JPH03291378A - Method for coating with hard carbon film - Google Patents
Method for coating with hard carbon filmInfo
- Publication number
- JPH03291378A JPH03291378A JP9027790A JP9027790A JPH03291378A JP H03291378 A JPH03291378 A JP H03291378A JP 9027790 A JP9027790 A JP 9027790A JP 9027790 A JP9027790 A JP 9027790A JP H03291378 A JPH03291378 A JP H03291378A
- Authority
- JP
- Japan
- Prior art keywords
- intermediate layer
- film
- hard carbon
- carbon
- 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
- 239000011248 coating agent Substances 0.000 title claims abstract description 7
- 238000000576 coating method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 11
- 229910021385 hard carbon Inorganic materials 0.000 title abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract 4
- 229910052799 carbon Inorganic materials 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 55
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000007733 ion plating Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 70
- 239000000463 material Substances 0.000 description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 150000001485 argon Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010849 ion bombardment Methods 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、工具、あるいは装飾品の表面にコーティング
するカーボン硬質膜と基材との間に設ける密着性を向上
するための中間層を含めたカーボン硬質膜の被覆方法に
関する。Detailed Description of the Invention [Field of Industrial Application] The present invention includes an intermediate layer for improving adhesion between a hard carbon film coated on the surface of a tool or decorative article and a base material. The present invention relates to a method of coating a carbon hard film.
カーボン硬質膜とは、１９７０年代後半からイギリスを
中心に研究されはじめた俗称ｉカーボンと呼ばれる超硬
質炭素膜のことであり、物性上ダイヤモンドと類似点が
多い。またカーボン硬質膜は、黒色を呈し、高硬度、低
摩擦係数、電気絶縁性、高熱伝導率、耐腐食性等の多く
の優れた特徴をもつ膜であることから、工具、装飾品、
あるいは電子部品などの表面コーティング分野で応用が
期待されている。しかし、カーボン硬質膜単層では、密
着よくコーティングできる基材は特殊な材質に限られる
。そこで通常のステンレス、工具鋼、超硬、その他の材
料の工具、装飾品にカーボン硬質膜を密着よく形成させ
るには、カーボン硬質膜と基材の間忙中間層を介在させ
る必要がある。The carbon hard film is an ultra-hard carbon film commonly called i-carbon, which began to be researched mainly in the UK in the late 1970s, and has many similarities with diamond in terms of physical properties. In addition, carbon hard films are black in color and have many excellent characteristics such as high hardness, low coefficient of friction, electrical insulation, high thermal conductivity, and corrosion resistance, so they are used in tools, decorations, etc.
It is also expected to be applied in the field of surface coating for electronic parts and other areas. However, with a single layer of carbon hard film, the substrates that can be coated with good adhesion are limited to special materials. Therefore, in order to form a carbon hard film with good adhesion on tools and accessories made of ordinary stainless steel, tool steel, carbide, and other materials, it is necessary to interpose a busy intermediate layer between the carbon hard film and the base material.
この中間層として、従来、多くの材料が提案されている
。例えば、清浄なステンレス基材に、蒸着法、イオンブ
レーティング法、スパッタリング法等によってチタニウ
ムの炭化物、窒化物、あるいは界化物、窒化物の固溶体
を中間層として形成し、その後カーボン硬質膜を形成す
る手法が提案されている。しかしながらこの構造では、
炭化チタニウム膜とステンレス基材の間の密着性は、良
好であるが、カーボン硬質膜と炭化チタニウム膜の間の
密着が悪い。そのため、工具、装飾品、あるいは電子部
品に使用するには、信頼性に欠ける。Conventionally, many materials have been proposed for this intermediate layer. For example, a solid solution of titanium carbide, nitride, or interlayer or nitride is formed as an intermediate layer on a clean stainless steel base material by vapor deposition, ion blasting, sputtering, etc., and then a hard carbon film is formed. A method has been proposed. However, with this structure,
The adhesion between the titanium carbide film and the stainless steel base material is good, but the adhesion between the hard carbon film and the titanium carbide film is poor. Therefore, it is unreliable for use in tools, ornaments, or electronic parts.
カーボン硬質膜を構成する炭素原子は、周期律表の第１
ｖｂ族の原子であるため、共有結合でしか結合できない
。従りてカーボン硬質膜が密着よく被覆できる中間層は
、炭素と共有結合できる材料からなる中間層に限られる
。炭化チタニウム膜の場合は、カーボン硬質膜の炭素と
炭化チタニウム膜の炭素が共有結合できると、密着性は
高い。しかし、通常の方法で炭化チタニウム膜を形成す
ると、その表面にはどうしても自然酸化による酸化チタ
ニウムの薄い層が存在してしまう。この酸化チタニウム
の薄い層が存在することによって、カーボン硬質膜と炭
化チタニウム膜間の炭素は共有結合できなくなってしま
い、密着性が悪くなる。The carbon atoms that make up the carbon hard film are the first in the periodic table.
Since it is a Vb group atom, it can only be bonded with covalent bonds. Therefore, the intermediate layer that can be tightly coated with the carbon hard film is limited to an intermediate layer made of a material that can covalently bond with carbon. In the case of a titanium carbide film, if the carbon of the hard carbon film and the carbon of the titanium carbide film can covalently bond, the adhesion is high. However, when a titanium carbide film is formed using a conventional method, a thin layer of titanium oxide due to natural oxidation inevitably exists on its surface. The presence of this thin layer of titanium oxide prevents carbon from covalently bonding between the hard carbon film and the titanium carbide film, resulting in poor adhesion.
結局、カーボン硬質膜と炭化チタニウム膜の間の密着は
、界面の酸化チタニウムの存在で大きく変化し、安定性
、信頼性に著しく欠ける欠点がある。As a result, the adhesion between the carbon hard film and the titanium carbide film changes greatly due to the presence of titanium oxide at the interface, resulting in a drawback of significantly lacking stability and reliability.
上記課題を解決して、中間層にカーボン硬質膜を密着よ
く形成する方法を提供することが、本発明の目的である
。It is an object of the present invention to solve the above problems and provide a method for forming a hard carbon film on an intermediate layer with good adhesion.
上記目的を達成するため本発明のカーボン硬質膜被覆方
法は、基材上に周期律表の■２族の金属すなわちチタン
、ジルコニウムあるいはハフニウムの炭化物からなる中
間層を形成した後、同一装置内で引き続き第１のカーボ
ン層を形成する工程と、次に第１のカーボン層より高い
圧力条件で第２のカーボン層を形成する工程を有する。In order to achieve the above object, the carbon hard film coating method of the present invention forms an intermediate layer made of a carbide of a metal of group 2 of the periodic table, that is, titanium, zirconium, or hafnium, on a substrate, and then coats it in the same apparatus. The method includes a subsequent step of forming a first carbon layer, and then a step of forming a second carbon layer under higher pressure conditions than the first carbon layer.
ステンレスに代表されるような一般的な基材を、電解脱
脂、及びアセトン、トリエタン等による有機洗浄を行い
、まず基材の表面の油脂分を除去する。その基材を反応
性イオンブレーティングｉｔにセットする。この装置は
通常の油拡散ポンプで排気を行い、蒸発材料を電子ビー
ムで加熱する。A common base material such as stainless steel is subjected to electrolytic degreasing and organic cleaning using acetone, triethane, etc. to first remove oil and fat from the surface of the base material. The substrate is placed in a reactive ion blating it. The device uses a conventional oil diffusion pump to evacuate and heat the evaporated material with an electron beam.
この時、反応ガスを、ガス導入口から導入し、プラズマ
を発生させる。そしてアノードリングには正電圧を印加
し、蒸発材料からの熱電子を集束させ、アノードリング
近傍のプラズマ密度を高めて反応を促進させる。At this time, a reaction gas is introduced from the gas inlet to generate plasma. Then, a positive voltage is applied to the anode ring to focus the thermal electrons from the evaporated material, increase the plasma density near the anode ring, and promote the reaction.
また基材には、高周波電源から高周波バイアス（１３，
５６Ｍ Ｈｚ）を印加することができるため、この装置
は、反応性イオンプレーティ−ング装置だけでなく、プ
ラズマ化学気相成長法の装置としても使用することがで
きる。例えば、蒸発材料の蒸発を止めて、反応ガスを、
ガス導入口から導入して適当な圧力に調整した後、基材
に高周波バイアスを印加すると、プラズマ化学気相成長
法として機能する。この手法を用いると、後で述べるよ
うに、中間層、第１のカーボン層、第２のカーボン層を
同一の装置内で連続して形成できる。In addition, the base material is supplied with a high frequency bias (13,
56 MHz), this device can be used not only as a reactive ion plating device but also as a plasma chemical vapor deposition device. For example, by stopping the evaporation of the evaporation material and releasing the reaction gas,
After introducing the gas through the gas inlet and adjusting the pressure to an appropriate level, applying a high frequency bias to the base material functions as a plasma chemical vapor deposition method. By using this method, the intermediate layer, the first carbon layer, and the second carbon layer can be successively formed in the same apparatus, as will be described later.
はじめに中間層を形成する前処理として、装置内にアル
ゴンガスを導入し、アルゴンイオンボンバードによって
、基材の表面クリーニングと表面活性化を行う。このア
ルゴンボンバードの条件を以下に示す。First, as a pretreatment for forming the intermediate layer, argon gas is introduced into the apparatus, and the surface of the substrate is cleaned and surface activated by argon ion bombardment. The conditions for this argon bombardment are shown below.
到達圧力 ３ Ｘ １０−５ｔｏｒｒ 以下Ａ
ｒ流量 ５０−１００ ｓｃｃｍボンバード圧力
２ Ｘ １０”３ｔｏｒｒアノード電圧 ４０Ｖ
高周波バイアス ５０〜１００Ｗ
以上のようにウェット、ドライ両方式で表面を前処理し
た基材に、中間層として、炭化チタニウムを膜厚５０〜
１１０００ｎ形成する。蒸発材料として、チタニウムを
、反応ガスとして、エチレンを用いる。この時、基材と
中間層の界面の密着を更に向上させるため、中間層の形
成初期に、エチレンガスを導入せず、チタニウム膜を形
成してもよい。チタニウム膜の膜厚は５〜１００ ｎｍ
程度である。Ultimate pressure: 3 x 10-5 torr or less A
r Flow rate: 50-100 sccm Bombardment pressure: 2 x 10" 3 torrr Anode voltage: 40 V High-frequency bias: 50-100 W Titanium carbide is coated as an intermediate layer with a thickness of 50 mm on the base material whose surface has been pretreated using both wet and dry methods as described above. ~
Form 11000n. Titanium is used as the evaporation material and ethylene is used as the reaction gas. At this time, in order to further improve the adhesion between the interface between the base material and the intermediate layer, a titanium film may be formed without introducing ethylene gas at the initial stage of forming the intermediate layer. The thickness of the titanium film is 5 to 100 nm.
That's about it.
中間層、すなわち炭化チタニウム膜の形成条件を以下に
示す。The conditions for forming the intermediate layer, ie, the titanium carbide film, are shown below.
到達圧力 ３ Ｘ １０−’ ｔｏｒｒ以下エチレ
ン流量 ５０−１００ ｓｃｃｍ反応圧力 ３Ｘ１
０ｔｏｒｒ
アノード電圧 ４０Ｖ
この中間層の材料は、周期律表の■ａ族の炭化物であれ
ばよく、反応ガスは、エチレンの他に、メタン、アセチ
レン等の炭素原子を含むガスが使用できる。Ultimate pressure: 3 x 10-' torr or less Ethylene flow rate: 50-100 sccm Reaction pressure: 3 x 1
0 torr Anode voltage 40 V The material of this intermediate layer may be a carbide of group Ⅰa of the periodic table, and the reaction gas may be a gas containing carbon atoms such as methane or acetylene in addition to ethylene.
この後連続して中間層の上に、真空を破らず反応ガスを
入れ換えずに、中間層を形成したエチレン雰囲気のまま
で、第１のカーボン層をプラズマ化学気相成長法により
、膜厚５０〜５００ｎｍ形成する。第１のカーボン層の
形成条件を以下に示す。After that, a first carbon layer was continuously deposited on the intermediate layer to a thickness of 50 mm by plasma chemical vapor deposition, without breaking the vacuum or replacing the reaction gas, and in the ethylene atmosphere in which the intermediate layer was formed. ~500 nm is formed. The conditions for forming the first carbon layer are shown below.
エチレン流量 ５０〜１１００５ＣＣ
反応圧力 ３ Ｘ １０−３ｔｏｒｒ高周波バイア
ス ２００Ｗ
最後に、第１のカーボン層の上に、第２のカーボン層を
反応ガスとしてエチレンを用い、プラズマ化学気相成長
法により膜厚１０００〜３０００ｎｍ形成する。この時
の反応圧力は、第１のカーボン層より２桁はど高い状態
である。Ethylene flow rate: 50 to 11,005 cc Reaction pressure: 3 x 10-3 torr High frequency bias: 200 W Finally, a second carbon layer is formed on the first carbon layer using ethylene as a reaction gas, and a film thickness of 1,000 cc is formed by plasma chemical vapor deposition. ~3000 nm is formed. The reaction pressure at this time is two orders of magnitude higher than that of the first carbon layer.
第２のカーボン層の形成条件を以下に示す。The conditions for forming the second carbon layer are shown below.
到達圧力 ３ Ｘ １ ｏ−１ｔｏｒｒ 以下
エチレン流量 ２００〜３００ｓｅｃｍ反応圧力
ｌＸ１０ｔｏｒｒ
ｒｆ電力 ２００Ｗ
この時の反応ガスは、エチレンの他に、メタン、アセチ
レン等の炭素原子を含むガスが使用できる。Ultimate pressure: 3 x 1 o-1 torr or less Ethylene flow rate: 200 to 300 seconds Reaction pressure
1×10 torr RF power 200 W As the reaction gas at this time, in addition to ethylene, gases containing carbon atoms such as methane and acetylene can be used.
上記の条件で形成される第１のカーボン層は、第２のカ
ーボン層と同じ組成であり、構造も同じアモルファスで
あるが、第２のカーボン層と異なり、中間層の上に非常
に密着よく形成することができる。The first carbon layer formed under the above conditions has the same composition and amorphous structure as the second carbon layer, but unlike the second carbon layer, it adheres very well to the intermediate layer. can be formed.
これは、上記の第１のカーボン層の形成条件では、第２
のカーボン層形成時に比ベエチレンの反応圧力が約２桁
低いために、プラズマ中のエチレン分子の衝突回数が極
端に少なく、衝突による分子のエネルギーの損失がない
。したがって中間層の表面に到達するエチレン分子は、
第２のカーボン層の形成時に比べ非常に高いエネルギー
を持っており、中間層との反応性が高い。また、第１の
カーボン層を形成するのは中間層を形成した直後である
から、中間層は非常に活性で反応性が高い表面状態を維
持している。さらに、同一装置内で連続的に形成するた
め、中間層の表面に、第１のカーボン層との反応を阻害
する酸化膜もできない。This is because under the above-mentioned conditions for forming the first carbon layer, the second carbon layer
Since the reaction pressure of ethylene is about two orders of magnitude lower when forming the carbon layer, the number of collisions of ethylene molecules in the plasma is extremely small, and there is no loss of molecular energy due to collisions. Therefore, the ethylene molecules that reach the surface of the intermediate layer are
It has much higher energy than when forming the second carbon layer, and has high reactivity with the intermediate layer. Furthermore, since the first carbon layer is formed immediately after forming the intermediate layer, the intermediate layer maintains a highly active and highly reactive surface state. Furthermore, since the intermediate layer is formed continuously in the same apparatus, an oxide film that inhibits reaction with the first carbon layer is not formed on the surface of the intermediate layer.
このように非常に高いエネルギーのエチレン分子を、活
性な中間層の表面で反応させることが、第１のカーボン
層の形成方法の特徴であり、このために中間層と良好な
密着をとることができる。A feature of the first carbon layer formation method is that ethylene molecules with very high energy are reacted on the surface of the active intermediate layer, and for this reason, it is possible to form good adhesion with the intermediate layer. can.
第２のカーボン層は、第１のカーボン層を形成する装置
で、真空を破らず連続的に上記条件で形成してもよいし
、別装置で形成してもよい。どちらであっても、第１の
カーボン層と第２のカーボン層は、同じ炭素原子からな
っており、また第１のカーボン層の表面には酸化膜がで
きないため。The second carbon layer may be formed continuously under the above conditions without breaking the vacuum in the apparatus that forms the first carbon layer, or may be formed using a separate apparatus. In either case, the first carbon layer and the second carbon layer are made of the same carbon atoms, and no oxide film is formed on the surface of the first carbon layer.
安定した共有結合状態をとることができて、密着性は非
常に良好である。A stable covalent bond state can be formed and the adhesion is very good.
以上述べたように、本発明の第１のカーボン層を形成す
る工程を設けることで、さきに述べた従来例に比べ 第
２のカーボン層の密着性を大幅に改善することができる
。As described above, by providing the step of forming the first carbon layer of the present invention, the adhesion of the second carbon layer can be significantly improved compared to the conventional example described above.
第１のカーボン層は、中間層の表面が活性な状態のまま
、真空を破ることなく、なおかつ第２のカーボン層より
高いエネルギーで形成するために、中間層と反応性が高
い。このことにより、第１のカーボン層は、第２のカー
ボン層と組成、構造が同じであるにもかかわらず、中間
層と非常に強固に密着する。さらに第１のカーボン層は
酸化物を作りやすい金属原子を一切含まないため、第２
のカーボン層との共有結合を阻害する表面の酸化膜もで
きない。すなわち、第１のカーボン層を形成する工程を
設けることで、基材表面を酸化膜が全くなく第２のカー
ボン層と強い共有結合できる層で被覆することができる
。そのため、第２のカーボン層は非常に安定な共有結合
状態を信頼性よく得ることができ、安定した密着性力１
得られる。The first carbon layer has high reactivity with the intermediate layer because it is formed with a higher energy than the second carbon layer without breaking the vacuum while keeping the surface of the intermediate layer active. As a result, the first carbon layer adheres very firmly to the intermediate layer even though it has the same composition and structure as the second carbon layer. Furthermore, since the first carbon layer does not contain any metal atoms that are likely to form oxides, the second carbon layer
There is also no oxide film on the surface that inhibits covalent bonding with the carbon layer. That is, by providing the step of forming the first carbon layer, the surface of the base material can be coated with a layer that has no oxide film and can form a strong covalent bond with the second carbon layer. Therefore, the second carbon layer can reliably obtain a very stable covalent bond state, and has a stable adhesion force of 1.
can get.
Claims (1)
手段と、基板に高周波電圧を印加する手段をそなえた真
空成膜装置を用いて、蒸発源からチタン、ジルコニウム
およびハフニウムの中から選ばれる少なくとも一種の金
属を蒸発させ、炭化水素ガスを含む雰囲気ガスと反応さ
せて前記金属の炭化物からなる膜を中間層として基板表
面に被覆する工程と、前記工程に引き続いて同一装置内
で前記金属の蒸発を停止し、雰囲気ガスの中の炭化水素
分圧を１〜３×１０＾−＾３ｔｏｒｒに設定し、基板に
高周波電圧を印加して高周波励起プラズマＣＶＤ法によ
り前記中間層の上に第１のカーボン硬質膜を被覆する工
程と、炭化水素ガス分圧を０．５〜１．５×１０＾−＾
１ｔｏｒｒに設定し、高周波励起プラズマＣＶＤ法によ
り前記第１のカーボン硬質膜の上に第２のカーボン硬質
膜を被覆する工程とを有することを特徴とするカーボン
硬質膜の被覆方法。At least one type selected from titanium, zirconium, and hafnium is removed from the evaporation source using a vacuum film forming apparatus equipped with means for ionizing the evaporated metal and atmospheric gas from the evaporation source and means for applying a high frequency voltage to the substrate. A step of evaporating the metal and reacting with an atmospheric gas containing hydrocarbon gas to coat the substrate surface with a film made of carbide of the metal as an intermediate layer, and following the step, stopping the evaporation of the metal in the same apparatus. Then, the hydrocarbon partial pressure in the atmospheric gas is set to 1 to 3 x 10^-^3 torr, a high frequency voltage is applied to the substrate, and a first carbon hard layer is deposited on the intermediate layer by high frequency excited plasma CVD. The process of coating the membrane and the partial pressure of hydrocarbon gas from 0.5 to 1.5 x 10^-^
1 Torr, and coating the first carbon hard film with a second carbon hard film by high-frequency excited plasma CVD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9027790A JP2898338B2 (en) | 1990-04-06 | 1990-04-06 | Coating method of carbon hard film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9027790A JP2898338B2 (en) | 1990-04-06 | 1990-04-06 | Coating method of carbon hard film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03291378A true JPH03291378A (en) | 1991-12-20 |
| JP2898338B2 JP2898338B2 (en) | 1999-05-31 |
Family
ID=13994024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9027790A Expired - Fee Related JP2898338B2 (en) | 1990-04-06 | 1990-04-06 | Coating method of carbon hard film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2898338B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022168648A1 (en) * | 2021-02-05 | 2022-08-11 | 東京エレクトロン株式会社 | Substrate processing method and substrate processing device |
-
1990
- 1990-04-06 JP JP9027790A patent/JP2898338B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022168648A1 (en) * | 2021-02-05 | 2022-08-11 | 東京エレクトロン株式会社 | Substrate processing method and substrate processing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2898338B2 (en) | 1999-05-31 |
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