JP2002088465A - Method for depositng hard carbon film on metal base material - Google Patents
Method for depositng hard carbon film on metal base materialInfo
- Publication number
- JP2002088465A JP2002088465A JP2000275444A JP2000275444A JP2002088465A JP 2002088465 A JP2002088465 A JP 2002088465A JP 2000275444 A JP2000275444 A JP 2000275444A JP 2000275444 A JP2000275444 A JP 2000275444A JP 2002088465 A JP2002088465 A JP 2002088465A
- Authority
- JP
- Japan
- Prior art keywords
- film
- intermediate layer
- forming
- hard carbon
- metal
- 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.)
- Pending
Links
Landscapes
- Sliding-Contact Bearings (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属基材上にダイ
アモンドライクカーボン（ＤＬＣ）と呼ばれる硬質炭素
膜を成膜するための方法に関する。特に、磁気ディスク
記録装置、光ディスク記録装置に用いられるスピンドル
モータの動圧軸受けの摺動部品における耐摩耗性を向上
させるための、炭素硬質膜の成膜技術に関する。The present invention relates to a method for forming a hard carbon film called diamond-like carbon (DLC) on a metal substrate. In particular, the present invention relates to a technique for forming a hard carbon film for improving wear resistance of sliding parts of a dynamic pressure bearing of a spindle motor used in a magnetic disk recording device and an optical disk recording device.
【０００２】[0002]
【従来の技術】硬質炭素膜（ＤＬＣ）は非常に硬度が高
いため、摩耗に強く、また、自己潤滑性に富み、表面粗
さも非常に小さくため、摩擦係数が非常に少ない。さら
に、物質的に安定であり、化学的な耐久性も高い。その
ため、磁気ディスク記録装置の記録面および記録ヘッド
表面やスピンドルモータの軸受け摺動部においる保護膜
として有望視されている。2. Description of the Related Art A hard carbon film (DLC) has a very high hardness, is resistant to abrasion, has a high self-lubricating property, has a very small surface roughness, and has a very small coefficient of friction. Furthermore, it is physically stable and has high chemical durability. For this reason, it is expected to be used as a protective film on the recording surface and recording head surface of a magnetic disk recording device and on a bearing sliding portion of a spindle motor.
【０００３】例えば、特開平11-125243号公報では、ECR
プラズマＣＶＤ装置を用いて、動圧軸受の回転軸および
軸受に硬質炭素膜を成膜している。その中で、硬質炭素
膜は、高硬度で耐摩耗性が高く、潤滑性が高いために、
モータの起動時の負荷を低減できることが記載されてい
る。しかし、硬質炭素膜は金属基材に対して基本的に密
着性が悪く、剥離等の問題を抱えている。特に、動圧軸
受の基材には、加工性の面から、アルミニウム、真鍮、
ステンレス等が用いられており、これらの金属は、硬質
炭素膜との密着性が良好でないものが多い。For example, Japanese Patent Application Laid-Open No. 11-125243 discloses an ECR
A hard carbon film is formed on a rotating shaft and a bearing of a dynamic pressure bearing using a plasma CVD apparatus. Among them, the hard carbon film has high hardness, high wear resistance, and high lubricity,
It describes that the load at the time of starting the motor can be reduced. However, the hard carbon film basically has poor adhesion to a metal substrate, and has problems such as peeling. In particular, for the base material of the dynamic pressure bearing, aluminum, brass,
Stainless steel or the like is used, and these metals often have poor adhesion to a hard carbon film.
【０００４】また、硬質炭素膜の密着性を改善する例と
して、特開平10-203896号公報では、基材と硬質炭素膜
の間に2層以上の中間層を成膜する方法、中間層と硬質
炭素膜の間に中間層の金属と硬質炭素膜の炭素の比率が
段階的に変化する層を成膜する方法、さらに、基材と中
間層の境界面を無くするイオン注入やイオンミキシング
法等が用いられている。As an example of improving the adhesion of a hard carbon film, Japanese Patent Application Laid-Open No. 10-203896 discloses a method of forming two or more intermediate layers between a substrate and a hard carbon film. A method of forming a layer in which the ratio of the metal of the intermediate layer and the carbon of the hard carbon film changes stepwise between the hard carbon films, and an ion implantation or ion mixing method for eliminating the interface between the base material and the intermediate layer Etc. are used.
【０００５】[0005]
【発明が解決しようとする課題】硬質炭素膜膜は、基本
的にアルミニウム、真鍮、ステンレス等に直接成膜する
と密着性が良好でなく、中間層を成膜することで密着性
を改善している。しかし、中間層が１層の場合は密着性
が十分ではなく、２層以上の中間層を用いる場合や，イ
オン注入や，イオンミキシング法等は、磁気ディスク記
録装置や光ディスク装置等の動圧軸受け等においては、
コストの面から用いることは難しい。When a hard carbon film is formed directly on aluminum, brass, stainless steel or the like, the adhesion is not good, and the adhesion is improved by forming an intermediate layer. I have. However, when the number of intermediate layers is one, the adhesion is not sufficient. When two or more intermediate layers are used, or when ion implantation or ion mixing is used, dynamic pressure bearings of magnetic disk recording devices, optical disk devices, and the like are used. Etc.
It is difficult to use in terms of cost.
【０００６】また、これらの金属は硬質炭素膜の基材と
して、十分な硬度とは言えない。例えば、硬質炭素膜の
一点に集中的荷重を受けた場合、基材そのものが塑性変
形を起こし、傷等が発生しやすく、保護膜としての機能
を十分に果たせない。Further, these metals are not sufficiently hard as a base material of a hard carbon film. For example, when an intensive load is applied to one point of the hard carbon film, the base material itself is plastically deformed, and is easily damaged, and cannot sufficiently function as a protective film.
【０００７】そこで、本発明は、一般のＰＶＤ装置を用
いて、従来の成膜プロセスを変更することで、基材と中
間層、および、中間層と硬質炭素膜膜との密着性の向上
を図り、さらに、基材を硬化させることで硬質炭素膜の
保護膜としての機能をより高めることを目的としたもの
である。Therefore, the present invention improves the adhesion between the substrate and the intermediate layer and between the intermediate layer and the hard carbon film by changing the conventional film forming process using a general PVD apparatus. The purpose is to further enhance the function of the hard carbon film as a protective film by curing the base material.
【０００８】[0008]
【課題を解決するための手段】前記課題を解決するた
め、本発明の金属基材への硬質炭素膜の成膜方法（第1
番目の方法）は、真空曹内部にプラズマを発生可能なＰ
ＶＤ（Pyhysical VaporDeposition）装置により、窒素
化合物を生成可能な金属を含む金属基材上に、硬質炭素
膜の成膜を行うに際して、前記真空曹内部の不活性ガス
と窒素ガスを混合し、予め基材を窒化可能な温度まで加
熱する第1の工程と、バイアス電圧を基材に印加し、前
記真空曹内部にプラズマを発生させ、同プラズマ中の不
活性ガスイオンと窒素イオンにより、前記金属基材表面
へのボンバードと窒化処理を行う第２の工程と、その
後、前記硬質炭膜膜を成膜する第３の工程とを含むこと
を特徴とする。In order to solve the above-mentioned problems, a method for forming a hard carbon film on a metal substrate according to the present invention (first method)
The second method) is a P that can generate plasma inside the vacuum soda.
When a hard carbon film is formed on a metal substrate containing a metal capable of forming a nitrogen compound by a VD (Pyhysical Vapor Deposition) apparatus, an inert gas and a nitrogen gas in the vacuum soda are mixed and preliminarily prepared. A first step of heating the material to a temperature at which it can be nitrided, and applying a bias voltage to the substrate to generate plasma inside the vacuum soda, and the inert gas ions and nitrogen ions in the plasma cause the metal substrate The method includes a second step of bombarding and nitriding the material surface, and a third step of subsequently forming the hard carbon film.
【０００９】前記方法においては、前記第2の工程と第3
の工程の間に、さらに、窒素化合物を生成可能な金属を
含む中間層を形成することが好ましい（以下第２番目の
方法）。In the above method, the second step and the third step
It is preferable to further form an intermediate layer containing a metal capable of producing a nitrogen compound during the step (hereinafter, a second method).
【００１０】次に本発明の第３番目の方法は、真空曹内
部にプラズマを発生可能なＰＶＤ装置により、金属基材
上に中間層を介して、硬質炭素膜の成膜を行うに際し
て、真空曹内部にプラズマを発生させ、蒸発源より前記
中間層の成膜粒子を蒸発させ、前記金属基材に印加する
バイアス電圧を制御して、前記金属基材の表面に前記成
膜粒子による前記中間層の成膜と不活性ガスおよび成膜
粒子のスパッタと注入を同時に行う第１の工程と、前記
バイアス電圧の電圧を段階的に下げて、前記金属基材の
表層に成膜粒子による中間層の成膜を行う第２の工程
と、中間層の表面に硬質炭素膜を成膜する第３の工程と
を含むことを特徴とする。Next, a third method of the present invention is a method for forming a hard carbon film on a metal substrate through an intermediate layer using a PVD apparatus capable of generating plasma inside a vacuum soda. A plasma is generated inside the soda, the film-forming particles of the intermediate layer are evaporated from an evaporation source, and a bias voltage applied to the metal base is controlled, so that the film-forming particles are formed on the surface of the metal base by the film forming particles. A first step of simultaneously forming a layer and sputtering and injecting an inert gas and a film-forming particle, and gradually lowering the bias voltage to form an intermediate layer of a film-forming particle on the surface layer of the metal base material. And a third step of forming a hard carbon film on the surface of the intermediate layer.
【００１１】次に本発明の第４番目の方法は、真空曹内
部にプラズマを発生可能なＰＶＤ装置により、窒素化合
物を生成可能な金属を含む金属基材上に、前記中間層を
介して硬質炭素膜の成膜を行うに際して、前記真空曹内
部の不活性ガスと窒素ガスを混合し、予め基材を窒化可
能な温度まで加熱する第1の工程とバイアス電圧を基材
に印加し、前記真空曹内部にプラズマを発生させ、同プ
ラズマ中の不活性ガスイオンと窒素イオンにより、前記
金属基材表面へのボンバードと窒化処理を行う第２の工
程と、蒸発源より前記中間層の成膜粒子を蒸発させ、前
記金属基材に印加するバイアス電圧を制御して、前記金
属基材の表面に前記成膜粒子による、中間層の成膜と不
活性ガスおよび成膜粒子のスパッタと注入を同時に行う
第３の工程と、前記バイアス電圧の電圧を段階的に下げ
て、前記金属基材の表層に成膜粒子による中間層の成膜
作用を行う第４の工程と、中間層の表面に硬質炭素膜を
成膜する第５の工程とを含むことを特徴とする。[0011] Next, a fourth method of the present invention is a method in which a PVD apparatus capable of generating plasma inside a vacuum soda is used to harden a metal substrate containing a metal capable of generating a nitrogen compound through the intermediate layer. When forming a carbon film, a first step of mixing an inert gas and a nitrogen gas inside the vacuum soda and heating the substrate to a temperature at which nitriding can be performed in advance, and applying a bias voltage to the substrate, A second step of generating plasma inside the vacuum soda and performing bombardment and nitriding on the surface of the metal substrate by inert gas ions and nitrogen ions in the plasma, and forming the intermediate layer from an evaporation source The particles are evaporated, and a bias voltage applied to the metal base is controlled to form a film of the intermediate layer on the surface of the metal base and sputter and inject the inert gas and the film-formed particles. A third step performed simultaneously; A fourth step of gradually lowering the bias voltage to form a film of the intermediate layer on the surface layer of the metal base material using film-forming particles; and a fifth step of forming a hard carbon film on the surface of the intermediate layer. And a step of:
【００１２】前記方法においては、中間層が窒素化合物
を生成可能な金属を含むことが好ましい（以下第５番目
の方法）。In the above method, it is preferable that the intermediate layer contains a metal capable of forming a nitrogen compound (hereinafter, a fifth method).
【００１３】次に本発明の第６番目の方法は、真空曹内
部にプラズマが発生可能なＰＶＤ装置により、金属基材
上に中間層と、前記中間層の金属と硬質炭素の比率が段
階的に変化する傾斜構造層を介して、硬質炭素膜の成膜
を行うに際して、前記真空曹内部に不活性ガスを導入し
をプラズマを発生させ、第１の蒸発源より前記中間層の
成膜粒子を蒸発させ、前記中間層の成膜を行う第１の工
程と、成膜時間により段階的に前記中間層の成膜粒子の
蒸発量を減少させると同時に第２の蒸発源より前記硬質
炭素膜の成膜粒子の蒸発量を増加させ、前記傾斜構層を
成膜する第２の工程と、前記中間層の成膜粒子の蒸発が
停止した後に、前記真空曹内部に窒素ガスを導入し、前
記不活性ガスと混合させ、硬質炭素膜を成膜する第３の
工程とを含むことを特徴とする。Next, in a sixth method of the present invention, an intermediate layer and a ratio of metal and hard carbon of the intermediate layer are stepwise formed on a metal substrate by a PVD apparatus capable of generating plasma inside a vacuum soda. When a hard carbon film is formed through the inclined structure layer which changes into an inert gas, an inert gas is introduced into the vacuum soda to generate plasma, and film forming particles of the intermediate layer are generated from the first evaporation source. A first step of evaporating the intermediate layer and forming the intermediate layer, and a step of reducing the evaporation amount of the film-forming particles of the intermediate layer in a stepwise manner according to the film forming time, and simultaneously forming the hard carbon film from a second evaporation source. Increasing the amount of evaporation of the film-forming particles of the second step of forming the inclined structure layer, and after the evaporation of the film-forming particles of the intermediate layer is stopped, introducing a nitrogen gas into the vacuum soda, Mixing with the inert gas to form a hard carbon film. And it features.
【００１４】次に本発明の第７番目の方法は、真空曹内
部にプラズマが発生可能なＰＶＤ装置により、金属基材
上に中間層と、前記中間層の金属と硬質炭素の比率が段
階的に変化する傾斜構造層を介して、硬質炭素膜の成膜
を行うに際して、真空曹内部にプラズマを発生させ、蒸
発源より前記中間層の成膜粒子を蒸発させ、前記金属基
材に印加するバイアス電圧を制御して、前記金属基材の
表面に前記成膜粒子による前記中間層の成膜と不活性ガ
スおよび成膜粒子のスパッタと注入を同時に行う第１の
工程と、前記バイアス電圧の電圧を段階的に下げて、前
記金属基材の表層に成膜粒子による中間層の成膜を行う
第２の工程と、成膜時間により段階的に前記中間層の成
膜粒子の蒸発量を減少させると同時に、第２の蒸発源よ
り前記硬質炭素膜の成膜粒子の蒸発量を増加させ、前記
傾斜構層を成膜する第３の工程と、前記中間層の成膜粒
子の蒸発が停止した後に、前記真空曹内部に窒素ガスを
導入し、前記不活性ガスと混合させ、硬質炭素膜を成膜
する第４の工程とを含むことを特徴とする。Next, in a seventh method of the present invention, the intermediate layer and the ratio of the metal and the hard carbon of the intermediate layer are stepwise formed on the metal substrate by a PVD apparatus capable of generating plasma inside the vacuum soda. When the hard carbon film is formed through the inclined structure layer that changes to, a plasma is generated inside the vacuum soda, the film-forming particles of the intermediate layer are evaporated from an evaporation source, and applied to the metal substrate. A first step of controlling a bias voltage to simultaneously form the intermediate layer with the film-forming particles and sputter and inject the inert gas and the film-forming particles on the surface of the metal substrate; A second step of stepping down the voltage and forming a film of the intermediate layer on the surface layer of the metal base material using the film-forming particles; and Simultaneously reducing the hard carbon film from the second evaporation source A third step of increasing the evaporation amount of the film-forming particles and forming the inclined structure layer, and after the evaporation of the film-forming particles of the intermediate layer is stopped, introducing a nitrogen gas into the vacuum soda, And a fourth step of forming a hard carbon film by mixing with an inert gas.
【００１５】次に本発明の第８番目の方法は、真空曹内
部にプラズマが発生可能なＰＶＤ装置により、窒素化合
物を生成可能な金属を含む金属基材上に、中間層と、中
間層の金属と硬質炭素の比率が段階的に変化する傾斜構
造層を介して、硬質炭素膜の成膜を行うに際して、前記
真空曹内部の不活性ガスと窒素ガスを混合し、予め基材
を窒化可能な温度まで加熱する第1の工程とバイアス電
圧を基材に印加し、前記真空曹内部にプラズマを発生さ
せ、同プラズマ中の不活性ガスイオンと窒素イオンによ
り、前記金属基材表面へのボンバードと窒化処理を行う
第２の工程と、蒸発源より前記中間層の成膜粒子を蒸発
させ、前記金属基材に印加するバイアス電圧を制御し
て、前記金属基材の表面に前記成膜粒子による、中間層
の成膜と不活性ガスおよび成膜粒子のスパッタと注入を
同時に行う第３の工程と、前記バイアス電圧の電圧を段
階的に下げて、前記金属基材の表層に成膜粒子による中
間層の成膜作用を行う第４の工程と、成膜時間により段
階的に前記中間層の成膜粒子の蒸発量を減少させると同
時に、第２の蒸発源より前記硬質炭素膜の成膜粒子の蒸
発量を増加させ、前記傾斜構層を成膜する第５の工程
と、前記中間層の成膜粒子の蒸発が停止した後に、前記
真空曹内部に窒素ガスを導入し、前記不活性ガスと混合
させ、硬質炭素膜を成膜する第６の工程とを含むことを
特徴とする。Next, in an eighth method of the present invention, an intermediate layer and an intermediate layer are formed on a metal substrate containing a metal capable of generating a nitrogen compound by a PVD apparatus capable of generating plasma inside a vacuum soda. When forming a hard carbon film through a gradient structure layer in which the ratio of metal and hard carbon changes stepwise, an inert gas and a nitrogen gas inside the vacuum soda can be mixed and the substrate can be nitrided in advance. A first step of heating to a temperature and applying a bias voltage to the substrate, generating plasma inside the vacuum soda, and bombarding the surface of the metal substrate by inert gas ions and nitrogen ions in the plasma. And a second step of performing a nitriding treatment; and evaporating the film-forming particles of the intermediate layer from an evaporation source, controlling a bias voltage applied to the metal base, and forming the film-forming particles on the surface of the metal base. Of intermediate layer and inert gas And a third step of simultaneously performing sputtering and injection of film-forming particles, and a fourth step of stepwise reducing the bias voltage to perform a film-forming operation of an intermediate layer by film-forming particles on the surface layer of the metal base material. And the step of reducing the amount of evaporation of the film-forming particles of the intermediate layer stepwise by the film-forming time, and simultaneously increasing the amount of evaporation of the film-forming particles of the hard carbon film from the second evaporation source, After the fifth step of forming the structural layer and after the evaporation of the film-forming particles of the intermediate layer are stopped, a nitrogen gas is introduced into the vacuum soda and mixed with the inert gas to form a hard carbon film. And a sixth step of forming a film.
【００１６】前記方法においては、中間層が窒素化合物
を生成可能な金属を含むことが好ましい（以下第９番目
の方法）。In the above method, the intermediate layer preferably contains a metal capable of forming a nitrogen compound (hereinafter, a ninth method).
【００１７】[0017]
【発明の実施形態】本発明によれば、ＰＶＤ装置を用い
た、金属基材上へ中間層と傾斜構造層と硬質炭素膜の成
膜法において、密着性の高い硬質炭素膜の成膜と金属基
材の硬化を同時に行うことができる。According to the present invention, in a method for forming an intermediate layer, a gradient structure layer, and a hard carbon film on a metal substrate using a PVD apparatus, it is possible to form a hard carbon film having high adhesion. Curing of the metal substrate can be performed simultaneously.
【００１８】本発明の第1番目の方法は、不活性ガスと
窒素ガスを混合させてボンバードを行うことにより、基
材のクリーニングと同時に窒化を行い、基材の硬度を高
くし、炭素系保護膜の耐摩耗性の効果を高める作用を有
する。In the first method of the present invention, the bombardment is performed by mixing an inert gas and a nitrogen gas, whereby nitriding is performed simultaneously with cleaning of the base material, the hardness of the base material is increased, and carbon-based protection is performed. It has the effect of increasing the wear resistance of the film.
【００１９】本発明の第2番目の方法は、不活性ガスと
窒素ガスを混合させてボンバードを行うことにより、基
材のクリーニングと同時に窒化を行い、基材の硬度を高
くし、炭素系保護膜の耐摩耗性の効果を高める作用を有
する。さらに、中間層が窒化物を生成可能な金属を含む
ため、窒素を介して中間層と基材との結合を図ること
で、密着性を高める作用を有する。In the second method of the present invention, the bombardment is carried out by mixing an inert gas and a nitrogen gas, so that the nitriding is performed simultaneously with the cleaning of the base material, the hardness of the base material is increased, and the carbon-based protection is achieved. It has the effect of increasing the wear resistance of the film. Further, since the intermediate layer contains a metal capable of forming a nitride, the intermediate layer has an effect of improving adhesion by bonding the intermediate layer and the base material through nitrogen.
【００２０】本発明の第3番目の方法は、不活性ガスイ
オンおよび中間層の成膜粒子イオンにより、基材表面お
よび中間層のスパッタ作用およびイオンの注入を起こ
し、基材と中間層との界面の拡散を促進し、密着性を高
める作用を有する。According to a third method of the present invention, the inert gas ions and the film-forming particle ions of the intermediate layer cause a sputtering action and ion implantation on the surface of the substrate and the intermediate layer, thereby causing a difference between the substrate and the intermediate layer. It has the effect of promoting interface diffusion and increasing adhesion.
【００２１】本発明の第4番目の方法は、不活性ガスと
窒素ガスを混合させてボンバードを行うことで、基材の
クリーニングと同時に窒化を図ることで基材の硬度を高
くし、炭素系保護膜の耐摩耗性の効果を高める作用を有
する。さらに、不活性ガスイオンおよび中間層の成膜粒
子イオンにより、基材表面および中間層のスパッタ作用
およびイオンの注入が起こり、基材と中間層との界面の
拡散を促進し、密着性を高める作用を有する。In the fourth method of the present invention, the hardness of the base material is increased by mixing the inert gas and the nitrogen gas and performing the bombardment, thereby cleaning the base material and nitriding simultaneously. It has the effect of increasing the effect of the wear resistance of the protective film. In addition, the inert gas ions and the film-forming particle ions of the intermediate layer cause a sputtering action and ion implantation on the substrate surface and the intermediate layer, thereby promoting diffusion at the interface between the substrate and the intermediate layer and improving adhesion. Has an action.
【００２２】本発明の第5番目の方法は、前記第4番目の
方法において、中間層が窒素化合物を生成可能な金属を
含むことで、不活性ガスと窒素ガスを混合させてボンバ
ードを行い、基材のクリーニングと同時に窒化を行うこ
とができる。これにより、基材の硬度を高くし、炭素系
保護膜の耐摩耗性の効果を高める作用を有する。また、
不活性ガスイオンおよび中間層の成膜粒子イオンによ
り、基材表面および中間層のスパッタ作用およびイオン
の注入が起こり、基材と中間層との界面の拡散を促進
し、密着性を高める作用を有する。さらに、中間層が窒
化物を生成可能な金属を含むため、窒素を介して中間層
と基材との結合を図ることで、密着性を高める作用を有
する。In a fifth method of the present invention, in the fourth method, the intermediate layer contains a metal capable of forming a nitrogen compound, and bombarding is performed by mixing an inert gas and a nitrogen gas. Nitriding can be performed simultaneously with cleaning of the substrate. This has the effect of increasing the hardness of the base material and increasing the wear resistance of the carbon-based protective film. Also,
The inert gas ions and the film-forming particle ions of the intermediate layer cause a sputtering effect on the substrate surface and the intermediate layer and an ion implantation, which promotes the diffusion of the interface between the substrate and the intermediate layer, and enhances the adhesion. Have. Further, since the intermediate layer contains a metal capable of forming a nitride, the intermediate layer has an effect of improving adhesion by bonding the intermediate layer and the base material through nitrogen.
【００２３】本発明の第6番目の方法は、傾斜構造層と
炭素系保護膜の密着性を高くする作用を有する。The sixth method of the present invention has the function of increasing the adhesion between the gradient structure layer and the carbon-based protective film.
【００２４】本発明の第7番目の方法は、不活性ガスイ
オンおよび中間層の成膜粒子イオンにより、基材表面お
よび中間層のスパッタ作用およびイオンの注入が起こ
り、基材と中間層との界面の拡散を促進し、密着性を高
める作用を有する。さらに、傾斜構造層と炭素系保護膜
の密着性を高くする作用を有する。According to a seventh method of the present invention, the inert gas ions and the film-forming particle ions of the intermediate layer cause a sputtering action and ion implantation on the surface of the substrate and the intermediate layer, and the ion-implantation between the substrate and the intermediate layer occurs. It has the effect of promoting interface diffusion and increasing adhesion. Further, it has the effect of increasing the adhesion between the gradient structure layer and the carbon-based protective film.
【００２５】本発明の第8番目の方法は、不活性ガスと
窒素ガスを混合させてボンバードを行うことで、基材の
クリーニングと同時に窒化を図ることで基材の硬度を高
くし、炭素系保護膜の耐摩耗性の効果を高める作用を有
するものである。さらに、不活性ガスイオンおよび中間
層の成膜粒子イオンにより、基材表面および中間層のス
パッタ作用およびイオンの注入が起こり、基材と中間層
との界面の拡散を促進し、密着性を高める作用を有す
る。また、傾斜構造層と炭素系保護膜の密着性を高くす
る作用を有する。In the eighth method of the present invention, the hardness of the base material is increased by mixing the inert gas and the nitrogen gas and performing bombardment, thereby cleaning the base material and nitriding simultaneously. It has an effect of enhancing the effect of the wear resistance of the protective film. In addition, the inert gas ions and the film-forming particle ions of the intermediate layer cause a sputtering action and ion implantation on the substrate surface and the intermediate layer, thereby promoting diffusion at the interface between the substrate and the intermediate layer and improving adhesion. Has an action. Further, it has an effect of increasing the adhesion between the gradient structure layer and the carbon-based protective film.
【００２６】本発明の第9番目の方法は、不活性ガスと
窒素ガスを混合させてボンバードを行うことにより、基
材のクリーニングと同時に窒化を図り、基材の硬度を高
くし、炭素系保護膜の耐摩耗性の効果を高める作用を有
する。さらに、不活性ガスイオンおよび中間層の成膜粒
子イオンにより、基材表面および中間層のスパッタ作用
およびイオンの注入が起こり、基材と中間層との界面の
拡散を促進し、密着性を高める作用を有する。また、傾
斜構造層と炭素系保護膜の密着性を高くする作用を有す
る。また、中間層が窒化物を生成可能な金属を含むた
め、窒素を介して中間層と基材との結合を図ることで、
密着性を高める作用を有する。In the ninth method of the present invention, the bombardment is performed by mixing an inert gas and a nitrogen gas, whereby nitriding is performed simultaneously with cleaning of the base material, hardness of the base material is increased, and carbon-based protection is performed. It has the effect of increasing the wear resistance of the film. In addition, the inert gas ions and the film-forming particle ions of the intermediate layer cause a sputtering action and ion implantation on the substrate surface and the intermediate layer, thereby promoting diffusion at the interface between the substrate and the intermediate layer and improving adhesion. Has an action. Further, it has an effect of increasing the adhesion between the gradient structure layer and the carbon-based protective film. Further, since the intermediate layer contains a metal capable of forming a nitride, by bonding the intermediate layer and the base material through nitrogen,
It has the effect of increasing the adhesion.
【００２７】本発明において、中間層の好ましい膜厚は
１００〜５００nmの範囲であり、このうち傾斜構造膜が
存在する場合、その好ましい膜厚は１００〜１０００nm
の範囲であり、硬質炭素膜の好ましい膜厚は１００〜４
０００nmの範囲である。In the present invention, the preferable thickness of the intermediate layer is in the range of 100 to 500 nm. When the gradient structure film is present, the preferable thickness is 100 to 1000 nm.
And the preferred thickness of the hard carbon film is 100 to 4
000 nm.
【００２８】以下に、本発明の実施形態を図１から図６
を用いて説明する。また、本発明に用いる成膜用装置と
しては、スパッタ装置、イオンプレーティング装置等を
用いることができるが、以下実施の形態１から３には、
非平衡型マグネトロンスパッタリング装置を用いた例に
ついて説明する。Hereinafter, an embodiment of the present invention will be described with reference to FIGS.
This will be described with reference to FIG. In addition, as a film forming apparatus used in the present invention, a sputtering apparatus, an ion plating apparatus, or the like can be used.
An example using a non-equilibrium type magnetron sputtering apparatus will be described.
【００２９】（実施の形態１）本発明の第１番目の方法
および第２番目の方法に関する第１の実施形態につい
て、図１から図４を用いて説明する。(Embodiment 1) A first embodiment of the first and second methods of the present invention will be described with reference to FIGS.
【００３０】まず、装置の概略について説明する。図３
に示す装置は、本発明に用いる非平衡マグネトロンスパ
ッタリング装置の概略を示す。図４は蒸発源および周辺
の詳細を示す。排気するための排気口１を備えた真空槽
２と、この真空槽２内の所定の位置の４個所に配置され
た蒸発源３と、蒸発源３に接続されたスパッタ用電源２
２と、スパッタ放電用ガスの導入口５と、不活性ガスと
窒素および水素等の流入ガス量を調整する調整用バルブ
６と、回転テーブル８上の所定位置に、ワーク７を保持
し、バイアス電源９よりバイアス電圧を印可するための
ワークホルダー１０を備えている。First, the outline of the apparatus will be described. FIG.
The device shown in Fig. 1 schematically shows a non-equilibrium magnetron sputtering device used in the present invention. FIG. 4 shows details of the evaporation source and surroundings. A vacuum chamber 2 having an exhaust port 1 for exhausting the gas; evaporating sources 3 arranged at four predetermined positions in the vacuum chamber 2; and a sputtering power source 2 connected to the evaporating source 3.
2, a spout discharge gas inlet 5, an inert gas, an adjusting valve 6 for adjusting the amount of inflow gas such as nitrogen and hydrogen, and a work 7 held at a predetermined position on the turntable 8, A work holder 10 for applying a bias voltage from a power supply 9 is provided.
【００３１】蒸発源３および４は全部で４個あり、蒸発
源３には、中間層に用いる金属からなるターゲット１２
を設置し、それ以外の蒸発源４には硬質炭素膜の成膜用
の炭素からなるターゲット１２を設置する。中間層の蒸
発源３と炭素の蒸発源４の個数は、１個対３個になって
いるが、中間層の成膜レートが遅い場合や、中間層の膜
厚を厚く成膜する場合は、中間層の蒸発源の割合を増や
してもよい。There are four evaporation sources 3 and 4 in total, and the evaporation source 3 has a target 12 made of metal used for the intermediate layer.
Is installed, and a target 12 made of carbon for forming a hard carbon film is installed in the other evaporation sources 4. The number of the intermediate layer evaporation sources 3 and the carbon evaporation sources 4 is one to three. However, when the film formation rate of the intermediate layer is slow, or when the film thickness of the intermediate layer is large, Alternatively, the ratio of the evaporation source in the intermediate layer may be increased.
【００３２】蒸発源３および４は、非平衡型マグネトロ
ンスパッタ型で、スパッタ用電極１１と、ターゲット１
２と、マグネット１３、１４からなる。また、蒸発源３
および４は、ボンバード時にプラズマを発生させるため
の熱陰極としてのフィラメント１８と、それに接続され
たフィラメント用電源１６および加熱用電源１７を有
し、また、ボンバード時にターゲットを保護するシャッ
ター１８を備えている。The evaporation sources 3 and 4 are of a non-equilibrium type magnetron sputtering type, and include a sputtering electrode 11 and a target 1.
2 and magnets 13 and 14. In addition, evaporation source 3
And 4 have a filament 18 as a hot cathode for generating plasma during bombardment, a filament power supply 16 and a heating power supply 17 connected thereto, and have a shutter 18 for protecting a target during bombardment. I have.
【００３３】磁力線２３は、マグネット１３とマグネッ
ト１４が相対的な磁力が非平衡となっており、また、補
助磁極１５を真空槽２内の蒸発源３および４の間で、回
転テーブル９の近傍に配置することで、ワーク７近くま
で伸ばすことが可能となり、ワーク７近傍のイオン密度
を高くすることができる。これにより、ワーク７の基材
表面および成膜表面を、イオンにより叩き、ボンバード
作用の促進および緻密な成膜等が可能となる。The magnetic lines of force 23 are such that the relative magnetic force of the magnet 13 and the magnet 14 is unbalanced, and the auxiliary magnetic pole 15 is placed between the evaporation sources 3 and 4 in the vacuum chamber 2 and near the rotary table 9. , It is possible to extend to the vicinity of the work 7, and the ion density near the work 7 can be increased. Thereby, the base material surface and the film formation surface of the work 7 are hit with ions, so that the bombarding effect can be promoted and dense film formation can be performed.
【００３４】次に工程について説明する。図２は、工程
の流れと各工程での温度、ガス濃度、フィラメントの電
圧を示す。また、図１に成膜断面図を示す。ここで、基
材３０は、ワーク７の成膜を行なう部分の下地である。Next, the steps will be described. FIG. 2 shows the process flow, and the temperature, gas concentration, and filament voltage in each process. FIG. 1 shows a cross-sectional view of the film formation. Here, the base material 30 is a base of a portion where the work 7 is formed.
【００３５】まず、真空槽２の内部のワークホルダー１
０に、通常の真空装置成膜用の洗浄を行ったワーク７を
設置する。ワーク７の基材３０として、アルミ合金、ス
テンレス、ＳＫ等の窒化可能な金属を含む物質が使用で
きる。First, the work holder 1 inside the vacuum chamber 2
At 0, the work 7 that has been cleaned for ordinary vacuum apparatus film formation is installed. As the base material 30 of the work 7, a substance containing a nitrideable metal such as an aluminum alloy, stainless steel, or SK can be used.
【００３６】次に、排気口１より排気を行い、真空槽内
２の圧力を所定の初期到達圧力１．３３×１０-3Paまで
減圧する。減圧後、ヒータ２０により、真空曹２内部を
４００℃から５００℃に加熱して洗浄を行う。その後、
回転テーブル９を回転させ、ガス導入口５より調整用バ
ルブ６を調整して不活性ガスであるアルゴンガスと窒素
ガスを所定の比率に混合させながら真空曹内部に導入
し、真空度が、４．３９×１０-1Paになるようにする。
ここで、アルゴンと窒素の混合ガスを用いているのは、
窒素ガスのスパッタ効果がアルゴンに比べて、約１０分
の１程の効果しかなく、窒素ガスのみでボンバードする
場合は、アルゴンガスのみの場合に比較して、１０倍程
の時間を要する。そこで、アルゴンガスと窒素ガスに混
合することで、ボンバードの時間の短縮を図る。また、
ボンバード中は、ターゲット１２を保護するためシャッ
ター１９により遮断をしておく。Next, air is exhausted from the exhaust port 1 to reduce the pressure in the vacuum chamber 2 to a predetermined initial ultimate pressure of 1.33 × 10 −3 Pa. After the pressure reduction, the inside of the vacuum soda 2 is heated by the heater 20 from 400 ° C. to 500 ° C. to perform cleaning. afterwards,
The rotating table 9 is rotated, and the adjusting valve 6 is adjusted from the gas inlet 5 to introduce argon gas and nitrogen gas, which are inert gases, into the vacuum soda while mixing them in a predetermined ratio. .39 × 10 -1 Pa.
Here, the reason that a mixed gas of argon and nitrogen is used
The sputtering effect of nitrogen gas is only about one tenth of the effect of argon, and when bombarding only with nitrogen gas, it takes about ten times as long as when only argon gas is used. Therefore, the time of bombarding is shortened by mixing with argon gas and nitrogen gas. Also,
During bombardment, the shutter 12 is shut off to protect the target 12.
【００３７】その後、ヒータ２０を用いて、温度モニタ
ー２１によるフィードバック制御をしながら、ボンバー
ド時の設定温度になるまで加熱する。この温度は、ワー
ク７の窒化可能な温度以上であり、かつ、ワーク７の加
熱後の変形が、必要な寸法精度を確保できる温度以下で
ある必要があり、事前に確認をして設定する。ステンレ
スの場合、約３００℃以上から５５０℃以下が望まし
い。加熱完了後、フィラメント１８を加熱し、さらにフ
ィラメント電源１６より負電圧を印可することで、真空
曹２内部にプラズマを発生させる。また、ワーク７を保
持しているワークホルダー１０にバイアス電圧として約
−３００〜−１０００Ｖ程度の負電圧を印可する。これ
により、基材３０近傍のアルゴンイオンおよび窒素イオ
ンが、バイアス電圧により加速され、基材３０の表面に
衝突し不純物や酸化膜を叩き出すことで、活性状態の高
い金属基材表面を露出させる。いわゆるプラズマクリー
ニングであり、ボンバード処理と呼ばれる。さらに、窒
素イオンは、基材３０の表面に、窒素化合物を生成し、
内部に拡散していくことで、基材３０の硬度を高めるこ
とが出来る。また、ボンバードによる基材３０の過加熱
を防止するために、放電と停止をそれぞれ所定の時間間
隔で規定の回数繰り返す。通常の場合、放電時間と停止
（冷却）が１サイクルとして、１サイクル約２分から７
分で、５から５０回繰り返す。放電時間と停止時間の比
率は、温度の上昇状況を確認しながら設定する。Thereafter, the heater 20 is used to perform heating until the temperature reaches the set temperature at the time of bombarding while performing feedback control by the temperature monitor 21. This temperature must be equal to or higher than the temperature at which the workpiece 7 can be nitrided, and must be equal to or lower than the temperature at which the deformation of the workpiece 7 after heating can ensure the required dimensional accuracy. In the case of stainless steel, the temperature is desirably about 300 ° C. to 550 ° C. After the heating is completed, the filament 18 is heated, and a negative voltage is applied from the filament power supply 16 to generate plasma inside the vacuum soda 2. A negative voltage of about -300 to -1000 V is applied to the work holder 10 holding the work 7 as a bias voltage. Thereby, the argon ions and the nitrogen ions near the substrate 30 are accelerated by the bias voltage and collide with the surface of the substrate 30 to strike out impurities and oxide films, thereby exposing the surface of the highly active metal substrate. . This is so-called plasma cleaning, which is called bombard processing. Furthermore, nitrogen ions generate a nitrogen compound on the surface of the base material 30,
By diffusing into the inside, the hardness of the base material 30 can be increased. Further, in order to prevent the substrate 30 from being overheated by bombardment, the discharge and the stop are repeated a predetermined number of times at predetermined time intervals. In the normal case, the discharge time and the stop (cooling) are one cycle, and one cycle is about 2 minutes to 7 minutes.
Repeat 5 to 50 times in minutes. The ratio between the discharge time and the stop time is set while checking the temperature rise.
【００３８】ボンバードの終了後、ガス量を調整する調
整用バルブ６を操作して、アルゴンガスのみを真空曹２
の内部に導入する。また、基材３０が中間層の成膜温度
になるように、再度、ヒータ２０の温度を設定する。真
空曹２の内部の温度が、設定温度になり、窒素ガスが排
気口１より十分排気された時点で、蒸発源３のターゲッ
ト１２を遮断しているシャッター１９を開く。そして、
ターゲット１２を取り付けてある電極１１にスパッタ用
電源２２より電圧を印可し、スパッタを開始する。一定
時間、基材３０上に中間層３１を成膜し、所定の膜厚に
なった時点で成膜を停止する。After completion of the bombardment, the adjusting valve 6 for adjusting the gas amount is operated to remove only argon gas from the vacuum
To be introduced inside. Further, the temperature of the heater 20 is set again so that the substrate 30 has the film forming temperature of the intermediate layer. When the temperature inside the vacuum soda 2 reaches the set temperature and the nitrogen gas is sufficiently exhausted from the exhaust port 1, the shutter 19 that shuts off the target 12 of the evaporation source 3 is opened. And
A voltage is applied from a sputtering power supply 22 to the electrode 11 on which the target 12 is attached, and sputtering is started. The intermediate layer 31 is formed on the substrate 30 for a certain period of time, and the film formation is stopped when the film thickness reaches a predetermined value.
【００３９】その後、中間層の成膜方法と同様の手順に
て、蒸発源４を用いて硬質炭素膜３３を成膜する。Thereafter, a hard carbon film 33 is formed using the evaporation source 4 in the same procedure as the method for forming the intermediate layer.
【００４０】中間層３１は、一般に炭素の化合物を生成
できる金属であり、Ti、W、Si、Mo、Cr、Al等を用いる
ことができる。特に、Ti、Cr、Al等の窒化物を成膜でき
る金属を中間層に成膜すると、基材３０表面の窒素化合
物の窒素原子が、中間層３１の金属とも化合物を形成
し、接着剤のように機能することで密着性が向上する。
また、アルゴンだけでなく窒素によるボンバードによ
り、アルゴンだけの場合と比較して、表面粗度が大きく
なり、この効果による密着性の向上も図れる。The intermediate layer 31 is generally a metal capable of forming a carbon compound, and may be Ti, W, Si, Mo, Cr, Al, or the like. In particular, when a metal capable of forming a nitride such as Ti, Cr, or Al is formed on the intermediate layer, the nitrogen atoms of the nitrogen compound on the surface of the base material 30 also form a compound with the metal of the intermediate layer 31 to form an adhesive. The function as described above improves the adhesion.
In addition, the bombardment of not only argon but also nitrogen increases the surface roughness as compared with the case of using only argon, thereby improving the adhesion due to this effect.
【００４１】また、基材３０と硬質炭素膜３３との密着
性が良好な場合、例えば、超硬などの場合は、中間層３
１を成膜せず、直接に硬質炭素膜３３を成膜することも
可能である。In the case where the adhesion between the base material 30 and the hard carbon film 33 is good, for example, in the case of superhardness, the intermediate layer 3
It is also possible to directly form the hard carbon film 33 without forming the film 1.
【００４２】また、ボンバード処理によるプラズマクリ
ーニングと窒化を同じに行なう方法について記載した
が、ワーク７とスパッタの蒸発源の電気極性を逆にす
る、逆スパッタによるプラズマ発生法を用いても良い。
さらに、ガスとしては、アルゴン等の不活性ガスと窒素
ガスの混合ガスを用いる方法を記載したが、アルゴン等
の不活性ガスによりボンバードをした後に、窒素ガス等
を混合して窒化を行ってもよい。Although the method of performing the plasma cleaning and the nitriding by the bombarding process in the same manner has been described, the plasma generation method by the reverse sputtering in which the electric polarity of the work 7 and the evaporation source of the sputtering is reversed may be used.
Further, as the gas, a method using a mixed gas of an inert gas such as argon and a nitrogen gas has been described.However, after bombarding with an inert gas such as an argon gas, nitriding may be performed by mixing a nitrogen gas or the like. Good.
【００４３】（実施の形態２）本発明の第3〜５番目の
方法に関する第２の実施形態について、図１〜５を用い
て説明する。なお、成膜用装置は実施の形態１で示した
装置と同じである。まず、図3に示す真空槽２の内部の
ワークホルダー１０に、通常の真空装置の成膜を行なう
ための洗浄を行ったワーク７を設置する。ワーク７の材
質として、真鍮、アルミ合金、ステンレス、炭素工具
鋼、合金工具鋼等の窒化可能な金属を含むものが使用で
きる。(Embodiment 2) A second embodiment of the third to fifth methods of the present invention will be described with reference to FIGS. Note that the film forming apparatus is the same as the apparatus described in Embodiment 1. First, a work 7 which has been cleaned for forming a film by a normal vacuum apparatus is placed in a work holder 10 inside the vacuum chamber 2 shown in FIG. As a material of the work 7, a material containing a nitridable metal such as brass, aluminum alloy, stainless steel, carbon tool steel, and alloy tool steel can be used.
【００４４】図５に中間層の膜厚と成膜時のワーク７に
印加するバイアス電圧の表を示す。FIG. 5 is a table showing the thickness of the intermediate layer and the bias voltage applied to the work 7 during film formation.
【００４５】図3に示す排気口１より排気を行い、真空
槽内２の圧力を所定の初期到達圧力１．３３×１０-3Pa
まで減圧する。減圧後、実施の形態１の加熱による洗浄
とボンバードを行うことも可能である。その後、回転テ
ーブル９を回転させ、ガス導入口５より調整用バルブ６
を調整して不活性ガスであるアルゴンガスを真空槽内部
に導入し、真空度を４．３９×１０-1Paになるようにす
る。その後、ヒータ２０を用いて、温度モニター２１に
よるフィードバック制御をしながら、成膜時の設定温度
になるまで加熱する。この温度は、ワーク７の加熱後の
変形が、必要な寸法精度を確保できる温度以下である必
要があり、事前に確認をして設定する。Evacuation is performed from the exhaust port 1 shown in FIG. 3, and the pressure in the vacuum chamber 2 is increased to a predetermined initial ultimate pressure of 1.33 × 10 −3 Pa.
Reduce pressure to After the pressure reduction, cleaning by heating and bombardment in Embodiment 1 can be performed. After that, the rotary table 9 is rotated, and the adjustment valve 6 is
Is adjusted, argon gas as an inert gas is introduced into the vacuum chamber, and the degree of vacuum is adjusted to 4.39 × 10 -1 Pa. Thereafter, heating is performed using the heater 20 until the temperature reaches the set temperature during film formation while performing feedback control by the temperature monitor 21. This temperature needs to be lower than the temperature at which the deformation of the work 7 after heating can ensure the required dimensional accuracy, and is set by confirming in advance.
【００４６】次に、ワーク７を保持しているワークホル
ダー１０に第１のバイアス電圧として−５００〜−２０
００Ｖ程度の高負電圧を印可する。そして、中間層用の
蒸発源３の電極１１にスパッタ用電源２２より電圧を印
可することにより、真空曹２内にプラズマを発生させ、
ターゲット１２から成膜粒子を発生させる。図５のＡで
示す部分である。プラズマ中のアルゴンイオンおよび成
膜粒子は、一部がイオン化され、ワーク７のバイアス電
圧により加速され、ワーク７の基材３０表面に衝突す
る。プラズマ中のイオンの持つエネルギーレベルは広範
囲にわたるため、基材３０に衝突したアルゴンおよび中
間層の成膜粒子のイオンは、一部は中間層３１として成
膜され、一部は基材３０および中間層３１をスパッタ
し、一部は基材３０の内部に注入される。また、表面に
細かい凹凸が発生する。これにより、中間層３１は、密
着性の弱い部分が叩きだされ、また中間層の金属粒子が
基材に拡散した形となり、さらに、表面に細かな凹凸が
発生することで、基材３０と中間層３１との密着性を向
上させることが可能となる。Next, the first bias voltage is applied to the work holder 10 holding the work 7 from -500 to -20.
A high negative voltage of about 00 V is applied. Then, by applying a voltage from the sputtering power supply 22 to the electrode 11 of the evaporation source 3 for the intermediate layer, a plasma is generated in the vacuum soda 2,
Film-forming particles are generated from the target 12. This is the portion indicated by A in FIG. Part of the argon ions and the film-forming particles in the plasma are ionized, accelerated by the bias voltage of the work 7, and collide with the surface of the base 30 of the work 7. Since the energy level of the ions in the plasma is wide, a part of the ions of the argon and the film-forming particles of the intermediate layer that have collided with the substrate 30 are formed as the intermediate layer 31 and a part of the ions are formed as the intermediate layer 31. The layer 31 is sputtered and partly injected into the substrate 30. In addition, fine irregularities occur on the surface. Thereby, the intermediate layer 31 has a shape in which the weak adhesion portion is beaten out, the metal particles of the intermediate layer are diffused into the base material, and fine irregularities are generated on the surface. Adhesion with the intermediate layer 31 can be improved.
【００４７】ワーク７に印加するバイアス電圧が高負電
圧の状態では、成膜レートが大きく低下し、また、ワー
ク７の温度が急激に上昇するため、一定時間成膜を行な
った時点で、段階的にバイアス電圧を低下させ、最終的
に成膜のみ起こるバイアス電圧の状態にする。最終的な
バイアス電圧は約−０Ｖ〜−５０Ｖ程度が望ましい。図
５のＢで示す。これにより中間層３１を所定の厚さに成
膜する。When the bias voltage applied to the work 7 is a high negative voltage, the film forming rate is greatly reduced, and the temperature of the work 7 is rapidly increased. Then, the bias voltage is lowered, and finally a state of the bias voltage at which only the film formation occurs is obtained. The final bias voltage is desirably about −0 V to −50 V. This is indicated by B in FIG. Thus, the intermediate layer 31 is formed to a predetermined thickness.
【００４８】その後、蒸発源３に印加しているスパッタ
用電源２２を切り、炭素の蒸発源４にスパッタ用電源２
２より印加すると同時に、ワーク７へ印加しているバイ
アス電圧を硬質炭素膜の成膜に最的な電圧に設定する。
その後、所定の時間成膜を行い、硬質炭素膜を中間層の
上部に成膜する。Thereafter, the sputtering power source 22 applied to the evaporation source 3 is turned off, and the sputtering power source 2 is applied to the carbon evaporation source 4.
2, the bias voltage applied to the work 7 is set to the voltage most suitable for forming the hard carbon film.
After that, a film is formed for a predetermined time, and a hard carbon film is formed on the intermediate layer.
【００４９】また、ワーク７の基材３０が窒化物を生成
可能な金属を含む場合、実施の形態１で示した、ボンバ
ードを行うことで窒化層を基材表面近傍に拡散させ基材
の硬度を向上させ、硬質炭素膜の耐摩耗性の特性をより
生かすことができる。When the base material 30 of the work 7 contains a metal capable of forming a nitride, the nitride layer is diffused to the vicinity of the base material surface by performing bombardment as described in the first embodiment, so that the hardness of the base material is increased. And the wear resistance characteristics of the hard carbon film can be further utilized.
【００５０】さらに、中間層３１も窒化物を生成できる
金属を含むことで、窒素介在させてより密着性を向上さ
せることが出来る。Further, since the intermediate layer 31 also contains a metal capable of forming a nitride, the adhesion can be further improved by interposing nitrogen.
【００５１】（実施の形態３）本発明の第6〜９番目の
方法に関する第３の実施形態について、図１、図２およ
び図６を用いて説明する。(Embodiment 3) A third embodiment of the sixth to ninth methods of the present invention will be described with reference to FIGS.
【００５２】まず、真空槽２内部のワークホルダー１０
に金属基材からなるワーク７を設置する。ワーク７は、
真鍮、アルミ合金、ステンレス、ＳＫ等が使用できる。First, the work holder 10 inside the vacuum chamber 2
A work 7 made of a metal base material is placed on the work piece. Work 7
Brass, aluminum alloy, stainless steel, SK, etc. can be used.
【００５３】まず、排気口１より排気を行い、真空槽内
２の圧力を所定の初期到達圧力１．３３×１０-3Paまで
減圧する。減圧後、加熱による洗浄とボンバードを行な
う。その後、回転テーブル９を回転させ、ガス導入口５
より調整用バルブ６を調整して不活性ガスであるアルゴ
ンガスを真空槽内部に導入し、真空度を４．３９×１０
-1Paになるようにする。その後、ヒータ２０により、真
空槽２内部に設けた温度モニター２１によるフィードバ
ック制御をしながら、設定温度になるまで加熱する。こ
の温度は、ワーク７の加熱後の変形が、必要な寸法精度
を確保できる温度以下である必要があり、事前に確認を
して設定する。First, air is exhausted from the exhaust port 1 to reduce the pressure in the vacuum chamber 2 to a predetermined initial ultimate pressure of 1.33 × 10 −3 Pa. After the pressure reduction, washing by heating and bombardment are performed. Thereafter, the rotary table 9 is rotated, and the gas inlet 5 is rotated.
The adjustment valve 6 was further adjusted to introduce argon gas, which is an inert gas, into the vacuum chamber, and the degree of vacuum was adjusted to 4.39 × 10 4
-1 Pa. Thereafter, the heater 20 is heated to a set temperature while performing feedback control by a temperature monitor 21 provided inside the vacuum chamber 2. This temperature needs to be lower than the temperature at which the deformation of the work 7 after heating can ensure the required dimensional accuracy, and is set by confirming in advance.
【００５４】次に、ワーク７を保持しているワークホル
ダー１０にバイアス電圧として負電圧を印可する。そし
て、中間層用のターゲット３の電極１２にスパッタ用に
電圧を印可する。バイアス電圧は−０〜−５０Ｖ程度に
設定する。これにより、真空槽２内にプラズマを発生さ
せ、蒸発源３から成膜粒子を発生させる。プラズマ中の
アルゴンイオンおよび成膜粒子は、一部がイオン化さ
れ、ワーク７の近傍のイオンシース内に引き込まれると
負電圧による電圧勾配により加速され、ワーク７の基材
表面に衝突し中間層が成膜される。中間層３１が所定の
膜厚になるまで、成膜を行なった後、中間層の蒸発源３
の電力を時間と共に段階的に下げると同時に、炭素の蒸
発源４の電極１１にスパッタ用電源２２より印加すると
同時に時間と共に段階的に電力を増加させる。これによ
り中間層の金属と硬質炭素膜の炭素の組成が膜厚の位置
により、段階的に変化するような傾斜構造層３２を中間
層３１の上部に成膜することができる。最終的に中間層
の蒸発源３に印加している電力が０Ｗになった時点で、
真空槽２内部に窒素を１〜１０vol.％程度添加し、ワー
ク７に印可するバイアス電圧を、−５０から−７００Ｖ
程度に設定する。この条件で所定の膜厚になるまで硬質
炭素膜３３を形成する。場合により、水素等を添加する
こともできる。一般に硬質炭素膜は、硬度が高い反面、
内部応力も高く、密着性の低下の原因となる。そこで、
硬質炭素膜中に、窒素または水素を混入させることで、
内部応力を低下させ密着性を向上させることができる。
但し、傾斜構造層の成膜時においては、窒素ガスをアル
ゴン等のスパッタガスに混入させると、逆に密着性が低
下する。Next, a negative voltage is applied to the work holder 10 holding the work 7 as a bias voltage. Then, a voltage is applied to the electrode 12 of the intermediate layer target 3 for sputtering. The bias voltage is set to about -0 to -50V. Thereby, plasma is generated in the vacuum chamber 2, and film-forming particles are generated from the evaporation source 3. When the argon ions and the film-forming particles in the plasma are partially ionized and drawn into the ion sheath near the work 7, they are accelerated by a voltage gradient due to a negative voltage, collide with the base material surface of the work 7, and the intermediate layer is formed. A film is formed. After the film formation is performed until the intermediate layer 31 has a predetermined film thickness, the evaporation source 3 of the intermediate layer is formed.
At the same time as the power of the sputtering source 22 is applied to the electrode 11 of the carbon evaporation source 4 and the power is increased stepwise with time. Thereby, the gradient structure layer 32 in which the composition of the metal of the intermediate layer and the carbon of the hard carbon film changes stepwise depending on the position of the film thickness can be formed on the intermediate layer 31. When the electric power finally applied to the evaporation source 3 of the intermediate layer becomes 0 W,
About 1 to 10 vol.% Of nitrogen is added to the inside of the vacuum chamber 2, and the bias voltage applied to the work 7 is changed from −50 to −700 V
Set to about. Under these conditions, the hard carbon film 33 is formed until a predetermined thickness is obtained. In some cases, hydrogen or the like can be added. Generally, a hard carbon film has high hardness,
The internal stress is also high, causing a decrease in adhesion. Therefore,
By mixing nitrogen or hydrogen in the hard carbon film,
Internal stress can be reduced and adhesion can be improved.
However, when a nitrogen gas is mixed into a sputtering gas such as argon during the formation of the inclined structure layer, the adhesion is reduced.
【００５５】また、ボンバードの方法として実施の形態
１の方法を用いても良い。ワーク７の基材が窒化物を生
成可能な金属を含む場合、実施の形態１で示した、ボン
バードを行うことで窒化層を基材表面近傍に拡散させ基
材の硬度を向上させ、硬質炭素膜の特性をより生かすこ
とができる。The method of Embodiment 1 may be used as the bombarding method. In the case where the base material of the work 7 includes a metal capable of forming a nitride, the nitride layer is diffused to the vicinity of the base material surface by performing bombardment as described in the first embodiment to improve the hardness of the base material, thereby reducing the hardness of the hard carbon. The characteristics of the film can be further utilized.
【００５６】また、中間層を成膜する場合、実施の形態
２で示した、中間層の成膜開始直後を高負電圧のバイア
スで成膜し、段階的に低負電圧のバイアスとすることで
更に密着性を向上させることが出来る。When the intermediate layer is formed, immediately after the start of the formation of the intermediate layer, the film is formed with a high negative voltage bias as described in the second embodiment, and the bias is gradually changed to a low negative voltage. Thus, the adhesion can be further improved.
【００５７】さらに、中間層も窒化物を生成できる金属
を用いることで、窒素を介在させてより密着性を向上さ
せることが出来る。Further, by using a metal capable of forming a nitride for the intermediate layer, the adhesion can be further improved by interposing nitrogen.
【００５８】[0058]
【実施例】次に本発明の具体例を説明する。Next, specific examples of the present invention will be described.
【００５９】ワークの基材として、テンレスＳＵＳ４２
０に、中間層をＴｉとして、硬質炭素膜を成膜した実施
例について説明する。As the base material of the work, Tenless SUS42
An example in which a hard carbon film is formed using Ti as the intermediate layer will be described.
【００６０】（実施例１）通常の表面処理を行う場合の
前洗浄工程を経た基材であるステンレスＳＵＳ４２０か
らなるワーク７に、非平衡型蒸発源を有するもつスパッ
タリング装置のワークホルダー１０に設置した。真空槽
２内部を６．６５×１０-5Paまで真空引きした後、回転
テーブル９の回転を開始し、ワーク７（基材３０）を約
４００℃まで加熱した。この状態を一定時間保持し、真
空槽２内部の洗浄を行った。(Example 1) A work 7 made of stainless steel SUS420, which is a base material subjected to a pre-cleaning step in the case of performing a normal surface treatment, was set on a work holder 10 of a sputtering apparatus having a non-equilibrium evaporation source. . After the inside of the vacuum chamber 2 was evacuated to 6.65 × 10 −5 Pa, the rotation of the turntable 9 was started, and the work 7 (base material 30) was heated to about 400 ° C. This state was maintained for a certain time, and the inside of the vacuum chamber 2 was cleaned.
【００６１】その後、温度調整して、基材３０を約３０
０℃に加熱した。アルゴンガスおよび窒素ガスを所定の
流量比である５０対５０に調整して、ガス導入口５より
導入した。ここでガス圧力が４．３９×１０-1Paになっ
たことを確認して、バイアス電源９よりワークホルダ１
０を通して、ワーク７に−７００Ｖ印可した。同時に、
フィラメント１８を加熱用電源で加熱し、フィラメント
用電源１６から負電圧を印可し熱電子を供給した。これ
により、真空層２内部にプラズマが発生し、ワーク７が
ボンバードされた。ボンバードと停止を１周期５分と
し、約３０回繰り返した。その後、窒素ガスとアルゴン
ガスの流量比を０対１００とし、ワーク７の温度を約２
５０℃に調整した。その後、中間層３１であるＴｉを蒸
発源３より蒸発させ成膜を行った。ワーク７のバイアス
電圧は約−５０Ｖで、中間層３１を１００nm成膜した。
そして、バイアス電圧を−２００Ｖにし、ターゲットと
して炭素を取り付けてある蒸発源４より炭素を蒸発さ
せ、中間層３１上に硬質炭素膜３３を５００ｎｍの膜厚
で成膜した。Thereafter, the temperature is adjusted so that the
Heated to 0 ° C. Argon gas and nitrogen gas were adjusted to a predetermined flow ratio of 50:50, and introduced through the gas inlet 5. Here, it was confirmed that the gas pressure became 4.39 × 10 -1 Pa, and the work holder 1 was supplied from the bias power supply 9.
0, -700 V was applied to the work 7. at the same time,
The filament 18 was heated by a heating power supply, and a negative voltage was applied from the filament power supply 16 to supply thermoelectrons. As a result, plasma was generated inside the vacuum layer 2, and the work 7 was bombarded. Bombarding and stopping were repeated for about 30 times in one cycle of 5 minutes. Thereafter, the flow ratio of the nitrogen gas and the argon gas is set to 0 to 100, and the temperature of the work 7 is set to about 2
The temperature was adjusted to 50 ° C. Thereafter, Ti as the intermediate layer 31 was evaporated from the evaporation source 3 to form a film. The bias voltage of the work 7 was about -50 V, and the intermediate layer 31 was formed to a thickness of 100 nm.
Then, the bias voltage was set to -200 V, carbon was evaporated from the evaporation source 4 to which carbon was attached as a target, and a hard carbon film 33 was formed on the intermediate layer 31 to a thickness of 500 nm.
【００６２】上記条件で成膜したサンプルについて、ボ
ンバード時に窒素とアルゴンを混合したことによる密着
性への効果を、スクラッチ試験により評価した結果を表
1に示す。これにより、ボンバード時に窒素を添加する
ことで、硬質炭素膜３３の基材３０への密着性を向上さ
せることが確認できた。Table 2 shows the results of a scratch test on the sample formed under the above conditions, which evaluated the effect on adhesion by mixing nitrogen and argon during bombardment.
Shown in 1. Thereby, it was confirmed that the addition of nitrogen at the time of bombardment improves the adhesion of the hard carbon film 33 to the substrate 30.
【００６３】[0063]
【表1】 【table 1】
【００６４】（実施例２）通常の表面処理を行う場合の
前洗浄工程を経た基材であるステンレスＳＵＳ４２０
を、非平衡型蒸発源を有するスパッタリング装置のワー
クホルダ１０に設置した。真空槽２内部を６．６５×１
０-5Pa台まで真空引きした後、回転テーブル９の回転を
開始し、ワーク７を約４００℃まで加熱した。この状態
を保持して、真空槽２内部の洗浄を行った。(Example 2) Stainless steel SUS420 which has been subjected to a pre-cleaning step in the case of performing a normal surface treatment
Was placed in a work holder 10 of a sputtering apparatus having a non-equilibrium evaporation source. 6.65 × 1 inside the vacuum chamber 2
After evacuation to the order of 0 −5 Pa, the rotation of the turntable 9 was started, and the work 7 was heated to about 400 ° C. While maintaining this state, the inside of the vacuum chamber 2 was cleaned.
【００６５】所定時間の後、ワーク温度を再調整して、
約３００℃に加熱した。アルゴンガスを所定の流量に調
整して、ガス導入口５より導入した。ここでスパッタ圧
力が６．６５×１０-5Paになったことを確認して、ワー
ク７に−７００Ｖ印可し、ワークをボンバードした。ボ
ンバードと停止を１周期５分とし、約２０回繰り返し
た。その後、ワーク温度を約２５０℃に再設定し、約１
０分間保持した後、中間層Ｔｉを成膜した。ワーク７の
初期バイアス電圧を約−５００から−１５００Ｖに設定
した。中間層Ｔｉは、電力は約２ＫＷで、６分間成膜
し、その後、ワーク７のバイアス電圧を−５０Ｖまで低
下させ、約２４分成膜した。これにより。約１００nm膜
厚の中間層３１を成膜した。最後に、硬質炭素膜３３
を、ワークの７バイアス電圧を−２００Ｖに、そして、
炭素の蒸発源４の電力を２ＫＷとして、中間層３１の上
に硬質炭素膜３３を５００ｎｍの膜厚で成膜した。After a predetermined time, the work temperature is readjusted,
Heated to about 300 ° C. Argon gas was adjusted to a predetermined flow rate and introduced through the gas inlet 5. After confirming that the sputtering pressure was 6.65 × 10 −5 Pa, −700 V was applied to the work 7 to bombard the work. Bombarding and stopping were repeated for about 20 times in one cycle of 5 minutes. After that, reset the work temperature to about 250 ° C,
After holding for 0 minutes, an intermediate layer Ti was formed. The initial bias voltage of the work 7 was set to about -500 to -1500V. The intermediate layer Ti was formed at a power of about 2 KW for 6 minutes, and thereafter, the bias voltage of the work 7 was reduced to −50 V, and the film was formed for about 24 minutes. By this. An intermediate layer 31 having a thickness of about 100 nm was formed. Finally, the hard carbon film 33
To a bias voltage of -200V for the workpiece, and
A hard carbon film 33 having a thickness of 500 nm was formed on the intermediate layer 31 with the power of the carbon evaporation source 4 set to 2 KW.
【００６６】この条件で成膜し、中間層３１の成膜時
に、高負電圧のバイアス電圧が密着性に与える影響を、
スクラッチ試験で評価した結果を表2に示す。Under the above conditions, when the intermediate layer 31 is formed, the influence of the high negative voltage on the adhesion is as follows.
Table 2 shows the results of the evaluation performed in the scratch test.
【００６７】[0067]
【表2】 [Table 2]
【００６８】このように、中間層の成膜開始時に−５０
０から−１０００Ｖの高負電圧のバイアスをワーク７
（基材３０）に印可することで、密着性を向上させるこ
とが確認できた。As described above, at the start of the formation of the intermediate layer, -50 is applied.
Apply a high negative voltage bias of 0 to -1000V to the work 7.
It was confirmed that the application to (base 30) improved the adhesion.
【００６９】（実施例３）通常の表面処理を行う場合の
前洗浄工程を経た基材であるステンレスＳＵＳ４２０
を、非平衡型蒸発源を有するもつスパッタリング装置の
ワークホルダー１０に設置した。真空槽２内部を６．６
５×１０-5Pa台まで真空引きした後、回転テーブル９の
回転を開始し、ワーク７を約４００℃まで加熱した。こ
の状態を保持して、真空槽２内部の洗浄を行った。(Example 3) Stainless steel SUS420 which has been subjected to a pre-cleaning step in the case of performing a normal surface treatment
Was placed in a work holder 10 of a sputtering apparatus having a non-equilibrium evaporation source. 6.6 vacuum chamber 2
After evacuation to the order of 5 × 10 −5 Pa, the rotation of the turntable 9 was started, and the work 7 was heated to about 400 ° C. While maintaining this state, the inside of the vacuum chamber 2 was cleaned.
【００７０】所定時間の後、ワーク温度を再調整して、
約３００℃に加熱した。アルゴンガスを所定の流量に調
整して、ガス導入口５より導入した。ここでスパッタ圧
力が６．６５×１０-5Paになったことを確認して、ワー
ク７に−７００Ｖ印可し、ワークをボンバードした。ボ
ンバードと停止を１周期５分とし、約２０回繰り返し
た。その後、ワーク７を約２５０℃に再設定し、約１０
分間保持した。その後、中間層３１としてＴｉを成膜し
た。ワーク７のバイアス電圧を約−５０Ｖに設定した。
中間層３１は、電力は約２ＫＷで、１２分間成膜した。
その後、炭素を取り付けてある蒸発源４の電力を０．５
ＫＷとして、炭素をスパッタさせた。その後、１７分か
け、Ｔｉ蒸発源３の電力を徐々に低下させると同じに、
炭素の蒸発源４の電力を最終的に２ＫＷとして徐々に増
加させ、中間層３１上にＴｉと硬質炭素膜の傾斜構造層
３２を成膜した。この時点においては窒素ガスを導入口
５より導入しなかった。中間層３１の膜厚は100nmであ
り、硬質炭素膜の傾斜構造層３２の膜厚は150nmであっ
た。そしてＴｉの蒸発源の電力が０ＫＷとなった時点
で、ワーク７のバイアス電圧を−２００Ｖにし、窒素ガ
スを導入口５より、約５％の流量で導入し硬質炭素膜を
５００ｎｍの膜厚まで成膜した。After a predetermined time, the work temperature is readjusted,
Heated to about 300 ° C. Argon gas was adjusted to a predetermined flow rate and introduced through the gas inlet 5. After confirming that the sputtering pressure was 6.65 × 10 −5 Pa, −700 V was applied to the work 7 to bombard the work. Bombarding and stopping were repeated for about 20 times in one cycle of 5 minutes. Thereafter, the work 7 is reset to about 250 ° C.
Hold for minutes. After that, Ti was formed as the intermediate layer 31. The bias voltage of the work 7 was set to about -50V.
The intermediate layer 31 was formed at a power of about 2 KW for 12 minutes.
Thereafter, the power of the evaporation source 4 to which carbon is attached is reduced by 0.5.
Carbon was sputtered as KW. After that, as in the case of gradually decreasing the power of the Ti evaporation source 3 over 17 minutes,
Finally, the power of the carbon evaporation source 4 was gradually increased to 2 KW, and a gradient structure layer 32 of Ti and a hard carbon film was formed on the intermediate layer 31. At this time, nitrogen gas was not introduced through the inlet 5. The thickness of the intermediate layer 31 was 100 nm, and the thickness of the hard carbon gradient structure layer 32 was 150 nm. When the power of the Ti evaporation source becomes 0 KW, the bias voltage of the work 7 is set to -200 V, nitrogen gas is introduced from the inlet 5 at a flow rate of about 5%, and the hard carbon film is formed to a thickness of 500 nm. A film was formed.
【００７１】この条件で成膜したサンプルを用いて、傾
斜構造層の成膜時および硬質炭素膜の成膜時における、
窒素ガスの添加による密着性への影響について、スクラ
ッチ試験による評価した結果を表3に示す。Using a sample formed under these conditions, a sample was formed at the time of forming the gradient structure layer and at the time of forming the hard carbon film.
Table 3 shows the results of the evaluation of the influence of the addition of nitrogen gas on the adhesion by a scratch test.
【００７２】[0072]
【表3】 [Table 3]
【００７３】このように、傾斜構造層の成膜時には、窒
素を混入させず、硬質炭素膜の成膜開始時に窒素を混入
させ成膜することで、密着性を向上させることが確認で
きた。As described above, it was confirmed that the adhesion was improved by mixing nitrogen at the start of the formation of the hard carbon film without mixing nitrogen when forming the inclined structure layer.
【００７４】[0074]
【発明の効果】以上のように本発明によれば、基材のボ
ンバード時に、不活性ガスに窒素ガスを添加すること
で、基材のクリーニングと同時に窒化層を形成し、基材
の硬化を図ることが可能となる。さらに、中間層も窒化
物を生成可能な金属であれば、窒素を介して基材との結
合を図り、中間層と基材との密着性を高めることが可能
となる。さらに、中間層の成膜開始の一定時間のみ、ワ
ークに印加するバイアス電圧を高くすることで、不活性
ガスおよび金属のイオンが、基材表面への成膜および、
スパッタおよび、イオンの注入を起こし、密着性の低い
中間層の除去と、基材中へ中間層の金属の拡散を行な
い、密着性を高めることが可能となる。さらに、炭素系
保護膜に窒素を混入させることで内部応力を緩和し、さ
らに、傾斜構造中に窒素を添加しないことで、炭素と中
間層の金属との密着性を高くすることが可能となる。こ
れらの、幾つかの効果を組みあわせせることで、総合的
に基材と炭素系保護膜との密着性を更に高めることが可
能である。As described above, according to the present invention, at the time of bombardment of the substrate, by adding nitrogen gas to the inert gas, a nitride layer is formed simultaneously with cleaning of the substrate, and curing of the substrate is performed. It becomes possible to plan. Furthermore, if the intermediate layer is also a metal capable of forming a nitride, the intermediate layer can be bonded to the substrate via nitrogen, and the adhesion between the intermediate layer and the substrate can be improved. Furthermore, by increasing the bias voltage applied to the workpiece only for a certain period of time during the start of the formation of the intermediate layer, the inert gas and metal ions are deposited on the surface of the base material and
Sputtering and ion implantation cause removal of the intermediate layer having low adhesion and diffusion of the metal of the intermediate layer into the base material, thereby improving the adhesion. Furthermore, by mixing nitrogen into the carbon-based protective film, internal stress is reduced, and by not adding nitrogen to the inclined structure, it is possible to increase the adhesion between carbon and the metal of the intermediate layer. . By combining some of these effects, it is possible to further enhance the adhesion between the base material and the carbon-based protective film.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の実施の形態1により形成された成膜部
の断面図FIG. 1 is a cross-sectional view of a film forming unit formed according to a first embodiment of the present invention.
【図２】本発明の実施の形態１〜３におけるボンバード
の工程図FIG. 2 is a process chart of bombard according to the first to third embodiments of the present invention.
【図３】本発明の実施の形態１〜３で使用した非平衡型
マグネトロンスパッタリング装置の概略図FIG. 3 is a schematic diagram of a non-equilibrium type magnetron sputtering apparatus used in Embodiments 1 to 3 of the present invention.
【図４】本発明の実施の形態１〜３で使用した非平衡型
マグネトロンスパッタリング装置の蒸発源の概略図FIG. 4 is a schematic diagram of an evaporation source of the non-equilibrium magnetron sputtering device used in the first to third embodiments of the present invention.
【図５】本発明の実施の形態２の成膜部断面図とバイア
ス電圧の関係図FIG. 5 is a diagram showing a relation between a cross-sectional view of a film forming part and a bias voltage according to a second embodiment of the present invention.
【図６】本発明の実施の形態３の成膜部断面図と添加ガ
ス濃度の関係図FIG. 6 is a diagram illustrating a relationship between a cross-sectional view of a film forming part and an additive gas concentration according to a third embodiment of the present invention.
１ 排気口 ２ 真空曹 ３ 蒸発源（中間層） ４ 蒸発源（炭素） ５ 導入口 ６ 調整用バルブ ７ ワーク ８ 回転テーブル ９ バイアス電源 １０ ワークホルダー １１ 電極 １２ ターゲット １３ マグネット（強） １４ マグネット（弱） １６ フィラメント用電源 １７ 加熱用電源 １８ フィラメント １９ シャッター ２０ ヒータ ２１ 温度モニター ２２ スパッタ用電源（中間層） ２３ スパッタ用電源（炭素） ２４ 磁力線 ２５ 成膜粒子 ２６ ガスイオン ２７ 加熱用電源 ２８ プラズマ領域 ３０ ワーク（基材） ３１ 中間層 ３２ 傾斜構造層 ３３ 硬質炭素膜 ３４ 窒化物 DESCRIPTION OF SYMBOLS 1 Exhaust port 2 Vacuum soda 3 Evaporation source (intermediate layer) 4 Evaporation source (carbon) 5 Inlet 6 Adjustment valve 7 Work 8 Rotary table 9 Bias power supply 10 Work holder 11 Electrode 12 Target 13 Magnet (strong) 14 Magnet (weak) ) 16 Filament power supply 17 Heating power supply 18 Filament 19 Shutter 20 Heater 21 Temperature monitor 22 Sputtering power supply (intermediate layer) 23 Sputtering power supply (Carbon) 24 Magnetic field lines 25 Film forming particles 26 Gas ions 27 Heating power supply 28 Plasma area 30 Work (base material) 31 Intermediate layer 32 Inclined structure layer 33 Hard carbon film 34 Nitride
Claims (9)
（Pyhysical Vapor Deposition）装置により、窒素化合
物を生成可能な金属を含む金属基材上に、硬質炭素膜の
成膜を行うに際して、 前記真空曹内部の不活性ガスと窒素ガスを混合し、予め
基材を窒化可能な温度まで加熱する第1の工程と、 バイアス電圧を基材に印加し、前記真空曹内部にプラズ
マを発生させ、同プラズマ中の不活性ガスイオンと窒素
イオンにより、前記金属基材表面へのボンバードと窒化
処理を行う第２の工程と、 その後、前記硬質炭膜膜を成膜する第３の工程とを含む
ことを特徴とする金属基材への硬質炭素膜の成膜方法。1. PVD capable of generating plasma inside a vacuum soda
When a hard carbon film is formed on a metal substrate containing a metal capable of generating a nitrogen compound by a (Pyhysical Vapor Deposition) apparatus, an inert gas and a nitrogen gas inside the vacuum soda are mixed and preliminarily prepared. A first step of heating the material to a temperature at which it can be nitrided; applying a bias voltage to the substrate to generate plasma inside the vacuum soda; and using the inert gas ions and nitrogen ions in the plasma to form the metal substrate. Forming a hard carbon film on a metal substrate, comprising: a second step of bombarding and nitriding the surface of the material; and a third step of forming the hard carbon film thereafter. Method.
に、窒素化合物を生成可能な金属を含む中間層を形成す
る請求項1に記載の金属基材への硬質炭素膜の成膜方
法。2. The method according to claim 1, wherein an intermediate layer containing a metal capable of generating a nitrogen compound is further formed between the second step and the third step. Film formation method.
装置により、金属基材上に中間層を介して、硬質炭素膜
の成膜を行うに際して、 真空曹内部にプラズマを発生させ、蒸発源より前記中間
層の成膜粒子を蒸発させ、前記金属基材に印加するバイ
アス電圧を制御して、前記金属基材の表面に前記成膜粒
子による前記中間層の成膜と不活性ガスおよび成膜粒子
のスパッタと注入を同時に行う第１の工程と、 前記バイアス電圧の電圧を段階的に下げて、前記金属基
材の表層に成膜粒子による中間層の成膜を行う第２の工
程と、 中間層の表面に硬質炭素膜を成膜する第３の工程とを含
むことを特徴とする金属基材への硬質炭素膜の成膜方
法。3. PVD capable of generating plasma inside a vacuum soda
When a hard carbon film is formed on a metal substrate via an intermediate layer by an apparatus, plasma is generated inside a vacuum soda, and the film-forming particles of the intermediate layer are evaporated from an evaporation source to form the metal substrate. Controlling a bias voltage applied to the material, a first step of simultaneously forming a film of the intermediate layer with the film-forming particles and sputtering and injecting the inert gas and the film-forming particles on the surface of the metal substrate; A second step of forming the intermediate layer on the surface layer of the metal base material by reducing the bias voltage stepwise, and forming a hard carbon film on the surface of the intermediate layer; A method for forming a hard carbon film on a metal substrate, comprising the steps of:
装置により、窒素化合物を生成可能な金属を含む金属基
材上に、前記中間層を介して硬質炭素膜の成膜を行うに
際して、 前記真空曹内部の不活性ガスと窒素ガスを混合し、予め
基材を窒化可能な温度まで加熱する第1の工程とバイア
ス電圧を基材に印加し、前記真空曹内部にプラズマを発
生させ、同プラズマ中の不活性ガスイオンと窒素イオン
により、前記金属基材表面へのボンバードと窒化処理を
行う第２の工程と、 蒸発源より前記中間層の成膜粒子を蒸発させ、前記金属
基材に印加するバイアス電圧を制御して、前記金属基材
の表面に前記成膜粒子による、中間層の成膜と不活性ガ
スおよび成膜粒子のスパッタと注入を同時に行う第３の
工程と、 前記バイアス電圧の電圧を段階的に下げて、前記金属基
材の表層に成膜粒子による中間層の成膜作用を行う第４
の工程と、 中間層の表面に硬質炭素膜を成膜する第５の工程とを含
むことを特徴とする金属基材への硬質炭素膜の成膜方
法。4. PVD capable of generating plasma inside a vacuum soda
When a hard carbon film is formed on the metal base material containing a metal capable of generating a nitrogen compound through the intermediate layer by an apparatus, an inert gas and a nitrogen gas in the vacuum soda are mixed, and A first step of heating the substrate to a temperature at which nitriding can be performed and a bias voltage is applied to the substrate to generate plasma inside the vacuum soda, and the inert gas ions and nitrogen ions in the plasma cause the metal substrate A second step of bombarding and nitriding the surface of the material, evaporating film-forming particles of the intermediate layer from an evaporation source, controlling a bias voltage applied to the metal substrate, and controlling the surface of the metal substrate. A third step of simultaneously forming an intermediate layer and sputtering and injecting the inert gas and the film-forming particles by the film-forming particles; Intermediate layer with film-forming particles on the surface 4th to perform film formation
And a fifth step of forming a hard carbon film on the surface of the intermediate layer.
む請求項4に記載の金属基材への硬質炭素膜の成膜方
法。5. The method for forming a hard carbon film on a metal substrate according to claim 4, wherein the intermediate layer contains a metal capable of generating a nitrogen compound.
装置により、金属基材上に中間層と、前記中間層の金属
と硬質炭素の比率が段階的に変化する傾斜構造層を介し
て、硬質炭素膜の成膜を行うに際して、 前記真空曹内部に不活性ガスを導入しをプラズマを発生
させ、第１の蒸発源より前記中間層の成膜粒子を蒸発さ
せ、前記中間層の成膜を行う第１の工程と、 成膜時間により段階的に前記中間層の成膜粒子の蒸発量
を減少させると同時に第２の蒸発源より前記硬質炭素膜
の成膜粒子の蒸発量を増加させ、前記傾斜構層を成膜す
る第２の工程と、 前記中間層の成膜粒子の蒸発が停止した後に、前記真空
曹内部に窒素ガスを導入し、前記不活性ガスと混合さ
せ、硬質炭素膜を成膜する第３の工程とを含むことを特
徴とする金属基材への硬質炭素膜の成膜方法。6. PVD capable of generating plasma inside a vacuum soda
By the apparatus, an intermediate layer on a metal substrate, through a gradient structure layer in which the ratio of the metal and the hard carbon of the intermediate layer is stepwise changed, when forming a hard carbon film, A first step of introducing an inert gas to generate plasma, evaporating film-forming particles of the intermediate layer from a first evaporation source, and forming a film of the intermediate layer; A second step of reducing the evaporation amount of the film-forming particles of the intermediate layer and simultaneously increasing the amount of evaporation of the film-forming particles of the hard carbon film from a second evaporation source to form the inclined structure layer; A third step of introducing a nitrogen gas into the vacuum soda after the evaporation of the film-forming particles of the intermediate layer is stopped, mixing the gas with the inert gas, and forming a hard carbon film. A method for forming a hard carbon film on a metal substrate.
装置により、金属基材上に中間層と、前記中間層の金属
と硬質炭素の比率が段階的に変化する傾斜構造層を介し
て、硬質炭素膜の成膜を行うに際して、 真空曹内部にプラズマを発生させ、蒸発源より前記中間
層の成膜粒子を蒸発させ、前記金属基材に印加するバイ
アス電圧を制御して、前記金属基材の表面に前記成膜粒
子による前記中間層の成膜と不活性ガスおよび成膜粒子
のスパッタと注入を同時に行う第１の工程と、 前記バイアス電圧の電圧を段階的に下げて、前記金属基
材の表層に成膜粒子による中間層の成膜を行う第２の工
程と、 成膜時間により段階的に前記中間層の成膜粒子の蒸発量
を減少させると同時に、第２の蒸発源より前記硬質炭素
膜の成膜粒子の蒸発量を増加させ、前記傾斜構層を成膜
する第３の工程と、 前記中間層の成膜粒子の蒸発が停止した後に、前記真空
曹内部に窒素ガスを導入し、前記不活性ガスと混合さ
せ、硬質炭素膜を成膜する第４の工程とを含むことを特
徴とする金属基材への硬質炭素膜の成膜方法。7. PVD capable of generating plasma inside a vacuum soda
When a hard carbon film is formed through an intermediate layer on a metal base material and an inclined structure layer in which the ratio of the metal to hard carbon in the intermediate layer changes stepwise, plasma is generated inside the vacuum soda. And evaporating the film-forming particles of the intermediate layer from an evaporation source, controlling a bias voltage applied to the metal base, and forming the film of the intermediate layer by the film-forming particles on the surface of the metal base. A first step of simultaneously performing sputtering and injection of inert gas and film-forming particles, and stepwise reducing the voltage of the bias voltage to form an intermediate layer by film-forming particles on the surface layer of the metal base material. A second step to be performed, wherein the evaporation amount of the film-forming particles of the intermediate layer is reduced stepwise according to the film-forming time, and the evaporation amount of the film-forming particles of the hard carbon film is increased from a second evaporation source. A third step of forming the inclined structure layer; A fourth step of introducing nitrogen gas into the vacuum soda after the evaporation of the film-forming particles is stopped, mixing the gas with the inert gas, and forming a hard carbon film. A method for forming a hard carbon film on a material.
装置により、窒素化合物を生成可能な金属を含む金属基
材上に、中間層と、中間層の金属と硬質炭素の比率が段
階的に変化する傾斜構造層を介して、硬質炭素膜の成膜
を行うに際して、 前記真空曹内部の不活性ガスと窒素ガスを混合し、予め
基材を窒化可能な温度まで加熱する第1の工程とバイア
ス電圧を基材に印加し、前記真空曹内部にプラズマを発
生させ、同プラズマ中の不活性ガスイオンと窒素イオン
により、前記金属基材表面へのボンバードと窒化処理を
行う第２の工程と、 蒸発源より前記中間層の成膜粒子を蒸発させ、前記金属
基材に印加するバイアス電圧を制御して、前記金属基材
の表面に前記成膜粒子による、中間層の成膜と不活性ガ
スおよび成膜粒子のスパッタと注入を同時に行う第３の
工程と、 前記バイアス電圧の電圧を段階的に下げて、前記金属基
材の表層に成膜粒子による中間層の成膜作用を行う第４
の工程と、 成膜時間により段階的に前記中間層の成膜粒子の蒸発量
を減少させると同時に、第２の蒸発源より前記硬質炭素
膜の成膜粒子の蒸発量を増加させ、前記傾斜構層を成膜
する第５の工程と、 前記中間層の成膜粒子の蒸発が停止した後に、前記真空
曹内部に窒素ガスを導入し、前記不活性ガスと混合さ
せ、硬質炭素膜を成膜する第６の工程とを含むことを特
徴とする金属基材への硬質炭素膜の成膜方法。8. PVD capable of generating plasma inside a vacuum soda
The apparatus forms a hard carbon film on a metal substrate containing a metal capable of generating a nitrogen compound through an intermediate layer and a gradient structure layer in which the ratio of the metal to the hard carbon in the intermediate layer changes stepwise. In performing, a first step of mixing the inert gas and nitrogen gas inside the vacuum soda and heating the substrate to a temperature at which nitriding can be performed in advance, and a bias voltage is applied to the substrate, and a plasma is applied inside the vacuum soda. A second step of bombarding and nitriding the surface of the metal substrate with inert gas ions and nitrogen ions in the plasma, and evaporating the film-forming particles of the intermediate layer from an evaporation source. Controlling a bias voltage to be applied to the metal base material to simultaneously form a film of the intermediate layer and sputter and inject the inert gas and the film formation particles on the surface of the metal base material by the film-forming particles; Process, and the voltage of the bias voltage Lowering stepwise to perform a film-forming operation of an intermediate layer by film-forming particles on the surface layer of the metal base material.
And evaporating the film-forming particles of the hard carbon film from a second evaporation source while decreasing the amount of evaporation of the film-forming particles of the intermediate layer stepwise by the film-forming time, A fifth step of forming a structural layer, and after the evaporation of the film-forming particles of the intermediate layer is stopped, a nitrogen gas is introduced into the vacuum soda and mixed with the inert gas to form a hard carbon film. A method for forming a hard carbon film on a metal substrate, comprising: a sixth step of forming a film.
む請求項8に記載の金属基材への硬質炭素膜の成膜方
法。9. The method for forming a hard carbon film on a metal substrate according to claim 8, wherein the intermediate layer contains a metal capable of generating a nitrogen compound.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000275444A JP2002088465A (en) | 2000-09-11 | 2000-09-11 | Method for depositng hard carbon film on metal base material |
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