JP3187487B2 - Article with diamond-like thin film protective film - Google Patents
Article with diamond-like thin film protective filmInfo
- Publication number
- JP3187487B2 JP3187487B2 JP30826491A JP30826491A JP3187487B2 JP 3187487 B2 JP3187487 B2 JP 3187487B2 JP 30826491 A JP30826491 A JP 30826491A JP 30826491 A JP30826491 A JP 30826491A JP 3187487 B2 JP3187487 B2 JP 3187487B2
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- JP
- Japan
- Prior art keywords
- diamond
- thin film
- substrate
- hardness
- intermediate layer
- Prior art date
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Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、難接着性の物品基体に
対するダイヤモンド様薄膜の接着性ないし結合性を向上
させる技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for improving the adhesion or bonding of a diamond-like thin film to a poorly adherent article substrate.
【０００２】[0002]
【従来技術】気相法により製造されるダイヤモンド様薄
膜は硬度が高く、耐摩耗性、耐久性、耐薬品性、耐食性
等に優れており、また任意形状の物品に被着できるた
め、こうした特性の一つ以上が必要な物品の保護膜とし
て有用である。気相法によるダイヤモンド様薄膜製造方
法には各種の形式がある（例えば「表面化学」第５巻第
１０８号（１９８４年）第１０８−１１５頁の各種の方
法参照）。ダイヤモンド様薄膜は任意形状の保護すべき
物品の表面に被覆され、耐食性、耐摩耗性などの保護膜
として広く利用される。2. Description of the Related Art A diamond-like thin film produced by a gas phase method has high hardness, excellent abrasion resistance, durability, chemical resistance, corrosion resistance, and the like. Is useful as a protective film for necessary articles. There are various types of methods for producing a diamond-like thin film by a vapor phase method (for example, see various methods in “Surface Chemistry”, Vol. 5, No. 108 (1984), pp. 108-115). The diamond-like thin film is coated on the surface of an article of any shape to be protected, and is widely used as a protective film such as corrosion resistance and abrasion resistance.
【０００３】ダイヤモンド様薄膜はシリコン等の基体に
は強固に結合し得るが、物品の種類によっては基体に対
する結合力が弱く、外力の作用で基体から剥離し易い問
題があった。そのため保護被覆として耐食性、耐摩耗性
等が必要な用途において充分に効果を発揮出来ない。特
にＦｅ系の金属又は合金（例えば軟鋼（ＳＴＣ）、ステ
ンレス鋼、焼き入れ鋼（ＳＫＤ、ＳＫＳ）等）、その他
Ｃｏ、Ｎｉなどの金属の合金、ガラス、セラミックス等
はダイヤモンド様薄膜に対する結合力が弱いことが知ら
れている。鉄を主成分とする基体は例えば機構部材、摺
動部材等最も工業的価値の高いものであるし、又ガラス
やセラミックスではサーマルヘッド等の摺動部分などに
使用されるなど、広い用途を有するので、これらの基体
の表面に形成されるダイヤモンド様薄膜の基体への接着
性を向上させることが重要である。[0003] Although a diamond-like thin film can be firmly bonded to a substrate such as silicon, there is a problem that the bonding force to the substrate is weak depending on the kind of an article, and the diamond-like thin film is easily peeled off from the substrate by the action of an external force. Therefore, the effect cannot be sufficiently exerted in applications requiring corrosion resistance, wear resistance, etc. as a protective coating. In particular, Fe-based metals or alloys (eg, mild steel (STC), stainless steel, quenched steel (SKD, SKS), etc.), other metal alloys such as Co, Ni, glass, ceramics, etc., have a bonding force to a diamond-like thin film. It is known to be weak. Substrates containing iron as a main component are of the highest industrial value, such as mechanical members and sliding members, and have a wide range of uses such as glass and ceramics used for sliding parts such as thermal heads. Therefore, it is important to improve the adhesion of the diamond-like thin film formed on the surface of these substrates to the substrate.
【０００４】この基体に前処理を行なって接着性を向上
することは特開昭６０−２００８９８号、同６０−２０
４６９５号、同６１−１７４３７６号等で提案されてい
る。It is disclosed in Japanese Patent Application Laid-Open Nos. 60-200898 and 60-20 to improve the adhesiveness by performing a pretreatment on the substrate.
4695 and 61-174376.
【０００５】[0005]
【発明が解決すべき課題】特開昭６０−２００８９８号
ではＣｏ−ＷＣ合金を基体とし、その表面にダイヤモン
ド様薄膜を高硬度膜として付けるに当たり、基体の表面
に予めグロー放電を直接作用させることによりイオンエ
ッチングすることを提案しているが、加速電圧は印加さ
れていないからエッチング効率は接着性向上の面からは
充分でなく本発明が目的する接着性の向上は充分に得ら
れない。特開昭６０−２０４６９５号も上記技術と同様
に成膜速度の向上を意図してＡｒガスを減圧室内に導入
し正負電極間に電圧を加えてプラズマを作りこれを基体
に作用させるのであるが、プラズマのイオン濃度は低い
のでエッチング効果は接着性向上の観点からは低い。特
開昭６１−１７４３７６号は基体の接着性を向上するた
めにプラズマガスで基体を処理した後、酸化処理して酸
化物被膜を形成することを記載している。しかし、プラ
ズマは先ず拡散によって正イオンが正電位のグリッドを
通り抜ける必要があり、成膜に必要な充分な量の正イオ
ンが基体に到達出来ないので結果として効率の悪い方法
である。従って従来公知の技術では基体とダイヤモンド
様薄膜との間の接着力が充分に高い成膜は可能でなかっ
た。また特開平３−８０１９０号にはイオンを加速して
基体表面を衝撃する方法が記載され、上記の各方法より
はすぐれているが必ずしも十分な結合力が得られていな
い。In Japanese Patent Application Laid-Open No. 60-200898, a Co-WC alloy is used as a substrate, and a glow discharge is directly applied to the surface of the substrate before applying a diamond-like thin film as a high hardness film on the surface. However, since no acceleration voltage is applied, the etching efficiency is not sufficient from the viewpoint of improving the adhesiveness, and the improvement of the adhesiveness intended by the present invention cannot be sufficiently obtained. In Japanese Patent Application Laid-Open No. 60-204695, Ar gas is introduced into a decompression chamber and a voltage is applied between the positive and negative electrodes to produce a plasma and act on the substrate, with the intention of improving the film forming rate in the same manner as the above technique. Since the plasma ion concentration is low, the etching effect is low from the viewpoint of improving the adhesiveness. JP-A-61-174376 describes that an oxide film is formed by treating a substrate with a plasma gas and then oxidizing the substrate in order to improve the adhesion of the substrate. However, plasma is a method of inefficiency because the positive ions must first pass through a grid of positive potential by diffusion, and a sufficient amount of positive ions required for film formation cannot reach the substrate. Therefore, it was not possible to form a film having sufficiently high adhesive force between the substrate and the diamond-like thin film by the conventionally known technique. JP-A-3-80190 describes a method of bombarding the surface of a substrate by accelerating ions, which is superior to the above-mentioned methods, but does not always provide a sufficient bonding force.
【０００６】そこで本発明者らは特願平３−１４２６７
８号でＭｏを中間層として接着性を改善することを提案
した。この中間層はすぐれた結合力を生じることがわか
った。本発明者は中間層として他の物質を試みたとこ
ろ、同出願に記載したものと同等以上の効果を得た。そ
のほか、結晶性の炭化けい素、結晶性の窒化けい素等の
中間層を形成することも知られているが、しかし、従来
の方法及び上記先願の方法は、成膜時にダイヤモンドと
は異質の原料を使用して中間層を形成する必要があり、
工程数が増加する。それに加えて特に公知の結晶性の中
間層は結合力が十分でない。したがって、本発明の目的
は、比較的簡単な方法で、基体に対する結合力ないし接
着力が大きく、耐剥離性で耐久性の向上したダイヤモン
ド様薄膜を具備した物品を提供することにある。Accordingly, the present inventors have filed a Japanese Patent Application No. Hei 3-14267.
No. 8 proposed using Mo as an intermediate layer to improve the adhesion. This intermediate layer was found to produce excellent bonding strength. The present inventor tried other substances as the intermediate layer, and obtained the same or better effects as those described in the same application. In addition, it is known to form an intermediate layer of crystalline silicon carbide, crystalline silicon nitride, etc. However, the conventional method and the method of the prior application are different from diamond at the time of film formation. It is necessary to form an intermediate layer using the raw materials of
The number of steps increases. In addition, particularly well-known crystalline interlayers do not have sufficient bonding strength. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an article provided with a diamond-like thin film having a large bonding strength or adhesion to a substrate, a peel resistance and an improved durability by a relatively simple method.
【０００７】[0007]
【課題を解決するための手段】本発明は、通常の基体は
もちろん、Ｃｏ、Ｎｉ、Ｆｅの少なくとも一種を含む合
金、セラミックス及びガラスよりなる群より選択され且
つダイヤモンド様薄膜との親和性が悪い基体の表面に、
前記基体よりも硬度が大きく且つ後記ダイヤモンド様薄
膜よりは硬度が小さいＨｖ＝１０００〜５０００ｋｇ／
ｍｍ2 の炭素中間層と、ダイヤモンド様薄膜とを順に形
成した保護膜を有する物品を提供する。特に好ましく
は、本発明の中間層は基体からダイヤモンド様薄膜に向
かって段階的または連続的に硬度が大きくなる。ただし
成形あるいは加工用金型への応用は別出願の対象とした
ので本発明からは除かれる。According to the present invention, not only a normal substrate but also an alloy containing at least one of Co, Ni and Fe, a ceramic and a glass are selected, and the affinity with a diamond-like thin film is poor. On the surface of the substrate,
Hv = 1000-5000 kg / has a higher hardness than the substrate and a lower hardness than the diamond-like thin film described later.
Provided is an article having a protective film in which a carbon intermediate layer of mm 2 and a diamond-like thin film are sequentially formed. Particularly preferably, the hardness of the intermediate layer of the present invention increases stepwise or continuously from the substrate toward the diamond-like thin film. However, the application to a molding or processing mold is excluded from the present invention since it is covered by a separate application.
【０００８】本発明では、イオン化蒸着法における負バ
イアス蒸着条件を制御することによりプラズマ中の水素
及び炭素の正イオンを基体の表面に蒸着して、前記基体
よりも硬度が大きく且つ後記ダイヤモンド様薄膜よりは
硬度が小さい炭素中間層を成膜し、次いで原料炭化水素
を変更することなく且つ同じイオン化蒸着法を使用して
成膜条件を変更しダイヤモンド様薄膜を成膜する。特に
中間層は硬度が基体からダイヤモンド様薄膜に向かって
大きくなる様に中間層自体の成膜時にも階段的または連
続的な成膜条件の変更を実施することが好ましい。In the present invention, a negative electrode in the ionization vapor deposition method is used.
Hydrogen in plasma by controlling ias deposition conditions
And depositing positive ions of carbon on the surface of the substrate to form a carbon intermediate layer having a higher hardness than the substrate and a lower hardness than the diamond-like thin film described below, and then changing the raw material hydrocarbons to the same level. A diamond-like thin film is formed by changing film forming conditions using an ionization vapor deposition method. In particular, it is preferable to change the film-forming conditions stepwise or continuously during the film formation of the intermediate layer itself so that the hardness of the intermediate layer increases from the substrate toward the diamond-like thin film.
【０００９】中間層を形成するための方法は、特開昭５
８−１７４５０７号及び特開平１−２３４３９６号に記
載されたイオンが化蒸着法を使用する。この方法によれ
ば、中間層の成膜後に、その層を空気にさらすことな
く、あるいは作業自体を中断することなく条件をダイヤ
モンド様薄膜の成膜条件に変更することにより、次のダ
イヤモンド様薄膜の形成工程に移行することができる。
このため本発明の方法は作業性が極めてよい。なお、好
ましくはこの工程に先立って、成膜装置の真空室内に前
記基体を配置し、Ａｒ等のボンバード用ガスを前記真空
室内に導入し、熱陰極フィラメントとその周りに設けら
れた対陰極とよりなるイオン化手段により電離してイオ
ンの流れを形成し、これを前記対陰極よりも低電位にあ
るグリッドにより加速して基体の表面をボンバードして
活性化する前工程を採用してもよい。A method for forming an intermediate layer is disclosed in
The ions described in JP-A-8-174507 and JP-A-1-234396 use a chemical vapor deposition method. According to this method, after the formation of the intermediate layer, the next diamond-like thin film can be formed by changing the conditions to the diamond-like thin film formation conditions without exposing the layer to air or without interrupting the operation itself. Can be shifted to the forming process.
For this reason, the method of the present invention has extremely good workability. Preferably, prior to this step, the substrate is placed in a vacuum chamber of a film forming apparatus, bombarding gas such as Ar is introduced into the vacuum chamber, and a hot cathode filament and a counter cathode provided therearound are provided. A pre-process may be employed in which ion flow is formed by ionization by the ionizing means, and the flow of ions is formed, accelerated by a grid having a lower potential than the counter electrode, and bombarded to activate the surface of the substrate.
【００１０】中間層は基体の硬度よりは大きく且つダイ
ヤモンド様薄膜の硬度よりは小さい一定の組成の膜でも
良いが、好ましくは基体側で低硬度、ダイヤモンド側で
高硬度にする。これにより結合性密着性を改善すること
ができる。中間層とダイヤモンド様薄膜の成膜は同一の
イオン化蒸着装置を使用し、同一の原料を使用し、単に
蒸着条件を連続的または段階的に変化させるだけで良
い。中間層の膜厚は０．０２〜３μｍが好適であり、更
に好ましくは０．０５〜０．５μｍである。余り薄いと
効果がなく、余り厚過ぎても効果が飽和する。The intermediate layer may be a film having a constant composition larger than the hardness of the substrate and smaller than the hardness of the diamond-like thin film, but preferably has a low hardness on the substrate side and a high hardness on the diamond side. Thereby, the bonding and adhesion can be improved. For forming the intermediate layer and the diamond-like thin film, the same ionized vapor deposition apparatus is used, the same raw material is used, and the vapor deposition conditions may be simply changed continuously or stepwise. The thickness of the intermediate layer is preferably 0.02 to 3 μm, more preferably 0.05 to 0.5 μm. If it is too thin, there is no effect, and if it is too thick, the effect is saturated.
【００１１】ダイヤモンド様薄膜の硬度はイオン化蒸着
法によるとき約６０００ｋｇ／ｍｍ2 以上である。一方
基板になる物品の硬度は材質によって異なるが、通常は
２００〜３０００ｋｇ／ｍｍ2 である。したがって、中
間層の硬度を基板の材料とダイヤモンド様薄膜の中間の
硬度である１０００〜５０００ｋｇ／ｍｍ2 の範囲で選
択すれば良い。[0011] The hardness of the diamond-like thin film is about 6000 kg / mm 2 or more as measured by ionization vapor deposition. On the other hand, the hardness of the article serving as the substrate varies depending on the material, but is usually 200 to 3000 kg / mm 2 . Therefore, the hardness of the intermediate layer may be selected in the range of 1000 to 5000 kg / mm 2 which is the intermediate hardness between the substrate material and the diamond-like thin film.
【００１２】イオン化蒸着法による中間層の形成にあっ
ては、前記の単独又は混合ガスを用いる。またダイヤモ
ンド様薄膜の形成にあっては、炭化水素原料ガス又は分
解又は反応により炭化水素を生成し得る原料ガス（ここ
に炭化水素とはメタン、エタン、プロパン等の飽和炭化
水素、エチレン、プロピレン、アセチレン等の不飽和炭
化水素等があり、分解して炭化水素を生成し得る原料ガ
スはメチルアルコール、エチルアルコール等のアルコー
ル類、アセトン、メチルエチルケトン等のケトン類など
があり、又反応して炭化水素ガスを生成する原料ガスに
は一酸化炭素、二酸化炭素と水素との混合ガス等があ
る。また前記原料にはヘリウム、ネオン、アルゴン等の
希ガスあるいは水素、酸素、窒素、水、一酸化炭素、二
酸化炭素、等の少なくとも一種を含ませることができ
る）を熱陰極フィラメント−対陰極間のアーク放電、陰
極熱フィラメント−対陰極間の熱電子放出によるイオン
化等の手段でイオン化してイオン流とし、この流れを電
場で加速して基体に差し向けることによりダイヤモンド
様薄膜を成膜する方法であり、詳細は特開昭５８−１７
４５０７号及び特開平１−２３４３９６号に記載されて
いる。In the formation of the intermediate layer by the ionization vapor deposition method, the above-mentioned single or mixed gas is used. In the formation of a diamond-like thin film, a hydrocarbon raw material gas or a raw material gas capable of generating hydrocarbons by decomposition or reaction (here, hydrocarbons are saturated hydrocarbons such as methane, ethane and propane, ethylene, propylene, There are unsaturated hydrocarbons such as acetylene, etc., and raw material gases that can be decomposed to produce hydrocarbons include alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, and hydrocarbons that react to produce hydrocarbons. Source gases for producing the gas include carbon monoxide, a mixed gas of carbon dioxide and hydrogen, etc. The above-mentioned raw materials include rare gases such as helium, neon, and argon, or hydrogen, oxygen, nitrogen, water, carbon monoxide. , Carbon dioxide, etc.) can be contained in the hot cathode filament-cathode arc discharge, the cathode hot filter. A method of forming a diamond-like thin film by ionizing by ionization by means of thermionic emission between the element and the cathode to form an ion stream, accelerating the stream with an electric field and directing the stream to a substrate. Kaisho 58-17
No. 4507 and JP-A-1-234396.
【００１３】第１図に特開昭５８−１７４５０７号に従
った成膜装置の好ましい例を示す。その他の公知のイオ
ン化蒸着装置を使用してもよいことはもちろんである。
図中３０は真空容器、３１はチャンバーであり、排気系
３８に接続されて１０-6Ｔｏｒｒ程度までの高真空に引
かれる。３２は基体Ｓの裏面に設けられ負の電位Ｖａに
保たれた電極である。基体Ｓの表面に近接又は接触して
ダイヤモンド様薄膜の形状を規制する窓を有するマスク
４２が設けられる。このマスクは基体に接していても良
いが膜の周部の厚みを薄くして割れ（クラック）を減じ
るためにはなるべくは離間させる。３３は基体と同一の
電位Ｖａを与えられたグリッドで成膜工程で炭化水素イ
オンの加速を行なうのに使用される。このグリッド３３
は膜の連続性を高め且つ表面を平滑にするため適正に定
めた空間率（単位面積あたりの穴の面積）と穴密度（単
位長さあたりの穴の数）のグリッドを使用し、或いはそ
の面内方向に振動するための手段を有していても良い。
３４は負の電位Ｖｄに維持された熱陰極フィラメントで
あり、交流電源からの電流Ｉｆによって加熱されて熱電
子を発生する。３５は原料でガスの供給口であり、３７
はガス供給通路、３７’はプラズマ励起室である。フィ
ラメント３４を取囲んで陽極３６が配置されている。こ
の陽極はこの場合接地されているが、フィラメントに対
しては正の電圧Ｖｄを有し、電極３２及びグリッド３３
に対しては正の電位Ｖａを与えられている。フィラメン
ト３４、陽極３６及び供給口３５の周りを取り囲んでイ
オン化ガスの閉じ込め用の磁界を発生するために電源Ｖ
ｃからの電流Ｉｃで励磁される電磁コイル３９が配置さ
れている。従って、Ｉｆ、Ｖａ、Ｖｄ、コイルの電流Ｉ
ｃを調整することにより膜質を変えることができる。特
にＶａ（基体電圧）及びＶｄ（熱陰極ー陽極間の電位
差）の制御が好ましい。このような成膜条件の制御は、
コンピュータによるプログラム制御により容易に実行す
ることができる。FIG. 1 shows a preferred example of a film forming apparatus according to JP-A-58-174507. Of course, other known ionized vapor deposition devices may be used.
In the figure, reference numeral 30 denotes a vacuum container, and 31 denotes a chamber, which is connected to an exhaust system 38 and is evacuated to a high vacuum of about 10 -6 Torr. Reference numeral 32 denotes an electrode provided on the back surface of the base S and maintained at a negative potential Va. A mask 42 having a window that regulates the shape of the diamond-like thin film in proximity to or in contact with the surface of the substrate S is provided. This mask may be in contact with the substrate, but should be separated as much as possible in order to reduce the thickness of the peripheral portion of the film and reduce cracks. Reference numeral 33 denotes a grid to which the same potential Va as that of the base is applied, which is used for accelerating hydrocarbon ions in a film forming process. This grid 33
Uses a grid of properly defined porosity (area of holes per unit area) and hole density (number of holes per unit length) to increase membrane continuity and smooth the surface, or A means for vibrating in the in-plane direction may be provided.
Numeral 34 denotes a hot cathode filament maintained at a negative potential Vd, which is heated by a current If from an AC power supply to generate thermoelectrons. Reference numeral 35 denotes a raw material gas supply port;
Is a gas supply passage, and 37 'is a plasma excitation chamber. An anode 36 is arranged around the filament 34. This anode is in this case grounded, but has a positive voltage Vd for the filament, and the electrode 32 and the grid 33
Is supplied with a positive potential Va. A power supply V is provided for generating a magnetic field for confining the ionized gas surrounding the filament 34, the anode 36 and the supply port 35.
An electromagnetic coil 39 that is excited by a current Ic from c is arranged. Therefore, If, Va, Vd and the coil current I
The film quality can be changed by adjusting c. In particular, control of Va (substrate voltage) and Vd (potential difference between hot cathode and anode) is preferable. Such control of film forming conditions is as follows.
It can be easily executed by program control by a computer.
【００１４】成膜にあたり、チャンバー３１内を１０-6
Ｔｏｒｒまで高真空とし、ガス供給通路３７のバルブを
操作して所定流量の中間層成膜用のガス、またはダイヤ
モンド成膜用のガス、場合によりそれと水素との混合ガ
ス、或いはそれとＡｒ、Ｈｅ、Ｎｅ等のキャリアガス等
を各供給口３５から導入しながら排気系３８を調整して
所定のガス圧例えば１０-1Ｔｏｒｒとする。一方、複数
の熱陰極フイラメント３４には交流電流Ｉｆを流して加
熱し、フイラメント３４と陽極３６の間には電位差Ｖｄ
を印加して放電を形成する。供給口３５から供給された
原料ガスは熱分解されるとともにフィラメントからの熱
電子と衝突してプラスのイオンと電子を生じる。この電
子は別の熱分解粒子と衝突する。電磁コイルの磁界によ
る閉じ込め作用の下に、このような現象を繰り返すこと
により原料ガスは熱分解物質のプラスイオンとなる。プ
ラスイオンは電極３２、グリッド３６に印加された負電
位Ｖａにより引き寄せられ、基体Ｓの方へ向けて加速さ
れ、基体に衝突して成膜反応を行ない、ダイヤモンド様
薄膜を形成する。なお、各部の電位、電流、温度等の条
件については上に述べた条件の他、先に引用した特許公
報を参照されたい。In forming a film, the inside of the chamber 31 is set to 10 −6.
A high vacuum was applied to Torr, and a valve for the gas supply passage 37 was operated to operate a predetermined flow rate of a gas for forming an intermediate layer, a gas for forming a diamond, a mixed gas of hydrogen and gas, or Ar, He, The exhaust system 38 is adjusted while introducing a carrier gas such as Ne from each supply port 35 to a predetermined gas pressure, for example, 10 -1 Torr. On the other hand, the plurality of hot cathode filaments 34 are heated by passing an alternating current If, and a potential difference Vd is applied between the filaments 34 and the anode 36.
Is applied to form a discharge. The raw material gas supplied from the supply port 35 is thermally decomposed and collides with thermoelectrons from the filament to generate positive ions and electrons. This electron collides with another pyrolysis particle. By repeating such a phenomenon under the confinement effect of the magnetic field of the electromagnetic coil, the raw material gas becomes a positive ion of the thermal decomposition substance. The positive ions are attracted by the negative potential Va applied to the electrode 32 and the grid 36, accelerated toward the substrate S, collide with the substrate, and perform a film forming reaction to form a diamond-like thin film. For the conditions such as the potential, current, and temperature of each part, refer to the above-mentioned patent publications in addition to the above-mentioned conditions.
【００１５】以下に本発明を例示する。Hereinafter, the present invention will be exemplified.
【実施例の説明】イオン化蒸着法を用い、ＳＫＤ１１及
び石英ガラス（ＳＵＰＲＡＳＬ：信越石英（株））より
なる物品基体の上に表１に示す条件で中間層を成膜し、
次いで表１の条件でダイヤモンド様薄膜を成膜した。フ
ィラメント３４はコイル状としその幅３ｍｍ、その周り
を取り囲む電極３６との隙間８ｍｍとした。グリッド３
３は５ｍｍ／分の速度で振動させた。Ｉｆ＝２５Ａ，フ
ィラメント電圧Ｖｄ可変、基体電圧Ｖａ可変、電磁コイ
ルの磁束密度３００Ｇの条件で、ＣＨ4 を導入し、各種
膜厚の中間層、次いで膜厚３．０μｍのダイヤモンド様
薄膜を得た。DESCRIPTION OF THE PREFERRED EMBODIMENTS An intermediate layer is formed on an article substrate made of SKD11 and quartz glass (SUPRASL: Shin-Etsu Quartz Co., Ltd.) under the conditions shown in Table 1 by ionization vapor deposition.
Next, a diamond-like thin film was formed under the conditions shown in Table 1. The filament 34 was coil-shaped and had a width of 3 mm and a gap of 8 mm with the electrode 36 surrounding the filament. Grid 3
3 was vibrated at a speed of 5 mm / min. CH 4 was introduced under the conditions of If = 25 A, a variable filament voltage Vd, a variable substrate voltage Va, and a magnetic flux density of the electromagnetic coil of 300 G to obtain an intermediate layer having various thicknesses, and then a diamond-like thin film having a thickness of 3.0 μm. .
【００１６】[0016]
【表１】 [Table 1]
【００１７】得られた保護膜付き物品の保護膜の特性表
２に示す通りであった。ただし密着力とスクラッチ力の
評価は次の通りであった。密着力は１ｃｍ角、長さ１０
ｃｍの角材をダイヤモンド様薄膜にエポキシ樹脂で接着
し、引張試験機（テンシロン−商品名）で引っ張って剥
離し測定を行なった。又スクラッチ力はＲｈｅｓｃａ社
製のＣＳＲ−０２試験機で測定した。いずれの値も表１
の第１行の値を基準とした相対値である。The properties of the protective film of the obtained article with a protective film were as shown in Table 2. However, the evaluation of adhesion and scratching power was as follows. Adhesion force 1cm square, length 10
cm square material was adhered to the diamond-like thin film with an epoxy resin, pulled and peeled off by a tensile tester (Tensilon-trade name), and measured. The scratch force was measured with a CSR-02 tester manufactured by Rhesca. Table 1 shows all values
Is a relative value based on the value in the first row of FIG.
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【発明の効果】本発明によると中間層を介在することに
よりダイヤモンド様薄膜を、通常では結合が困難な物品
基体に施すことが可能になった。According to the present invention, it becomes possible to apply a diamond-like thin film to an article substrate, which is usually difficult to bond, by interposing an intermediate layer.
【図１】本発明に使用するイオン化蒸着装置の概要を示
す。FIG. 1 shows an outline of an ionization vapor deposition apparatus used in the present invention.
３０ 真空容器 ３１ チャンバー ３２ 負電極 ４２ マスク ３３ グリッド ３４ 熱陰極フィラメント ３５ 原料ガスの供給口 ３６ 陽極 ３７ ガス供給通路 ３７’ プラズマ励起室 Reference Signs List 30 vacuum vessel 31 chamber 32 negative electrode 42 mask 33 grid 34 hot cathode filament 35 source gas supply port 36 anode 37 gas supply passage 37 ′ plasma excitation chamber
Claims (5)
炭化水素プラズマに対して第１の負バイアス条件下に蒸
着して得た、前記基体よりも硬度が大きく且つ後記ダイ
ヤモンド様薄膜よりは硬度が小さい硬度Ｈｖ＝１０００
〜５０００ｋｇ／ｍｍ2 の炭素中間層と、その上に炭化
水素プラズマから、炭化水素プラズマに対してより大き
い第２の負バイアス条件下に蒸着して得たダイヤモンド
様薄膜とよりなる保護膜を有する物品。1. The method according to claim 1, wherein the surface of the substrate is converted from the hydrocarbon plasma to
Under a first negative bias condition with respect to the hydrocarbon plasma,
Hardness Hv = 1000, which is higher in hardness than the substrate and lower in hardness than the diamond-like thin film described later , obtained by
~ 5000 kg / mm 2 carbon intermediate layer and carbonized on it
Larger to hydrogen plasma from hydrogen plasma
An article having a protective film comprising a diamond-like thin film obtained by vapor deposition under a second negative bias condition .
む合金、セラミックス及びガラスよりなる群より選択さ
れ且つダイヤモンド様薄膜との親和性が悪い基体の表面
に、前記基体よりも硬度が大きく且つ後記ダイヤモンド
様薄膜よりは硬度が小さい炭素中間層と、ダイヤモンド
様薄膜を順に形成した請求項１に記載の保護膜付き物
品。2. The surface of a substrate selected from the group consisting of an alloy containing at least one of Co, Ni, and Fe, ceramics, and glass and having a poor affinity for a diamond-like thin film, has a higher hardness than the substrate and is described later. The article with a protective film according to claim 1, wherein a carbon intermediate layer having a lower hardness than the diamond-like thin film and a diamond-like thin film are sequentially formed.
向かって段階的または連続的に硬度が大きくなる請求項
１または２に記載の保護膜付き物品。3. The article with a protective film according to claim 1, wherein the hardness of the intermediate layer increases stepwise or continuously from the substrate toward the diamond-like thin film.
ある請求項１〜４のいずれかに記載の保護膜付き物品。4. The article with a protective film according to claim 1, wherein the thickness of the intermediate layer is 0.02 to 3.0 μm.
面に、前記基体よりも硬度が大きく且つ後記ダイヤモン
ド様薄膜よりは硬度が小さい硬度Ｈｖ＝１０００〜５０
００ｋｇ／ｍｍ 2 の炭素中間層がえられるように第１の
負バイアス条件下に蒸着させ、次いで前記中間層の上に
前記負バイアス条件をより大きい第２の負バイアス条件
に変えて、より硬質であるダイヤモンド様薄膜を形成す
ることを特徴とする物品の保護膜形成方法。5. The method according to claim 1, wherein the hydrocarbon gas is converted into plasma, and
The surface has a higher hardness than the substrate and
Hardness Hv = 1000 to 50, which is smaller than the hardness of the thin film
First, a carbon intermediate layer of 00 kg / mm 2 was obtained.
Deposited under negative bias conditions, then over the interlayer
A second negative bias condition greater than the negative bias condition
To form a harder diamond-like thin film
A method for forming a protective film on an article .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30826491A JP3187487B2 (en) | 1991-10-29 | 1991-10-29 | Article with diamond-like thin film protective film |
| US08/209,573 US5707717A (en) | 1991-10-29 | 1994-03-10 | Articles having diamond-like protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30826491A JP3187487B2 (en) | 1991-10-29 | 1991-10-29 | Article with diamond-like thin film protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05117087A JPH05117087A (en) | 1993-05-14 |
| JP3187487B2 true JP3187487B2 (en) | 2001-07-11 |
Family
ID=17978922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30826491A Expired - Fee Related JP3187487B2 (en) | 1991-10-29 | 1991-10-29 | Article with diamond-like thin film protective film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3187487B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3119172B2 (en) | 1995-09-13 | 2000-12-18 | 日新電機株式会社 | Plasma CVD method and apparatus |
| DE69736790T2 (en) * | 1996-06-27 | 2007-08-16 | Nissin Electric Co., Ltd. | Carbon film coated article and method of making the same |
| US6893720B1 (en) | 1997-06-27 | 2005-05-17 | Nissin Electric Co., Ltd. | Object coated with carbon film and method of manufacturing the same |
| EP1067211B1 (en) | 1999-07-08 | 2008-10-01 | Sumitomo Electric Industries, Ltd. | Hard coating and coated member |
| US7820293B2 (en) * | 2005-08-18 | 2010-10-26 | Nv Bekaert Sa | Substrate coated with a layered structure comprising a tetrahedral carbon coating |
| JP2007070667A (en) * | 2005-09-05 | 2007-03-22 | Kobe Steel Ltd | Formed article with hard multilayer film of diamond-like carbon, and production method therefor |
| JP2009167512A (en) | 2008-01-21 | 2009-07-30 | Kobe Steel Ltd | Diamond-like carbon film for sliding component and method for manufacturing the same |
| CN111908935B (en) * | 2020-01-19 | 2022-12-09 | 湖南碳康生物科技有限公司 | Carbon-based composite material bone screw and preparation method thereof |
-
1991
- 1991-10-29 JP JP30826491A patent/JP3187487B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05117087A (en) | 1993-05-14 |
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