JPH04341558A - Article with diamondlike protective film and its production - Google Patents
Article with diamondlike protective film and its productionInfo
- Publication number
- JPH04341558A JPH04341558A JP14267891A JP14267891A JPH04341558A JP H04341558 A JPH04341558 A JP H04341558A JP 14267891 A JP14267891 A JP 14267891A JP 14267891 A JP14267891 A JP 14267891A JP H04341558 A JPH04341558 A JP H04341558A
- Authority
- JP
- Japan
- Prior art keywords
- film
- diamond
- substrate
- grid
- molecular weight
- 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
- 230000001681 protective effect Effects 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000010408 film Substances 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 239000010409 thin film Substances 0.000 claims abstract description 28
- 150000002500 ions Chemical class 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract 3
- 239000007789 gas Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 24
- -1 hydrocarbon ions Chemical class 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000011109 contamination Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229910003460 diamond Inorganic materials 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000760 Hardened steel Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 101150019161 SKS2 gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ダイヤモンド様薄膜で
保護した物品の製造方法に関し、特に難接着性ないし難
結合性の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成膜技術に関する。ただし焼入れ
鋼製金型は別個の出願の対象にしたので本発明には含ま
れない。[Field of Industrial Application] The present invention relates to a method for manufacturing an article protected with a diamond-like thin film, and more particularly to a film-forming technique for improving the adhesion or bonding properties of a diamond-like thin film to a substrate that is difficult to adhere or bond to. . However, the hardened steel mold is the subject of a separate application and is therefore not included in the present invention.
【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
有用であり、或は有望視されている。[Prior Art] Diamond-like thin films produced by the vapor phase method have high hardness, excellent wear resistance, durability, chemical resistance, corrosion resistance, etc., and can be applied to articles of arbitrary shapes, so these properties It is considered to be useful or promising as a protective film for articles that require one or more of the following.
【０００３】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１
０８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。There are various methods for producing diamond-like thin films using the vapor phase method (for example, "Surface Chemistry", Vol. 5, No. 1).
08 (1984), pp. 108-115). A diamond-like thin film is coated on the surface of an article to be protected of any shape, and is widely used as a protective film for corrosion resistance, wear resistance, etc.
【０００４】しかしこれらの従来技術によって製造され
たダイヤモンド様薄膜は基体の種類によって基体に対す
る結合力が弱く、ダイヤモンド様薄膜が微結晶の集まり
であるため表面粗度が大きいことも原因となって、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
する基体は例えば金型、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。However, the diamond-like thin films produced by these conventional techniques have weak bonding force to the substrate depending on the type of substrate, and because the diamond-like thin film is a collection of microcrystals, the surface roughness is large. There was a problem in that it was easy to peel off from the substrate due to the action of external force. Therefore, it cannot be sufficiently effective as a protective coating in applications where corrosion resistance, abrasion resistance, etc. are required. Especially Fe-based metals or alloys (e.g. mild steel (STC), stainless steel, hardened steel (
SKD, SKS), alloys of other metals such as Co and Ni, glass, ceramics, etc. are known to have weak bonding strength to diamond-like thin films. Substrates whose main component is iron have the highest industrial value, such as molds and sliding parts, and glass and ceramics have a wide range of uses, such as being used in sliding parts of thermal heads, etc. Therefore, it is important to improve the adhesion of the diamond-like thin film formed on the surface of these substrates to the substrate.
【０００５】これらの基体に前処理を行なうことは特開
昭６０−２００８９８号、同６０−２０４６９５号、同
６１−１７４３７６号等で提案されている。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、基体の表面に予め直流又は交流グロー放電を直接
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、その目的はダイヤモンド結晶の成長核を増
大して成膜速度を上げることにあり、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
ズマの生成には高周波を使用し、その中の正イオンで正
電位のグリッドを通り抜けたイオンが負電位に接続され
た金属基体に向けて加速する方法を採用しているため、
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接着性の向上の面から
は不十分である。本発明者らはこれらの欠点を改善する
ために特願平１−２１４９１３号において基板を高エネ
ルギーのＡｒイオン等でボンバード（衝撃）して前処理
することを提案したが、なお接着性は不十分である。Pretreatment of these substrates has been proposed in Japanese Patent Laid-open Nos. 60-200898, 60-204695, and 61-174376. Tokukai 1986
In No. 200898, a Co-WC alloy is used as a substrate, and in order to attach a diamond-like thin film as a highly hard film to the surface thereof, it is proposed that ion etching is performed by directly applying direct current or alternating current glow discharge to the surface of the substrate in advance. However, the purpose of this is to increase the growth rate of diamond crystals and increase the film formation rate, and since no accelerating voltage is applied, the etching efficiency is not sufficient from the viewpoint of improving adhesion, which is the purpose of the present invention. Adhesion cannot be sufficiently improved. JP-A No. 60-204695 also introduces Ar gas into a reduced pressure chamber and applies voltage between positive and negative electrodes to create plasma, which acts on the substrate, in the same way as the above-mentioned technique, with the intention of increasing the film formation rate. Since the ion concentration of the plasma is low, the etching effect is low from the viewpoint of improving adhesion. JP-A-61-174376 discloses that in order to improve the adhesion of the substrate, the substrate is treated with plasma gas and then subjected to oxidation treatment to form an oxide film. However, high frequency waves are used to generate plasma, and the positive ions in the plasma are accelerated toward a metal base connected to a negative potential after passing through a grid with a positive potential.
In plasma, positive ions must first pass through a grid of positive potential by diffusion, and a sufficient amount of positive ions necessary for film formation cannot reach the substrate, which is insufficient in terms of improving adhesion. In order to improve these drawbacks, the present inventors proposed in Japanese Patent Application No. 1-214913 to pre-treat the substrate by bombarding it with high-energy Ar ions, etc., but the adhesiveness was still poor. It is enough.
【０００６】これらの方法の欠点を改良して接着性を向
上させるために、中間層を介在させることが特開昭６４
−６２４６８号により提案されている。中間層としては
シリコン、アルミニウム、タングステン、コバルト、ニ
ッケル等の金属層、炭化珪素、炭化タングステン等の金
属炭化物層、窒化珪素、窒化タングステン、窒化チタン
等の金属窒化物層、シリカ、アルミナ、ジルコニア等の
金属酸化物層などが使用されている。[0006] In order to improve the adhesion by improving the drawbacks of these methods, it was proposed in JP-A-64
It is proposed by No.-62468. Intermediate layers include metal layers such as silicon, aluminum, tungsten, cobalt, and nickel, metal carbide layers such as silicon carbide and tungsten carbide, metal nitride layers such as silicon nitride, tungsten nitride, and titanium nitride, silica, alumina, and zirconia. metal oxide layers, etc. are used.
【０００７】[0007]
【発明が解決すべき課題】しかし、これらの中間層は蒸
着、ＣＶＤ法により成膜されるもので工程が複雑となり
ダイヤモンド成膜装置とは別の装置を要する問題があり
、又中間層の特性も充分でない。本発明の目的は、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で保護した物品及びそ
の製造方法を提供することにある。[Problems to be Solved by the Invention] However, these intermediate layers are formed by vapor deposition or CVD, which makes the process complicated and requires equipment separate from the diamond film forming equipment, and the characteristics of the intermediate layer is also not enough. An object of the present invention is to provide an article protected by a diamond-like thin film that has a high bonding force or adhesive force to a substrate, has improved peeling resistance and durability, and a method for manufacturing the same.
【０００８】[0008]
【課題を解決するための手段】本発明は、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近接して、Ｍｏ製のグリッ
ドを配置し、前記グリッドをＡｒ等の不活性ガス原子よ
りなるボンバード用ガスで衝撃してＭｏ原子を放出させ
、これを前記基板上に付着させることにより表面の汚染
を除くと共にＭｏ膜を生成し、ついで低分子量炭化水素
又は分解又は反応により低分子量炭化水素を生成し得る
原料ガスをイオン化させてイオンを生成し、これらのイ
オンを加速して前記Ｍｏ膜上に付着させることによりダ
イヤモンド様膜を形成すること及びこうして得られるダ
イヤモンド様保護膜を有する物品である。[Means for Solving the Problems] The present invention provides Co, Ni,
A grid made of Mo is placed close to the surface of a substrate selected from the group consisting of alloys containing at least one type of Fe, ceramics, and glasses and has poor affinity with diamond-like thin films, and the grid is surrounded by a non-containing material such as Ar. Mo atoms are released by bombardment with a bombardment gas consisting of active gas atoms, and the Mo atoms are deposited on the substrate to remove surface contamination and form a Mo film, followed by low molecular weight hydrocarbons or decomposition or reaction. Forming a diamond-like film by ionizing a raw material gas capable of producing low molecular weight hydrocarbons to produce ions, accelerating these ions and depositing them on the Mo film, and the diamond-like protective film thus obtained. It is an article that has
【０００９】本発明によると、特願平１−２１４９１３
号における基板のＡｒボンバード（衝撃）効果と同時に
、基板のＭｏによる成膜が同時に実施されてＭｏの基板
への強固な接着と、ダイヤモンド様保護膜のＭｏ中間層
への強固な接着が達成出来る。この基板への接着性、密
着性の改善により厳しい条件で評価される耐摩耗性の用
途にも利用できる。又本発明によると、Ｍｏ成膜工程と
ダイヤモンド成膜工程とが同一の装置を使用して前後し
て実施出来るので工程の単純化、コスト低下が実現出来
る。According to the present invention, patent application No. 1-214913
Simultaneously with the Ar bombardment (impact) effect on the substrate, the Mo film deposition on the substrate is carried out at the same time, achieving strong adhesion of Mo to the substrate and strong adhesion of the diamond-like protective film to the Mo intermediate layer. . This improved adhesion and adhesion to substrates can also be used for wear resistance applications that are evaluated under severe conditions. Further, according to the present invention, the Mo film forming process and the diamond film forming process can be performed back and forth using the same apparatus, so that process simplification and cost reduction can be realized.
【００１０】本発明はイオン化蒸着法によるダイヤモン
ド成膜法が、熱電子電離手段と電離された炭化水素イオ
ンを加速するための電界付与グリッドを有することに着
目し、同じ装置でグリッドをＭｏより構成し、これをア
ルゴン（Ａｒ）等をイオン化し加速した高エネルギーボ
ンバードガスで衝撃することにより、初期の目的を達成
出来た。The present invention focuses on the fact that a diamond film forming method using ionization vapor deposition has a thermionic ionization means and an electric field applying grid for accelerating ionized hydrocarbon ions, and the grid is made of Mo using the same device. However, by bombarding this with a high-energy bombardment gas made by ionizing and accelerating argon (Ar), the initial objective was achieved.
【００１１】イオン化蒸着法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−陽極間のアーク放電、陰極熱フ
ィラメント−陽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、特願平１−２１４９１３号に記載
されている通り、イオン化蒸着法は基体温度として従来
のような７００℃以上の高温度を用いる必要がなく（例
えば「表面化学」第５巻第１０８号（１９８４年）第１
０８−１１５頁の各種の方法参照）、成膜効率も良く、
成膜されたダイヤモンド様膜が良好な表面性、高硬度、
高熱伝導性、高屈折率を有し、仕上表面処理が不要であ
る等、優れた方法である。The ionization vapor deposition method uses a hydrocarbon raw material gas or a raw material gas that can produce hydrocarbons by decomposition or reaction (here, hydrocarbons include saturated hydrocarbons such as methane, ethane, and propane, and non-saturated hydrocarbons such as ethylene, propylene, and acetylene). There are saturated hydrocarbons, etc., and the raw material gases that can be decomposed to produce hydrocarbons include alcohols such as methyl alcohol and ethyl alcohol, and ketones such as acetone and methyl ethyl ketone, and they also react to produce hydrocarbon gases. Raw material gases include carbon monoxide, a mixed gas of carbon dioxide and hydrogen, etc. The raw materials also include rare gases such as helium, neon, and argon, or hydrogen, oxygen, nitrogen, water, carbon monoxide, carbon dioxide, etc.)
is ionized by means such as arc discharge between the hot cathode filament and the anode, ionization by thermionic emission between the cathode hot filament and the anode, etc. to form an ion flow, and this flow is accelerated by an electric field and directed toward the substrate, making it diamond-like. As described in Japanese Patent Application No. 1-214913, the ionization vapor deposition method is a method for forming a thin film, and as described in Japanese Patent Application No. 1-214913, it is not necessary to use a high temperature of 700°C or higher as the substrate temperature (for example, "surface chemical ” Volume 5, No. 108 (1984) No. 1
(Refer to various methods on pages 08-115), the film formation efficiency is also good,
The deposited diamond-like film has good surface properties, high hardness,
This is an excellent method as it has high thermal conductivity, high refractive index, and does not require finishing surface treatment.
【００１２】成膜装置
第１図にＭｏ中間層及びダイヤモンド様膜の成膜装置の
好ましい例を示す。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（保護すべき
物品）Ｓの裏面に設けられ負電位Ｖａに保たれた電極で
ある（基体が金属である場合にはそれ自体を電極として
良い）。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
るべくは離して配置する。３３は基体と同一の負電位Ｖ
ａを与えられたＭｏ製の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３
３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は原料である炭化水素ガスの供給口、
及びアルゴン等のボンバードガスの供給口である。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
しては正の電圧となり、電極３２及びグリッド３３に対
しては正の電位を与えられている。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Ｖｃ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、Ｖｄ、Ｖａ、コイルの電流Ｉｃ、イオ
ン電流Ｉａを調整することによりＭｏ中間層とダイヤモ
ンド様保護膜の調整が出来る。Film Forming Apparatus FIG. 1 shows a preferred example of a film forming apparatus for a Mo intermediate layer and a diamond-like film. In the figure, 30 is a vacuum container, 31 is a chamber, which is connected to an exhaust system 38 and has a pressure of 10-6 Torr.
It is drawn to a high vacuum up to a certain degree. Reference numeral 32 denotes an electrode provided on the back surface of the substrate (article to be protected) S and maintained at a negative potential Va (if the substrate is made of metal, it may itself be used as an electrode). A mask 42 having a window close to or in contact with the surface of the substrate S to regulate the shape of the diamond-like thin film is provided. This mask may be in contact with the substrate, but in order to reduce the thickness of the peripheral portion of the film and reduce cracks, it should be placed as far away as possible. 33 is the same negative potential V as the substrate
A Mo grid given a is used to accelerate hydrocarbon ions in the film forming process. This grid 3
3 is the porosity (area of holes per unit area) and hole density (area of holes per unit area) that are properly determined in order to increase the continuity of the membrane and smooth the surface.
(number of holes per unit length), or may have means for vibrating in its plane. A hot cathode filament 34 is maintained at a negative potential Vd, and is heated by a current If from an AC power source to generate thermoelectrons. 35 is a supply port for hydrocarbon gas, which is a raw material;
and a supply port for bombarded gas such as argon. An anode 36 is disposed surrounding the filament 34. This anode is grounded in this case, but has a positive voltage with respect to the filament and a positive potential with respect to the electrode 32 and the grid 33. filament 34,
An electromagnetic coil 39 is disposed surrounding the anode 36 and the supply port 35 and is excited by a current Ic from a power source Vc to generate a magnetic field for confining the ionized gas. Therefore, by adjusting If, Vd, Va, coil current Ic, and ion current Ia, the Mo intermediate layer and the diamond-like protective film can be adjusted.
【００１３】第３図は第１図のＡ−Ａ線から見た平面斜
視図であり、膜の形が長方形の場合には例えば図示のよ
うな複数フィラメントの配列体を用いるとか、コイル状
に巻いたものを用いる。又広い面積の成膜を行なうには
基体を長尺ものとして構成し、それを低速で送るとか、
イオンビームを走査させるとかの方法が可能である。な
お第１図においては、炭化水素ガスの原料導入通路３７
にプラズマ励起室３７’が設けられており、これにより
イオン化装置の効率を高めている。プラズマ励起は例え
ばマイクロ波、高周波（ＲＦ波）、放射線、紫外線など
が利用できる。FIG. 3 is a plan perspective view taken along the line A-A in FIG. Use rolled ones. In addition, in order to form a film over a wide area, the substrate must be made long and fed at low speed.
A method such as scanning an ion beam is possible. In addition, in FIG. 1, the raw material introduction passage 37 for hydrocarbon gas
A plasma excitation chamber 37' is provided in the ionizer, thereby increasing the efficiency of the ionization device. For example, microwaves, radio frequency (RF waves), radiation, ultraviolet rays, etc. can be used for plasma excitation.
【００１４】また、第２図に示したように第１図の構成
の一部を変更して固定又は可変強度の磁石４０をフィラ
メント３４の上部に配置してプラズマ状のイオンビーム
の偏向用に用いても良い。磁石４０の磁界強度は固定又
は可変にし、磁石の磁界はイオン流の走行方向にたいし
て交差する方向にする。このようにしてＣＨ３＋、ＣＨ
４ ＋ イオン等の所望するイオンに対して偏向角度θ
を得る。固定の場合一方、質量がこれらのイオンと大き
く異なるイオン例えば水素イオンはさらに大きく曲げら
れ、また中性粒子や重質の多量体イオンは直進する。従
って、直進方向にマスクを配置すれば結晶性の高いイオ
ンのみが基体Ｓに付着する。In addition, as shown in FIG. 2, a part of the configuration shown in FIG. 1 is changed, and a fixed or variable strength magnet 40 is placed above the filament 34 to deflect a plasma-like ion beam. May be used. The magnetic field strength of the magnet 40 is fixed or variable, and the magnetic field of the magnet is set in a direction perpendicular to the traveling direction of the ion flow. In this way, CH3+, CH
Deflection angle θ for desired ions such as 4 + ions
get. In the fixed case, on the other hand, ions whose mass is significantly different from these ions, such as hydrogen ions, are bent even more, and neutral particles and heavy multimer ions travel straight. Therefore, if the mask is placed in the straight direction, only highly crystalline ions will adhere to the substrate S.
【００１５】Ｍｏの成膜
Ｆｅまたはその合金、ガラス、セラミックス等の難接着
性基体にＭｏ中間層を形成するには、真空室を１０−６
Ｔｏｒｒ程度に排気した後、供給口３５からアルゴン、
窒素、水素、ヘリウム、ネオン、等から選んだボンバー
ドガスを０．１Ｔｏｒｒ程度に導入し、フィラメント３
４により電離し、得られたアルゴンイオンをグリッド３
３により加速する。アルゴンイオンは基体Ｓの表面を衝
撃して清浄化して接着性を改善し、同時にＭｏをグリッ
ドからたたき出して基体に被着させる。各部に印加され
る電圧、或いは電流、ボンバードガスの分子量（混合ガ
スでは平均分子量）、処理時間などが必要な制御因子と
なる。Formation of Mo film In order to form a Mo intermediate layer on a difficult-to-adhesive substrate such as Fe or its alloy, glass, or ceramics, the vacuum chamber is heated to 10-6
After exhausting to about Torr, argon,
A bombardment gas selected from nitrogen, hydrogen, helium, neon, etc. is introduced at approximately 0.1 Torr, and the filament 3
4, and the obtained argon ions are transferred to grid 3.
Accelerate by 3. The argon ions impact and clean the surface of the substrate S to improve adhesion, and at the same time knock out Mo from the grid and deposit it on the substrate. Necessary control factors include the voltage or current applied to each part, the molecular weight of the bombarded gas (average molecular weight in the case of a mixed gas), and the processing time.
【００１６】ボンバード用ガスのエネルギーは、分子量
、ボンバードの処理時間、及びイオン電流Ｉａ とした
とき、分子量×Ｉａ （ｍＡ）×時間（Ｈｒ）で表わさ
れ、５００＜分子量×Ｉａ （ｍＡ）×時間（Ｈｒ）＜
８００を満足することが好ましい。この値が小さ過ぎる
と、Ｍｏグリッドへのボンバードエネルギーが不十分と
なり、Ｍｏ膜の成膜が充分い出来ない。又この値が大き
過ぎると装置の他の構成部分がエッチングされてしまい
、膜中に不純物が混入することによって密着性が低下す
る。The energy of the bombardment gas is expressed as molecular weight × Ia (mA) × time (Hr), where the molecular weight, bombardment processing time, and ion current Ia are expressed as 500<molecular weight × Ia (mA) × Time (Hr)<
It is preferable to satisfy 800. If this value is too small, the bombardment energy to the Mo grid will be insufficient, making it impossible to form a sufficient Mo film. If this value is too large, other constituent parts of the device will be etched, and impurities will be mixed into the film, resulting in a decrease in adhesion.
【００１７】ダイヤモンド様膜の成膜
次工程のダイヤモンド様保護膜の成膜工程では、チャン
バー３１内を１０−６Ｔｏｒｒ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メタンガス、
それと水素との混合ガス、或いはそれとＡｒ、Ｈｅ、Ｎ
ｅ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１０−１Ｔｏ
ｒｒ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から供給されたメタンガス等の炭化水素は熱分
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メタンガ
スは熱分解物質のプラスイオンと成る。Formation of Diamond-like Film In the next process of forming a diamond-like protective film, the inside of the chamber 31 is brought to a high vacuum of 10 −6 Torr, and the valve of the gas supply passage 37 is operated to supply a predetermined flow rate of methane gas,
A mixed gas of it and hydrogen, or it and Ar, He, N
While introducing a carrier gas such as e from each supply port 35, the exhaust system 38 is adjusted to a predetermined gas pressure, e.g. 10-1To.
Let it be rr. On the other hand, an alternating current If is passed through the plurality of hot cathode filaments 34 to heat them, and a potential difference Vd is applied between the filaments 34 and the anode 36 to form a discharge. Hydrocarbons such as methane gas supplied from the supply port 35 are thermally decomposed and collide with thermoelectrons from the filament to generate positive ions and electrons. This electron collides with another pyrolysis particle. By repeating this phenomenon under the confinement effect of the magnetic field of the electromagnetic coil, methane gas becomes positive ions of thermally decomposed substances.
【００１８】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。所望により、上に述べ
た固定磁石を利用して更に品質の良い薄膜を得ることが
できる。形成する膜の厚さは好ましくは１００ 〜１０
００００Åであり、厚さが上記の範囲よりも薄いと耐摩
耗性等の効果が減じ又厚すぎても効果が増大せず製造時
間が長くなる。以下に本発明を例示する。The positive ions are attracted by the negative potential Va applied to the electrode 32 and the grid 36, are accelerated toward the substrate S, collide with the substrate, and perform a film-forming reaction.
Forms a diamond-like thin film. If desired, even better quality thin films can be obtained using the fixed magnets described above. The thickness of the film to be formed is preferably 100 to 10
0,000 Å, and if the thickness is thinner than the above range, effects such as wear resistance will be reduced, and if it is too thick, the effects will not increase and the manufacturing time will increase. The present invention will be illustrated below.
【００１９】実施例及び比較例
第１図の装置を使用し、真空室１０内に基体Ｓとして板
状はがね鋼ＳＫＳ２、ＳＫＤ１１を配置し、その面から
距離約６．０ｍｍのところにＭｏ、Ｗ、及びＳＵＳ３０
３製のグリッド３３を配置した。基体Ｓから陽極までの
距離は約４０ｍｍであった。グリッド３３の穴密度は６
０個／２５．４ｍｍ、空間率は４１％であった。EXAMPLES AND COMPARATIVE EXAMPLES Using the apparatus shown in FIG. 1, plate-shaped steel sheets SKS2 and SKD11 are placed as substrates S in a vacuum chamber 10, and a Mo , W, and SUS30
A grid 33 manufactured by No. 3 was placed. The distance from the substrate S to the anode was about 40 mm. The hole density of grid 33 is 6
0 piece/25.4mm, void ratio was 41%.
【００２０】Ｍｏの成膜・・・真空室１０を１０−６Ｔ
ｏｒｒに排気してからＡｒ、及びＨ２ガスを導入した。
ガス圧を０．１Ｔｏｒｒとして熱陰極フィラメント３４
に放電を起こさせた。電磁コイル１９の磁束密度は４０
０ガウス、基体電圧及びグリッド電圧Ｖａ＝− ３０
０Ｖ、基体温度２００℃とした。またフィラメント３４
には電流Ｉｆ＝２０Ａを流した。更にフィラメント電圧
Ｖｄ＝−１０Ｖとし、Ｉａ可変とした。フィラメント３
４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３３は５ｍｍ／
分の速度で振動させた。[0020] Mo film formation...vacuum chamber 10 at 10-6T
After exhausting to orr, Ar and H2 gas were introduced. Hot cathode filament 34 with gas pressure of 0.1 Torr
caused a discharge to occur. The magnetic flux density of the electromagnetic coil 19 is 40
0 Gauss, base voltage and grid voltage Va=-30
The temperature was 0V and the substrate temperature was 200°C. Also filament 34
A current If=20A was applied to the battery. Further, the filament voltage Vd was set to -10V, and Ia was made variable. filament 3
4 was coiled, had a width of 3 mm, and had a gap of 8 mm between it and the surrounding electrode 36. Grid 33 is 5mm/
vibrated at a speed of 1 minute.
【００２１】ダイヤモンド様保護膜の成膜・・・次ぎに
Ａｒの導入を止め、真空室１０を１０−６Ｔｏｒｒに排
気してからメタンガスを導入しガス圧を１０−１Ｔｏｒ
ｒとして熱陰極フィラメント３４に放電を起こさせた。
電磁コイル１９の磁束密度は４００ガウス、基体電圧Ｖ
ａ＝−３００Ｖ、基体温度２００℃とした。またフィラ
メント１４には電流Ｉｆ＝２５Ａを流した。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３３は５ｍ
ｍ／分の速度で振動させた。フィラメント電圧Ｖｄ＝−
３０Ｖ、Ｖｃ＝３０Ｖの条件で、膜厚１．０μｍのダイ
ヤモンド様膜を得た。Formation of a diamond-like protective film...Next, the introduction of Ar is stopped, the vacuum chamber 10 is evacuated to 10-6 Torr, and then methane gas is introduced and the gas pressure is reduced to 10-1 Torr.
A discharge was caused in the hot cathode filament 34 as r. The magnetic flux density of the electromagnetic coil 19 is 400 Gauss, and the base voltage is V.
a=-300V, and the substrate temperature was 200°C. Further, a current If=25 A was passed through the filament 14. The filament 34 was coiled, had a width of 3 mm, and had a gap of 8 mm between it and the surrounding electrode 36. Grid 33 is 5m
It was vibrated at a speed of m/min. Filament voltage Vd=-
A diamond-like film with a thickness of 1.0 μm was obtained under the conditions of 30V and Vc=30V.
【００２２】得られた膜の顕微鏡観察による密着力とス
クラッチ力を測定した。その結果を表１に示す。ここに
密着力は１ｃｍ角の長さ１０ｃｍの角柱をダイヤモンド
様薄膜を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Ｒｅｓｃａ社製のＣＳＲスクラッチ試
験機で測定した。これらの結果は処理エネルギー（分子
量×Ｉａ（Ａ）×時間（Ｈｒ）を１００に設定したとき
を基準１．０にして対比した。比較のためグリッドにＷ
及び鋼鉄ＳＵＳ３０３の結果を併記する。The adhesion force and scratch force of the obtained film were measured by microscopic observation. The results are shown in Table 1. The adhesion strength was measured by adhering a diamond-like thin film to a 1 cm square prism with a length of 10 cm using epoxy resin, and then peeling it off by pulling it with a tensile tester (Tensilon, trade name). The scratch force was measured using a CSR scratch tester manufactured by Resca. These results were compared using the processing energy (molecular weight x Ia (A) x time (Hr) set to 100 as the standard 1.0. For comparison, W
The results for steel SUS303 are also listed.
【００２３】[0023]
【表１】
表１から分かるように、Ａｒイオンの分子量×Ｉａ
×時間は約６００前後で良好な密着力及びスクラッチ力
を生じることが分る。より広くはこの値は５００より大
きく８００よりも小さく、更に広くは５０より大きく１
０００より小さい。一方Ｗは通常のグリッド材であるＳ
ＵＳ３０３よりも良好な結果を与えるがＭｏを使用する
場合よりも劣る。[Table 1] As can be seen from Table 1, molecular weight of Ar ion x Ia
It can be seen that good adhesion and scratching force are produced when the x time is around 600 hours. More broadly, this value is greater than 500 and less than 800; even more broadly, this value is greater than 50 and less than 1.
Less than 000. On the other hand, W is a normal grid material S
Gives better results than US303 but worse than when using Mo.
【発明の作用効果】本発明は保護すべき基体にイオン化
蒸着法によりダイヤモンド成膜を行なう装置において、
電離された炭化水素イオンを加速するための電界付与グ
リッドをＭｏより構成し、これをアルゴン（Ａｒ）等を
イオン化し加速した高エネルギーボンバードガスで衝撃
することにより、基体上にＭｏを成膜し、その上にダイ
ヤモンド様薄膜を形成することにより基体との結合性の
高いダイヤモンド様保護膜薄膜を有する物品を製造する
ことが出来た。さらに本発明によると、基体が金属であ
る必要はなくガラス、セラミックスのような電気絶縁性
の基体に対しても支障なく成膜を実施することが実施出
来る。[Operations and Effects of the Invention] The present invention provides an apparatus for forming a diamond film on a substrate to be protected by an ionization vapor deposition method.
An electric field applying grid for accelerating ionized hydrocarbon ions is made of Mo, and by bombarding it with a high-energy bombarded gas made by ionizing and accelerating argon (Ar), etc., a Mo film is formed on the substrate. By forming a diamond-like thin film thereon, it was possible to produce an article having a diamond-like protective film thin film with high bonding properties to the substrate. Further, according to the present invention, the substrate does not need to be metal, and film formation can be carried out without any problem even on electrically insulating substrates such as glass and ceramics.
【図１】 本発明のＭｏ−ダイヤモンド様保護膜の成
膜装置の一例を示す断面図である。FIG. 1 is a sectional view showing an example of a film forming apparatus for a Mo-diamond-like protective film of the present invention.
【図２】 本発明のＭｏ−ダイヤモンド様保護膜の製
造装置の他の例を示す断面図である。FIG. 2 is a sectional view showing another example of the Mo-diamond-like protective film manufacturing apparatus of the present invention.
【図３】 本発明のＭｏ−ダイヤモンド様保護膜の製
造装置のフィラメント部分の構造を示す平面斜視図であ
る。FIG. 3 is a plan perspective view showing the structure of the filament portion of the Mo-diamond-like protective film manufacturing apparatus of the present invention.
３０：真空容器、３１：チャンバー、３２：電極、３３
：グリッド、３４：熱陰極フィラメント、３５：原料炭
化水素及びアルゴンガス供給口、３６：陽極、３７：炭
化水素ガスの導入通路３７、３７’：プラズマ励起室、
３８：排気系、３９：電磁コイル３９、４０：磁石、４
２：マスク、Ｓ：基体、30: Vacuum container, 31: Chamber, 32: Electrode, 33
: grid, 34: hot cathode filament, 35: raw material hydrocarbon and argon gas supply port, 36: anode, 37: hydrocarbon gas introduction passage 37, 37': plasma excitation chamber,
38: Exhaust system, 39: Electromagnetic coil 39, 40: Magnet, 4
2: Mask, S: Substrate,
Claims (4)
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、Ｍｏの膜と、ダイヤモンド様薄膜とを順に形成し
た、ダイヤモンド様保護膜を有する物品。1. A Mo film and a diamond-like thin film are placed on the surface of a substrate selected from the group consisting of alloys containing at least one of Co, Ni, and Fe, ceramics, and glasses, and which has poor affinity with diamond-like thin films. An article having a diamond-like protective film formed in this order.
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
面に近接して、Ｍｏ製のグリッドを配置し、前記グリッ
ドをＡｒ等の不活性ガス原子よりなるボンバード用ガス
で衝撃して表面の汚染を除くと共にＭｏ原子を前記基板
上に付着させることによりＭｏ膜を生成し、ついで低分
子量炭化水素又は分解又は反応により低分子量炭化水素
を生成し得る原料ガスをイオン化させてイオンを生成し
、これらのイオンを加速して前記Ｍｏ膜上に付着させる
ことによりダイヤモンド様膜を形成することを特徴とす
る、ダイヤモンド様保護膜を有する物品の製造方法。2. A grid made of Mo is placed close to the surface of a substrate selected from the group consisting of alloys containing at least one of Co, Ni, and Fe, ceramics, and glasses, and which has poor affinity with diamond-like thin films. Then, the grid is bombarded with a bombardment gas consisting of inert gas atoms such as Ar to remove surface contamination and deposit Mo atoms onto the substrate to form a Mo film, and then bombarded with low molecular weight hydrocarbon or A diamond-like film is formed by ionizing a raw material gas capable of producing low molecular weight hydrocarbons through decomposition or reaction to produce ions, accelerating these ions, and depositing them on the Mo film. , a method of manufacturing an article having a diamond-like protective film.
Ａｒ等の不活性ガスを前記真空室内に導入し、これを熱
陰極フィラメントとその周りに設けられた陽極とよりな
るイオン化手段により電離してイオンの流れを形成し、
これを前記陽極よりも低電位にあるＭｏグリッドに衝突
させて基体の表面をＭｏ膜で被覆し、ついで、（ｂ）真
空室内に低分子量炭化水素、又は分解又は反応により低
分子量炭化水素を生成し得る原料ガスを導入し、前記イ
オン化手段により電離して炭化水素イオンの流れを形成
し、これを前記Ｍｏグリッドにより加速して基体上で成
膜反応させることを特徴とする、請求項２に記載のダイ
ヤモンド様保護膜を有する物品の製造方法。(a) placing the substrate in a vacuum chamber;
Introducing an inert gas such as Ar into the vacuum chamber, ionizing it by an ionization means consisting of a hot cathode filament and an anode provided around it to form a flow of ions,
This is made to collide with a Mo grid at a lower potential than the anode to coat the surface of the substrate with a Mo film, and then (b) generate low molecular weight hydrocarbons in the vacuum chamber or low molecular weight hydrocarbons by decomposition or reaction. 3. The method of claim 2, characterized in that a raw material gas that can be used is introduced and ionized by the ionization means to form a flow of hydrocarbon ions, which is accelerated by the Mo grid to cause a film forming reaction on the substrate. A method of manufacturing an article having a diamond-like protective film as described.
ガスの分子量、ボンバード処理時間、及びイオン電流Ｉ
ａ が条件式 ５００＜分子量×Ｉａ （ｍＡ）×時間（Ｈｒ）＜８０
０を満足することを特徴とする請求項３に記載のダイヤ
モンド様保護膜を有する物品の製造方法。4. In the step (a), the molecular weight of the bombardment gas, the bombardment treatment time, and the ion current I
a is the conditional expression 500<molecular weight×Ia (mA)×time (Hr)<80
4. The method for manufacturing an article having a diamond-like protective film according to claim 3, wherein the diamond-like protective film satisfies 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3142678A JP3056827B2 (en) | 1991-05-20 | 1991-05-20 | Article having a diamond-like carbon protective film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3142678A JP3056827B2 (en) | 1991-05-20 | 1991-05-20 | Article having a diamond-like carbon protective film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04341558A true JPH04341558A (en) | 1992-11-27 |
| JP3056827B2 JP3056827B2 (en) | 2000-06-26 |
Family
ID=15320973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3142678A Expired - Fee Related JP3056827B2 (en) | 1991-05-20 | 1991-05-20 | Article having a diamond-like carbon protective film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3056827B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841140A3 (en) * | 1996-11-12 | 2000-02-23 | Bae Hyeock Chun | Method of enhancing releasing effect of mould using low temperature plasma processes |
| JP2010202978A (en) * | 2000-02-25 | 2010-09-16 | Sumitomo Electric Ind Ltd | Amorphous carbon covered member |
| CN114059036A (en) * | 2021-11-23 | 2022-02-18 | 南京大学 | Application of iron film in auxiliary stripping of diamond polycrystalline film |
| WO2024048261A1 (en) * | 2022-08-29 | 2024-03-07 | 株式会社神戸製鋼所 | Ion bombardment device and ion bombardment processing method |
-
1991
- 1991-05-20 JP JP3142678A patent/JP3056827B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841140A3 (en) * | 1996-11-12 | 2000-02-23 | Bae Hyeock Chun | Method of enhancing releasing effect of mould using low temperature plasma processes |
| JP2010202978A (en) * | 2000-02-25 | 2010-09-16 | Sumitomo Electric Ind Ltd | Amorphous carbon covered member |
| CN114059036A (en) * | 2021-11-23 | 2022-02-18 | 南京大学 | Application of iron film in auxiliary stripping of diamond polycrystalline film |
| WO2024048261A1 (en) * | 2022-08-29 | 2024-03-07 | 株式会社神戸製鋼所 | Ion bombardment device and ion bombardment processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3056827B2 (en) | 2000-06-26 |
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