一般に
用いられるメタン（ＣＨ4 ）、エタン（Ｃ2 Ｈ6 ）、プ
ロパン（Ｃ3 Ｈ8 ）、ブタン（Ｃ4 Ｈ10）、アセチレン
（Ｃ2 Ｈ2 ）、ベンゼン（Ｃ 6 Ｈ6 ）等の炭化水素化合
物ガス、及び必要に応じて、これらの炭化水素化合物ガ
スにキャリアガスとして水素ガス、不活性ガス等を混合
したものを用いることができる。A carbon film is formed by the plasma CVD method.
In this case, the plasma source gas is generally used for carbon film formation.
Methane used (CHFour), Ethane (C2H6),
Lopin (CThreeH8), Butane (CFourHTen),acetylene
(C2H2), Benzene (C 6H6) Hydrocarbon compounds such as
Gas and, if necessary, these hydrocarbon compounds
Mixed with hydrogen gas and inert gas as carrier gas
Can be used.
【００１３】本発明の炭素膜の形成方法によると、有機
材料からなる被成膜基体上への炭素膜の形成に先立ち、
該基体をフッ素含有ガス、水素ガス及び酸素ガスのうち
１以上のガスのプラズマに曝す。これにより、該基体表
面が該プラズマにより清浄化されるとともに、フッ素含
有ガスプラズマを採用するときはこれによって基体表面
がフッ素終端され、水素ガスプラズマを採用するときは
これによって該基体表面が水素終端される。そしてこれ
らのことから、その後形成する炭素膜と該基体との密着
性を向上させることができる。特に、フッ素−炭素結合
及び水素−炭素結合は安定であるため、前記のように終
端処理することで膜中の炭素原子が基体表面部分のフッ
素原子又は（及び）水素原子と安定に結合を形成する。
また、酸素ガスプラズマを採用するときは基体表面に付
着した有機物等の汚れを特に効率良く除去できる。According to the method for forming a carbon film of the present invention, prior to the formation of the carbon film on the film-forming substrate made of an organic material,
The substrate is exposed to plasma of at least one of fluorine-containing gas, hydrogen gas and oxygen gas. As a result, the surface of the substrate is cleaned by the plasma, and when the fluorine-containing gas plasma is adopted, the surface of the substrate is terminated with fluorine. When the hydrogen gas plasma is adopted, the surface of the substrate is terminated with hydrogen. To be done. From these facts, it is possible to improve the adhesion between the carbon film to be subsequently formed and the substrate. In particular, since the fluorine-carbon bond and the hydrogen-carbon bond are stable, the carbon atom in the film forms a stable bond with the fluorine atom or (and) hydrogen atom on the surface portion of the substrate by terminating as described above. To do.
Further, when oxygen gas plasma is adopted, stains such as organic substances attached to the surface of the substrate can be removed particularly efficiently.
【００１４】本発明方法において、炭素膜形成に先立っ
て行うプラズマによる被成膜基体の前処理は、同種類の
プラズマを用いて或いは異なる種類のプラズマを用いて
複数回行っても構わない。例えば、基体を酸素ガスプラ
ズマに曝した後、フッ素含有ガスプラズマ又は水素ガス
プラズマに曝し、さらにその上に炭素膜を形成するとき
には、基体表面がクリーニングされた後、該面がフッ素
終端又は水素終端されて、その後形成する炭素膜と該基
体との密着性は非常に良好なものとなる。In the method of the present invention, the pretreatment of the film-forming substrate with plasma prior to the formation of the carbon film may be performed a plurality of times using the same type of plasma or different types of plasma. For example, when the substrate is exposed to oxygen gas plasma and then exposed to fluorine-containing gas plasma or hydrogen gas plasma and a carbon film is further formed thereon, after the substrate surface is cleaned, the surface is fluorine-terminated or hydrogen-terminated. As a result, the adhesion between the carbon film formed thereafter and the substrate becomes very good.
【００１５】[0015]
【発明の実施の形態】以下、本発明の実施の形態を図面
を参照して説明する。図１は本発明に係る炭素膜形成方
法の実施に用いることができる成膜装置の概略構成を示
す図である。この装置は、図２に示すプラズマＣＶＤ装
置において、基体ホルダを兼ねる電極２に直流電源２１
が接続されておらず、直接接地されているものである。
その他の構成は図２の装置と同様であり、同じ部品には
同じ符号を付してある。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a diagram showing a schematic configuration of a film forming apparatus that can be used for carrying out the carbon film forming method according to the present invention. This apparatus is the same as the plasma CVD apparatus shown in FIG.
Is not connected and is directly grounded.
The other structure is similar to that of the apparatus of FIG. 2, and the same parts are denoted by the same reference numerals.
【００１６】この装置を用いて本発明方法を実施するに
あたっては、有機材料からなる被成膜基体Ｓを真空チャ
ンバ１内に搬入し、基体ホルダ２に支持させ、排気装置
１１の運転にてチャンバ１内部を所定の真空度にする。
次いで、ガス供給部４からチャンバ１内にフッ素含有ガ
ス、水素ガス及び酸素ガスのうち１種以上のガスを前処
理用ガスとして導入するとともに高周波電源３３からマ
ッチングボックス３２を介して電極３１に高周波電力を
印加し、これにより前記導入した前処理用ガスをプラズ
マ化し、該プラズマの下で被成膜基体Ｓの表面処理を行
う。In carrying out the method of the present invention using this apparatus, the film-forming substrate S made of an organic material is loaded into the vacuum chamber 1, supported by the substrate holder 2, and the chamber 11 is operated by operating the exhaust device 11. 1 The inside is made to have a predetermined vacuum degree.
Then, at least one of fluorine-containing gas, hydrogen gas and oxygen gas is introduced as a pretreatment gas from the gas supply unit 4 into the chamber 1, and a high frequency power is supplied to the electrode 31 from the high frequency power supply 33 through the matching box 32. By applying electric power, the introduced pretreatment gas is turned into plasma, and the surface treatment of the film-forming substrate S is performed under the plasma.
【００１７】次いで、必要に応じてチャンバ１内を再び
真空引きした後、ガス供給部４からチャンバ１内に成膜
用原料ガスとして炭化水素化合物ガスを導入するととも
に高周波電源３３から電極３１に高周波電圧を印加し、
これにより前記導入した炭化水素化合物ガスをプラズマ
化し、該プラズマの下で被成膜基体Ｓ上に炭素膜を形成
する。Then, after the chamber 1 is evacuated again if necessary, a hydrocarbon compound gas is introduced into the chamber 1 from the gas supply unit 4 as a film forming raw material gas, and a high frequency power is supplied from the high frequency power supply 33 to the electrode 31. Apply voltage,
As a result, the introduced hydrocarbon compound gas is turned into plasma, and a carbon film is formed on the deposition target substrate S under the plasma.
【００１８】以上説明した本発明の炭素膜形成方法によ
ると、成膜に先立ち有機材料からなる被成膜基体Ｓ表面
をフッ素含有ガスプラズマ、水素ガスプラズマ及び酸素
ガスプラズマの１又は２以上に曝すことで、基体Ｓ表面
のクリーニングが行われると共に、フッ素含有ガスプラ
ズマ又は（及び）水素ガスプラズマを採用するときには
基体Ｓ表面のフッ素終端又は（及び）水素終端が行わ
れ、これらにより炭素膜と基体Ｓとの密着性は良好なも
のとなる。According to the carbon film forming method of the present invention described above, the surface of the film-forming substrate S made of an organic material is exposed to one or more of fluorine-containing gas plasma, hydrogen gas plasma and oxygen gas plasma prior to film formation. As a result, the surface of the substrate S is cleaned, and when fluorine-containing gas plasma or (and) hydrogen gas plasma is adopted, fluorine termination or (and) hydrogen termination of the substrate S surface is performed. Adhesion with S becomes good.
【００１９】次に、図１の装置を用いてウレタンゴムか
らなる被成膜基体Ｓ上にＤＬＣ膜を形成した本発明方法
実施の具体例を説明する。 実施例１ 被成膜基体Ｓ材質 ウレタンゴム サイズ 厚さ２ｍｍ×１００ｍｍ×１００ｍｍ 高周波電極３１サイズ 直径２８０ｍｍ 前処理条件 前処理用ガス 水素（Ｈ2 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 処理真空度 ０．１Ｔｏｒｒ 処理時間 ５ｍｉｎ 成膜条件 成膜用原料ガス メタン（ＣＨ4 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 成膜真空度 ０．１Ｔｏｒｒ 成膜速度 ２０００Å／ｍｉｎ 成膜時間 １０ｍｉｎ 実施例２ 被成膜基体Ｓ材質 ウレタンゴム サイズ 厚さ２ｍｍ×１００ｍｍ×１００ｍｍ 高周波電極３１サイズ 直径２８０ｍｍ 前処理条件 前処理用ガス ６フッ化硫黄（ＳＦ6 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 処理真空度 ０．１５Ｔｏｒｒ 処理時間 ５ｍｉｎ 成膜条件 成膜用原料ガス メタン（ＣＨ4 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 成膜真空度 ０．１Ｔｏｒｒ 成膜速度 ２０００Å／ｍｉｎ 成膜時間 １０ｍｉｎ 実施例３ 被成膜基体Ｓ材質 ウレタンゴム サイズ 厚さ２ｍｍ×１００ｍｍ×１００ｍｍ 高周波電極３１サイズ 直径２８０ｍｍ 第１前処理条件 前処理用ガス 酸素（Ｏ2 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、１５０Ｗ 処理真空度 ０．２Ｔｏｒｒ 処理時間 ５ｍｉｎ 第２前処理条件 前処理用ガス 水素（Ｈ2 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 処理真空度 ０．１Ｔｏｒｒ 処理時間 ５ｍｉｎ 成膜条件 成膜用原料ガス メタン（ＣＨ4 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 成膜真空度 ０．１Ｔｏｒｒ 成膜速度 ２０００Å／ｍｉｎ 成膜時間 １０ｍｉｎ 実施例４ 被成膜基体Ｓ材質 ウレタンゴム サイズ 厚さ２ｍｍ×１００ｍｍ×１００ｍｍ 高周波電極３１サイズ 直径２８０ｍｍ 第１前処理条件 前処理用ガス 酸素（Ｏ2 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、１５０Ｗ 処理真空度 ０．２Ｔｏｒｒ 処理時間 ５ｍｉｎ 第２前処理条件 前処理用ガス ６フッ化硫黄（ＳＦ6 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 処理真空度 ０．１５Ｔｏｒｒ 処理時間 ５ｍｉｎ 成膜条件 成膜用原料ガス メタン（ＣＨ4 ） ５０ｓｃｃｍ 高周波電力 周波数１３．５６ＭＨｚ、２００Ｗ 成膜真空度 ０．１Ｔｏｒｒ 成膜速度 ２０００Å／ｍｉｎ 成膜時間 １０ｍｉｎ また、比較例として、ウレタンゴムからなる厚さ２ｍｍ
×１００ｍｍ×１００ｍｍの被成膜基体Ｓ上に実施例
１、２、３及び４と同様の条件で、但しプラズマによる
前処理を行わずＤＬＣ膜を形成した。Next, a specific example of the method of the present invention in which a DLC film is formed on a film-forming substrate S made of urethane rubber by using the apparatus shown in FIG. 1 will be described. Example 1 Material of film-forming substrate S Urethane rubber size Thickness 2 mm × 100 mm × 100 mm High frequency electrode 31 size Diameter 280 mm Pretreatment condition Pretreatment gas Hydrogen (H 2 ) 50 sccm High frequency power frequency 13.56 MHz, 200 W Treatment vacuum degree 0 .1 Torr processing time 5 min film forming conditions film forming source gas methane (CH 4 ) 50 sccm high frequency power frequency 13.56 MHz, 200 W film forming vacuum degree 0.1 Torr film forming rate 2000 Å / min film forming time 10 min Example 2 film forming Substrate S Material Urethane rubber size Thickness 2 mm × 100 mm × 100 mm High frequency electrode 31 size Diameter 280 mm Pretreatment condition Pretreatment gas Sulfur hexafluoride (SF 6 ) 50 sccm High frequency power frequency 13.56 MHz, 200 W Vacuum degree 0.15 Torr treatment time 5 min film forming conditions film forming material gas methane (CH 4 ) 50 sccm high frequency power frequency 13.56 MHz, 200 W film forming vacuum degree 0.1 Torr film forming speed 2000 Å / min film forming time 10 min Example 3 film forming substrate S material urethane Rubber size Thickness 2 mm × 100 mm × 100 mm High frequency electrode 31 size Diameter 280 mm First pretreatment condition Pretreatment gas Oxygen (O 2 ) 50 sccm High frequency power frequency 13.56 MHz, 150 W Vacuum degree 0.2 Torr Treatment time 5 min Second previous Processing conditions Pretreatment gas Hydrogen (H 2 ) 50 sccm High frequency power frequency 13.56 MHz, 200 W Processing vacuum degree 0.1 Torr Processing time 5 min Film forming conditions Film forming source gas methane (CH 4 ) 50 sccm High frequency power frequency 13.56 MHz, 200W composition Degree of vacuum 0.1 Torr Film formation speed 2000Å / min Film formation time 10 min Example 4 Material of substrate S to be formed Urethane rubber size Thickness 2 mm × 100 mm × 100 mm High frequency electrode 31 size Diameter 280 mm First pretreatment condition Pretreatment gas Oxygen (O 2 ) 50 sccm High frequency power Frequency 13.56 MHz, 150 W Processing vacuum degree 0.2 Torr Processing time 5 min Second pretreatment condition Pretreatment gas Sulfur hexafluoride (SF 6 ) 50 sccm High frequency power frequency 13.56 MHz, 200 W Processing vacuum Degree 0.15 Torr processing time 5 min film forming conditions film forming source gas methane (CH 4 ) 50 sccm high frequency power frequency 13.56 MHz, 200 W film forming vacuum degree 0.1 Torr film forming speed 2000 Å / min film forming time 10 min As Ureta Thickness 2mm made of rubber
A DLC film was formed on a film-forming substrate S having a size of × 100 mm × 100 mm under the same conditions as in Examples 1, 2, 3 and 4, but without pretreatment with plasma.
【００２０】次に、前記実施例１、２、３、４及び比較
例により得られた各ＤＬＣ膜の基体Ｓとの密着性を評価
した。膜密着性は、円柱状部材を接着剤を用いて膜表面
に接合させ、該円柱状部材を膜に対して垂直方向に引っ
張って該膜を基体Ｓから剥離させ、剥離に要した力を測
定する引っ張り法により評価した。この結果、水素ガス
プラズマによる前処理を行った実施例１、フッ素含有ガ
スプラズマにより前処理を行った実施例２により得られ
た各ＤＬＣ膜の基体との密着強度は従来例により得られ
たＤＬＣ膜と基体との密着強度のそれぞれ５倍、７倍で
あった。また、酸素ガスプラズマによる第１前処理の
後、水素ガスプラズマによる第２前処理を行った実施例
３、酸素ガスプラズマによる第１前処理の後、フッ素含
有ガスプラズマによる第２前処理を行った実施例４によ
り得られた各ＤＬＣ膜の基体との密着強度は従来例によ
り得られたＤＬＣ膜と基体との密着強度のそれぞれ６
倍、８倍であった。Next, the adhesion of each DLC film obtained in Examples 1, 2, 3, 4 and Comparative Example to the substrate S was evaluated. The film adhesion is measured by bonding a columnar member to the film surface with an adhesive, pulling the columnar member in a direction perpendicular to the film to peel the film from the substrate S, and measuring the force required for the peeling. It was evaluated by the pulling method. As a result, the adhesion strength of each DLC film to the substrate obtained in Example 1 pretreated with hydrogen gas plasma and Example 2 pretreated with fluorine-containing gas plasma was the DLC obtained in the conventional example. The adhesion strength between the film and the substrate was 5 times and 7 times, respectively. Example 3 in which the second pretreatment with hydrogen gas plasma was performed after the first pretreatment with oxygen gas plasma, and the second pretreatment with fluorine-containing gas plasma was performed after the first pretreatment with oxygen gas plasma. The adhesion strength of each DLC film obtained in Example 4 to the substrate is 6 times the adhesion strength between the DLC film obtained in the conventional example and the substrate.
It was twice and eight times.
【００２１】このことから、ＤＬＣ膜等の炭素膜を有機
材料からなる基体上に形成するに先立ち、該基体をフッ
素含有ガスプラズマや水素ガスプラズマや酸素ガスプラ
ズマに曝すことで、該基体上に後に形成する炭素膜と該
基体との密着性が向上したことが分かる。Therefore, prior to forming a carbon film such as a DLC film on a substrate made of an organic material, the substrate is exposed to a fluorine-containing gas plasma, a hydrogen gas plasma or an oxygen gas plasma so that the substrate is formed on the substrate. It can be seen that the adhesion between the carbon film formed later and the substrate is improved.
【００２２】[0022]
【発明の効果】以上のように本発明は、有機材料からな
る被成膜基体上に炭素膜を密着性良好に形成できる炭素
膜の形成方法を提供することができる。INDUSTRIAL APPLICABILITY As described above, the present invention can provide a method for forming a carbon film which can form a carbon film on a film-forming substrate made of an organic material with good adhesion.
【図１】本発明に係る炭素膜形成方法の実施に用いるこ
とができる成膜装置の概略構成を示す図である。FIG. 1 is a diagram showing a schematic configuration of a film forming apparatus that can be used for carrying out a carbon film forming method according to the present invention.
【図２】従来方法による炭素膜形成に用いる成膜装置の
１例の概略構成を示す図である。FIG. 2 is a diagram showing a schematic configuration of an example of a film forming apparatus used for forming a carbon film by a conventional method.
【図３】従来方法による炭素膜形成に用いる成膜装置の
他の例の概略構成を示す図である。FIG. 3 is a diagram showing a schematic configuration of another example of a film forming apparatus used for forming a carbon film by a conventional method.
１ 真空チャンバ １１ 排気装置 ２ 基体ホルダ ２０ ヒータ ２１ 直流電源 ３１ 高周波電極 ３２ マッチングボックス ３３ 高周波電源 ４ プラズマ原料ガス供給部 ５ 接地電極 Ｓ 有機材料からなる被成膜基体 Ｓ１ 金属材料からなる被成膜基体 DESCRIPTION OF SYMBOLS 1 Vacuum chamber 11 Exhaust device 2 Substrate holder 20 Heater 21 DC power supply 31 High frequency electrode 32 Matching box 33 High frequency power supply 4 Plasma raw material gas supply section 5 Ground electrode S Film-forming substrate made of organic material S1 Film-forming substrate made of metal material
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ３０Ｂ 29/04 Ｃ３０Ｂ 29/04 Ｑ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C30B 29/04 C30B 29/04 Q
Claims (3)
（Ｆ）含有ガス、水素（Ｈ2 ）ガス及び酸素（Ｏ2 ）ガ
スから選ばれた少なくとも１種のガスのプラズマに曝し
た後、該基体上に炭素膜を形成することを特徴とする炭
素膜の形成方法。1. A film-forming substrate made of an organic material is exposed to plasma of at least one gas selected from fluorine (F) -containing gas, hydrogen (H 2 ) gas and oxygen (O 2 ) gas, A method for forming a carbon film, which comprises forming a carbon film on the substrate.
成する請求項１記載の炭素膜の形成方法。2. The method for forming a carbon film according to claim 1, wherein the carbon film is formed by a plasma CVD method.
求項１又は２記載の炭素膜の形成方法。3. The method for forming a carbon film according to claim 1, wherein a DLC film is formed as the carbon film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25494995A JP3355892B2 (en) | 1995-10-02 | 1995-10-02 | Method of forming carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25494995A JP3355892B2 (en) | 1995-10-02 | 1995-10-02 | Method of forming carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0995784A true JPH0995784A (en) | 1997-04-08 |
| JP3355892B2 JP3355892B2 (en) | 2002-12-09 |
Family
ID=17272100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25494995A Expired - Fee Related JP3355892B2 (en) | 1995-10-02 | 1995-10-02 | Method of forming carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3355892B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11333773A (en) * | 1998-05-26 | 1999-12-07 | Nissin Electric Co Ltd | Sucking member of vacuum suction equipment, and its manufacture |
| US6136386A (en) * | 1996-06-27 | 2000-10-24 | Nissin Electric Co., Ltd. | Method of coating polymer or glass objects with carbon films |
| JP2005015850A (en) * | 2003-06-26 | 2005-01-20 | Konica Minolta Holdings Inc | Thin film deposition method, thin film manufacturing apparatus, and thin film deposited body |
| JP2005015851A (en) * | 2003-06-26 | 2005-01-20 | Konica Minolta Holdings Inc | Thin film deposition method, thin film manufacturing apparatus, and thin film deposited body |
| US6893720B1 (en) | 1997-06-27 | 2005-05-17 | Nissin Electric Co., Ltd. | Object coated with carbon film and method of manufacturing the same |
| JP2006057008A (en) * | 2004-08-20 | 2006-03-02 | Plasma Ion Assist Co Ltd | Sealant and method for producing the same |
| JP2008081239A (en) * | 2006-09-27 | 2008-04-10 | Toray Ind Inc | Winding device for roll and electrical insulating sheet |
| WO2023286673A1 (en) * | 2021-07-14 | 2023-01-19 | 東京エレクトロン株式会社 | Film forming method and plasma processing apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3637687B2 (en) * | 1996-07-13 | 2005-04-13 | 日新電機株式会社 | Manufacturing method of diaphragm for automobile |
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1995
- 1995-10-02 JP JP25494995A patent/JP3355892B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136386A (en) * | 1996-06-27 | 2000-10-24 | Nissin Electric Co., Ltd. | Method of coating polymer or glass objects with carbon films |
| US6893720B1 (en) | 1997-06-27 | 2005-05-17 | Nissin Electric Co., Ltd. | Object coated with carbon film and method of manufacturing the same |
| JPH11333773A (en) * | 1998-05-26 | 1999-12-07 | Nissin Electric Co Ltd | Sucking member of vacuum suction equipment, and its manufacture |
| JP2005015850A (en) * | 2003-06-26 | 2005-01-20 | Konica Minolta Holdings Inc | Thin film deposition method, thin film manufacturing apparatus, and thin film deposited body |
| JP2005015851A (en) * | 2003-06-26 | 2005-01-20 | Konica Minolta Holdings Inc | Thin film deposition method, thin film manufacturing apparatus, and thin film deposited body |
| JP2006057008A (en) * | 2004-08-20 | 2006-03-02 | Plasma Ion Assist Co Ltd | Sealant and method for producing the same |
| JP4733941B2 (en) * | 2004-08-20 | 2011-07-27 | 株式会社プラズマイオンアシスト | Sealing material and manufacturing method thereof |
| JP2008081239A (en) * | 2006-09-27 | 2008-04-10 | Toray Ind Inc | Winding device for roll and electrical insulating sheet |
| WO2023286673A1 (en) * | 2021-07-14 | 2023-01-19 | 東京エレクトロン株式会社 | Film forming method and plasma processing apparatus |
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| Publication number | Publication date |
|---|---|
| JP3355892B2 (en) | 2002-12-09 |
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