JPH07102377A - Carbon coating film or coating film essentially comprising carbon - Google Patents
Carbon coating film or coating film essentially comprising carbonInfo
- Publication number
- JPH07102377A JPH07102377A JP6197516A JP19751694A JPH07102377A JP H07102377 A JPH07102377 A JP H07102377A JP 6197516 A JP6197516 A JP 6197516A JP 19751694 A JP19751694 A JP 19751694A JP H07102377 A JPH07102377 A JP H07102377A
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- Japan
- Prior art keywords
- carbon
- film
- hardness
- coating film
- main component
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の利用分野】本発明は光学的エネルギバンド巾が
1.0eV 以上特に1.5 〜5.5eV を有する炭素または炭素を
主成とする被膜を被形成面上にコーティングすることに
より、これら固体の表面の補強材、または機械ストレス
にたいする保護材を得ようとする複合体に関するもので
ある。FIELD OF THE INVENTION The present invention has an optical energy bandwidth of
A composite material that is intended to obtain a reinforcing material for these solid surfaces, or a protective material against mechanical stress, by coating the surface to be formed with carbon or a carbon-based film having at least 1.0 eV, especially 1.5 to 5.5 eV. It is about the body.
【０００２】[0002]
【従来の技術】炭素膜のコーティングに関しては、本発
明人の出願になる特許願「炭素被膜を有する複合体及び
その作製方法」（特願昭56-146930 号昭和56年 9月17日
出願）が知られている。また炭素膜は耐摩耗材であると
同時に高平滑性、高熱伝導性等多くの特性を有してお
り、電気部品その他に応用が期待されている。2. Description of the Related Art Regarding the coating of a carbon film, a patent application filed by the present inventor "Composite having carbon film and method for producing the same" (Japanese Patent Application No. 56-146930, filed on September 17, 1981) It has been known. In addition, the carbon film is a wear resistant material and has many characteristics such as high smoothness and high thermal conductivity, and is expected to be applied to electric parts and others.
【０００３】被形成面上にダイヤモンド類似の硬さを有
するアモルファス（非晶質）または5 〜200 Åの大きさ
の微結晶性を有するセミアモルファス( 半非晶質) 構造
を有する炭素または炭素を主成分とする被膜を形成する
場合、被形成面を有する基板を設けた高周波印加電極の
近傍において、プラズマ中の電子が高周波印加電極に蓄
積されることによって生じるセルフバイアスにより加速
された正イオン( 例えばH + ) を、形成中の炭素または
炭素を主成分とする被膜に衝突させることにより、その
炭素または炭素を主成分とする被膜をより硬度の大き
な、ダイヤモンドに近い構造を持った炭素膜を作ること
を行なってきた。これは正イオンを衝突させることでＣ
＝Ｃのような二重結合を有する炭素の割合を減らしてＣ
−Ｃの結合をゆうする炭素を増やしたり、あるいは炭素
原子に結合している水素原子をなくすことにより sp2混
成軌道をもついわゆる三方炭素やsp混成軌道をもついわ
ゆる二方炭素を無くし sp3混成軌道をもったいわゆる四
方炭素の割合を増やすことによりダイヤモンド結合を生
じやすくするためである。従ってより硬度の大きい炭素
または炭素を主成分とする被膜を作成しようとするとき
は、電極間に発生するセルフバイアスを大きくして正イ
オンの加速を大きくしなければならない。このセルフバ
イアスを増加させるために行われている方法としては、
先ず第１に反応圧力を減少させる方法がある。これは炭
素または炭素を主成分とする被膜形成に使用する炭化水
素化物気体の圧力を減少させることにより単位体積中に
含まれる炭化水素化物気体分子の個数が減少するため、
相対的に気体を分解するために加えられている高周波エ
ネルギの出力が大きくなりプラズマ中の電子が増大して
高周波印加電極に蓄積されるためセルスバイアスが増大
するということに基づくものである。Amorphous (amorphous) having a hardness similar to that of diamond or carbon or carbon having a semi-amorphous (semi-amorphous) structure having a microcrystalline size of 5 to 200 Å is formed on the surface to be formed. When forming a film containing the main component, in the vicinity of the high frequency applying electrode provided with the substrate having the surface to be formed, positive ions accelerated by self-bias generated by the electrons in the plasma being accumulated in the high frequency applying electrode ( For example, (H + ) is made to collide with carbon or a film containing carbon as a main component during formation to form a carbon film having a structure similar to diamond with a higher hardness in the carbon or the film containing carbon as a main component. I've been making things. This is caused by colliding positive ions with C
C by reducing the proportion of carbons having a double bond such as ═C
-By increasing the number of carbon atoms that bond to C, or by eliminating the hydrogen atoms that are bonded to carbon atoms, the so-called three-way carbon having an sp 2 hybrid orbital and the so-called two-way carbon having an sp hybrid orbital are eliminated and sp 3 hybridized. This is because it is easy to cause diamond bonding by increasing the proportion of so-called tetragonal carbon having orbital. Therefore, in order to form a carbon film having a higher hardness or a film containing carbon as a main component, it is necessary to increase the self-bias generated between the electrodes to increase the acceleration of positive ions. The methods that are being used to increase this self-bias are:
First, there is a method of reducing the reaction pressure. This is because the number of hydrocarbon gas molecules contained in a unit volume is reduced by reducing the pressure of carbon or a hydrocarbon gas used for forming a film containing carbon as a main component.
This is based on the fact that the output of the high-frequency energy applied to relatively decompose the gas is increased and the electrons in the plasma are increased and accumulated in the high-frequency applying electrode to increase the cell bias.
【０００４】また、高周波エネルギの出力を増大させる
方法があるが、これは上述した如く、気体を分解するエ
ネルギが増大するとプラズマ中の電子が増大するため
に、高周波印加電極への電子の蓄積が増大してセルフバ
イアスが大きくなることによるものである。There is also a method of increasing the output of high-frequency energy. This is because accumulation of electrons in the high-frequency application electrode is increased because the number of electrons in plasma increases as the energy for decomposing gas increases, as described above. This is because the self-bias increases with the increase.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、このよ
うな方法により被形成面上に硬度の大きい炭素または炭
素を主成分とする被膜を形成しようとした場合、セルフ
バイアスを大きくすることにより成膜することになるた
め、大きなセルフバイアスで加速された大きな運動エネ
ルギを持った正イオンが成膜中の炭素または炭素を主成
分とする被膜に衝突すると同時に形成面にも衝突してし
まい被形成面をスパッタしてしまう結果硬度の大きな炭
素または炭素を主成分とする被膜を被形成面に損傷を与
えることなく形成することは困難であった。また硬度の
大きな膜は被形成面や炭素または炭素を主成分とする被
膜自体の膨張、収縮または応力等のために被形成面との
整合性が悪く剥離や脱離をおこしてしまい密着性の悪い
ものであった。However, when an attempt is made to form carbon having a high hardness or a film containing carbon as a main component on the surface to be formed by such a method, the film is formed by increasing the self-bias. Therefore, positive ions having a large kinetic energy accelerated by a large self-bias collide with the carbon or the coating film containing carbon as the main component during the film formation, and at the same time, they collide with the surface to be formed. As a result of sputtering, it has been difficult to form carbon having a high hardness or a coating film containing carbon as a main component without damaging the surface to be formed. In addition, a film having a high hardness has poor compatibility with the surface to be formed due to expansion, contraction, or stress of the surface to be formed or carbon or a film containing carbon as a main component, and peeling or detachment occurs, resulting in poor adhesion. It was bad.
【０００６】本発明は上記のような問題点を解決し光学
的エネルギバンド巾（Egという）が1.0eV 以上、好まし
くは1.5 〜5.5eV を有し、硬度がビッカース硬度におい
て2000Kg/mm2 以上、好ましくは4500Kg/mm2以上、理想
的には6500Kg/mm2というダイヤモンドに類似の絶縁性と
硬さを有するアモルファスまたは5 〜200 Åの大きさの
微結晶性を有するアモルファス( 半非晶質) 構造を有す
る炭素またはこの炭素中に水素、ハロゲン元素が25原子
％以下またはIII 価またはＶ価の不純物が５原子％以
下、また窒素がN/C ≦0.05の濃度に添加されたいわゆる
炭素を主成分とする炭素を被形成面上に、密着性良くま
た被形成面に対して整合性良く設けることを目的として
成されたものである。The present invention solves the above problems and has an optical energy band width (called Eg) of 1.0 eV or more, preferably 1.5 to 5.5 eV, and a hardness of 2000 Kg / mm 2 or more in Vickers hardness, Amorphous with an insulation and hardness similar to diamond, preferably 4500 Kg / mm 2 or more, ideally 6500 Kg / mm 2 , or microcrystalline amorphous (semi-amorphous) with a size of 5 to 200 Å. Mainly carbon having a structure or so-called carbon in which hydrogen or halogen element is contained at 25 atomic% or less or III-valent or V-valent impurity is contained at 5 atomic% or less, and nitrogen is added in a concentration of N / C ≤0.05 The purpose is to provide carbon as a component on the surface to be formed with good adhesion and with good conformity to the surface to be formed.
【０００７】[0007]
【課題を解決するための手段】本発明は上記の目的を達
成するために第１の電極と被形成面を有する基板に接し
て設けられた第２の電極との間に直流または高周波エネ
ルギを加えて、発生させたプラズマにより炭化水素化物
気体とまたはこれに加えて添加物気体とを分解反応せし
めて上記被形成面上に炭素または炭素を主成分とする被
膜を形成する方法において、炭素または炭素を主成分と
する被膜形成の際、反応圧力を減少させるあるいは高周
波エネルギを増加させるまたは添加物気体の添加量を変
化させる若しくはそれらの条件を複数併用することによ
り形成される炭素または炭素を主成分とする被膜の硬度
を被形成面側より表面に向かって増加させることとした
ものである。In order to achieve the above-mentioned object, the present invention applies direct current or high frequency energy between a first electrode and a second electrode provided in contact with a substrate having a surface to be formed. In addition, in the method of decomposing and reacting the hydrocarbon gas and the additive gas with the generated plasma to form carbon or a coating film containing carbon as a main component on the formation surface, carbon or When forming a film containing carbon as a main component, the reaction pressure is decreased, the high frequency energy is increased, the amount of additive gas is changed, or a combination of these conditions is used. The hardness of the coating film as a component is increased from the surface to be formed toward the surface.
【０００８】即ち本発明は被形成面上に炭素または炭素
を主成分とする被膜をコーティングし、その表面での耐
摩耗性等の機械的強度を補強しようというものであり、
そのためのダイヤモンド類似の硬さを有した炭素または
炭素を主成分とする被膜を被形成面上に直接形成させる
のではなく、被形成面に密接する部分から徐々に硬度を
上げてゆき、所望の膜厚のときに所望の硬度の炭素また
は炭素を主成分とする被膜が得られるように反応圧力を
減少あるいは高周波エネルギを増加または添加物気体の
添加量を変化させることに特徴を有する。That is, the present invention is to coat the surface to be formed with carbon or a film containing carbon as a main component to reinforce mechanical strength such as abrasion resistance on the surface.
Therefore, instead of directly forming a carbon or carbon-based coating having a hardness similar to diamond on the formation surface, gradually increase the hardness from the portion in close contact with the formation surface, It is characterized in that the reaction pressure is decreased or the high frequency energy is increased or the amount of the additive gas added is changed so that a carbon film having a desired hardness or a film containing carbon as a main component can be obtained at a film thickness.
【０００９】被形成面上に直接ダイヤモンド類似の硬さ
を有した膜を形成させようとするとセルフバイアスを大
きくして炭素または炭素を主成分とする被膜を形成させ
ることを行わなければならず、被形成面へのスパッタは
避けることはできないが、被形成面上に密接した炭素ま
たは炭素を主成分とする被膜は、被形成面に損傷を与え
ない程度のセルフバイアスで作り得る硬さの炭素または
炭素を主成分とする被膜にしておき、徐々に硬度を上げ
た膜を積層させて、表面には所望の硬度を有した炭素ま
たは炭素を主成分とする被膜を形成すれば、被形成面と
の密接性も良くしかも大きな硬度を有した炭素または炭
素を主成分とする被膜を形成することができる。When a film having a hardness similar to that of diamond is to be formed directly on the surface to be formed, it is necessary to increase self-bias and form carbon or a film containing carbon as a main component. Although spattering on the surface to be formed is unavoidable, carbon or a film mainly composed of carbon that is in close contact with the surface to be formed has a carbon hardness that can be created by self-bias that does not damage the surface to be formed. Alternatively, if a coating film containing carbon as a main component is formed, and films having a gradually increasing hardness are laminated, and carbon having a desired hardness or a coating film containing carbon as a main component is formed on the surface to be formed, It is possible to form carbon or a coating film containing carbon as a main component, which has good close contact with and has a large hardness.
【００１０】この場合、図６(A) に示すように硬度の小
さい膜から硬度の大きい膜を何層かに別けて積層する方
法と、図６(B) に示すように硬度を連続的に変えて、単
層の中で硬度が連続的に変化した炭素または炭素を主成
分とする被膜を形成させる方法とがある。また本発明に
おいてセルフバイアスを大きくする方法としては反応圧
力を減少させる方法、高周波エネルギを増加させる方
法、添加物気体の添加量を変化させる方法及び上記３つ
の方法を２つまたは３つ組あわせる方法がある。In this case, as shown in FIG. 6 (A), a method of laminating a film having a small hardness to a film having a large hardness separately in several layers, and a method of continuously changing the hardness as shown in FIG. 6 (B). Alternatively, there is a method of forming carbon or a coating film containing carbon as a main component whose hardness continuously changes in a single layer. Further, in the present invention, as a method for increasing the self-bias, there is a method of decreasing the reaction pressure, a method of increasing the high frequency energy, a method of changing the amount of additive gas added, and a method of combining two or three of the above three methods. There is.
【００１１】本発明に用いられる被形成面としては、Ｐ
ＥＴ（ポリエチレンテレフタレート）、ＰＥＳ、ＰＭＭ
Ａ、テフロン、エポキシ、ポリイミド等の有機樹脂基体
または金属メッシュ状キャリア、紙等テープ状キャリ
ア、ガラス、金属、セラミック、半導体、磁気ヘッド用
部材、磁気ディスク等がある。以下に実施例と共に本発
明を具体的に説明する。The surface to be formed used in the present invention is P
ET (polyethylene terephthalate), PES, PMM
A, an organic resin substrate such as Teflon, epoxy, polyimide, or a metal mesh carrier, a tape carrier such as paper, glass, metal, ceramic, semiconductor, magnetic head member, magnetic disk and the like. The present invention will be specifically described below with reference to examples.
【００１２】[0012]
【実施例】図１は本発明の炭素または炭素を主成分とす
る被膜を形成するためのプラズマＣＶＤ装置の概要を示
す。図面において、ドーピング系(1) において、キャリ
アガスである水素を(2) より、反応性気体である炭化水
素気体例えばメタン、エチレンを(3) より、III 価不純
物のジボラン（水素希釈）(4) 、Ｖ価不純物のアンモニ
アまたはフォスヒンを(5) よりバルブ(6) 、流量計(7)
をへて反応系(8) 中にノズル(9) より導入される。この
ノズルに至る前に、反応性気体の励起用にマイクロ波エ
ネルギを(10)で加えて予め活性化させることは有効であ
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an outline of a plasma CVD apparatus for forming carbon or a film containing carbon as a main component of the present invention. In the figure, in the doping system (1), hydrogen as a carrier gas is used from (2), a hydrocarbon gas that is a reactive gas such as methane and ethylene is used from (3), and diborane (hydrogen dilution) (4 ), V-impurity ammonia or foshin from (5) valve (6), flow meter (7)
It is introduced through a nozzle (9) into the reaction system (8). Before reaching this nozzle, it is effective to add microwave energy at (10) to excite the reactive gas and preactivate it.
【００１３】反応系(8) には第１の電極(11)、第２の電
極(12)を設けた。この場合（第１の電極面積／第２の電
極面積）＜１の条件を満たすようにした。一対の電極(1
1)、(12)間には高周波電源(13)、マッチングトランス(1
4)、直流バイヤス電源(15)より電気エネルギが加えら
れ、プラズマが発生する。排気系(16)は圧力調整バルブ
(17)、ターボ分子ポンプ(18)、ロータリーポンプ(19)を
へて不要気体を排気する。 反応性気体には、反応空間
(20)における圧力が0.001 〜10torr代表的には0.01〜0.
5torr の下で高周波もしくは直流によるエネルギにより
0.1 〜5KW のエネルギが加えられる。特に励起源が 1GH
Z 以上、例えば2.45GHZ の周波数にあっては、C-H 結合
より水素を分離し、さらに周波数源が0.1 〜50MHZ 例え
ば13.56MHzの周波数にあってはC-C 結合、C=C 結合を分
解し、-C-C- 結合を作り、炭素の不対結合手同志を互い
に衝突させて共有結合させ、安定なダイヤモンド構造を
局部的に有した構造とさせ得る。The reaction system (8) was provided with a first electrode (11) and a second electrode (12). In this case, the condition of (first electrode area / second electrode area) <1 was satisfied. A pair of electrodes (1
High frequency power supply (13) and matching transformer (1) between (1) and (12)
4), electric energy is applied from the DC bias power source (15) to generate plasma. Exhaust system (16) is a pressure regulating valve
(17), the turbo molecular pump (18) and the rotary pump (19) are exhausted to exhaust unnecessary gas. The reaction space for the reactive gas
The pressure at (20) is 0.001 to 10 torr, typically 0.01 to 0.
By high frequency or direct current energy under 5torr
Energy of 0.1-5KW is applied. Especially excitation source is 1GH
Z above, for example In the frequency of 2.45 GHz Z, to separate hydrogen from the CH bond, further frequency source CC bonds In the frequency of 0.1 ～50MH Z for example 13.56 MHz, to decompose the C = C bond, A -CC- bond can be formed, and unpaired carbon bonds of carbon atoms can be caused to collide with each other to form a covalent bond, thereby forming a stable diamond structure locally.
【００１４】直流バイアスは-200〜600V( 実質的には-4
00〜+400V)を加える。なぜなら、直流バイアスが零のと
きは自己バイアスが-200V(第２の電極を接地レベルとし
て）を有しているためである。反応性気体は、水素で一
部を希釈した。例えばメタン：Ｈ素＝１：１とした。第
１の電極は冷却手段を有しており、被形成面上の温度を
250 〜-100℃に保持させた。DC bias is -200 to 600V (substantially -4
00- + 400V) is added. This is because the self-bias has -200 V (with the second electrode at the ground level) when the DC bias is zero. The reactive gas was partially diluted with hydrogen. For example, methane: H = 1: 1. The first electrode has a cooling means and controls the temperature on the formation surface.
It was kept at 250 to -100 ° C.
【００１５】本発明では被形成面をカソード電極に置い
た。これは被形成面をアノード側に置いたときとカソー
ド側に置いたときとの形成された炭素膜の膜質を比較し
た場合図２に示すようにカソード側に被形成面を置いた
ときの方が硬度の大きな炭素膜が速い成膜速度で得られ
るからである。尚、図２中の○は触針式表面粗さ計、◇
はエリプソメーターで測定した膜厚、△はエリプソメー
ターによる膜の屈折率を示す。また実験条件は、高周波
エネルギー６０Ｗ、圧力0.015torr メタンの流量 100S
CCM 、基板温度を室温、成膜時間 180分で行った。In the present invention, the surface to be formed is placed on the cathode electrode. This is when comparing the film qualities of the formed carbon film when the formation surface is placed on the anode side and the cathode side, as shown in FIG. 2, when the formation surface is placed on the cathode side. The reason is that a carbon film having high hardness can be obtained at a high film forming rate. The circles in Fig. 2 are stylus-type surface roughness meters, and
Indicates the film thickness measured by an ellipsometer, and Δ indicates the refractive index of the film measured by the ellipsometer. The experimental conditions are: high frequency energy 60 W, pressure 0.015 torr methane flow 100 S
CCM, substrate temperature was room temperature, and film formation time was 180 minutes.
【００１６】以上のようにしてプラズマにより被形成面
上にビッカース硬度2000Kg/mm2以上を有するとともに、
熱伝導度2.5W/cm deg 以上のC-C 結合を多数形成したア
モルファス構造または微結晶構造を有するアモルファス
構造の炭素を生成させた。さらにこの電磁エネルギは50
W 〜1KW を供給し、単位面積あたり0.03〜3W/cm2のプラ
ズマエネルギを加えた。As described above, the plasma has a Vickers hardness of 2000 Kg / mm 2 or more on the surface to be formed, and
Carbon with an amorphous structure or a microcrystalline structure having a large number of CC bonds with a thermal conductivity of 2.5 W / cm deg or more was formed. Furthermore, this electromagnetic energy is 50
W ~ 1 KW was supplied, and plasma energy of 0.03 ~ 3 W / cm 2 was applied per unit area.
【００１７】図３には本発明に用いる装置において加え
る高周波エネルギーを変えて炭素膜を形成させたときの
成膜速度と膜のビッカース硬度を示した。 加える高周
波エネルギーが大きい程、硬い膜が形成される。図４に
は、反応圧力を変化させて炭素膜を形成させたときの成
膜速度と膜のビッカース硬度とを示した。反応圧力が小
さい程、硬い膜が形成されている。図５は加える高周波
エネルギーと反応圧力及びセルフバイアスとの関係を示
したものである。高周波エネルギーが大きい程セルフバ
イアスが大きくなり、また反応圧力は小さい方がセルフ
バイアスが大きくなる。この図５と図３及び図４とによ
りセルフトバイアスが大きい程形成された炭素膜も硬い
ものが得られることがわかる。FIG. 3 shows the deposition rate and the Vickers hardness of the film when the carbon film was formed by changing the high frequency energy applied in the apparatus used in the present invention. The higher the applied high frequency energy, the harder the film is formed. FIG. 4 shows the film forming rate and the Vickers hardness of the film when the carbon film was formed by changing the reaction pressure. The smaller the reaction pressure is, the harder the film is formed. FIG. 5 shows the relationship between the applied high frequency energy, the reaction pressure and the self-bias. The larger the high-frequency energy, the larger the self-bias, and the smaller the reaction pressure, the larger the self-bias. From FIGS. 5 and 3 and 4, it can be seen that the harder the carbon film formed, the larger the self bias.
【００１８】〔実施例１〕図１に示した装置において、
被形成面を有した基板上に本発明方法により炭素膜を形
成しした。 先ず反応系にノズルより水素の添加された
メタンを１００SCCMの流量で導入し、圧力を0.03torrに
保持し、メタンに対し５０Ｗの高周波エネルギを加え、
セルフバイアス−１５０Ｖの条件で室温に保持されたSi
基板上に１５０分間膜形成を行い、第１の層を形成し
た。次にノズルより水素の添加されたメタンを１００SC
CMの流量で導入し、圧力を0.015 torrに保持してメタン
に対し１００Ｗの高周波エネルギを加え、セルフバイア
ス−２００Ｖの条件で被形成面を１５０℃に保持して１
５０分間膜形成を行い第２の層とした。そして第２の層
上にノズルより水素の添加されたメタンを１００SCCMの
流量で導入し、反応系を0/015 torrに保持してメタンに
対し２００Ｗの高周波エネルギを加え、セルフバイアス
−２８０Ｖの条件で被形成面を室温に保持して６０分間
膜形成を行い第３の層とした。これら３つの層のビッカ
ース硬度を測定したところ第１の層は２２００Kg/mm2、
第２の層は３５００Kg/mm2、第３の層は４２００Kg/m
m2、でありダイヤモンド類似の硬さを表面に有した炭素
膜を被形成面との密着性を良く形成させることができ
た。[Embodiment 1] In the apparatus shown in FIG.
A carbon film was formed by the method of the present invention on a substrate having a formation surface. First, methane to which hydrogen was added was introduced into the reaction system from the nozzle at a flow rate of 100 SCCM, the pressure was maintained at 0.03 torr, and high-frequency energy of 50 W was added to methane,
Si kept at room temperature under the condition of self-bias -150V
A film was formed on the substrate for 150 minutes to form a first layer. Next, 100 SC of methane with hydrogen added from the nozzle
It was introduced at a flow rate of CM, the pressure was kept at 0.015 torr, and high-frequency energy of 100 W was applied to methane.
A film was formed for 50 minutes to form a second layer. Then, hydrogen-added methane was introduced from the nozzle onto the second layer at a flow rate of 100 SCCM, the reaction system was maintained at 0/015 torr, and high-frequency energy of 200 W was applied to the methane under the condition of self-bias-280V. Then, the surface to be formed was kept at room temperature to form a film for 60 minutes to form a third layer. When the Vickers hardness of these three layers was measured, the first layer was 2200 Kg / mm 2 ,
The second layer is 3500 Kg / mm 2 , the third layer is 4200 Kg / m 2.
It was possible to form a carbon film having m 2 and a hardness similar to that of diamond on the surface with good adhesion to the formation surface.
【００１９】〔実施例２〕被形成面を有する基板の置か
れた反応系に水素の添加されたメタンを１００SCCMの流
量で導入し、圧力を0/03torrに保持し、メタンに対し５
０Ｗの高周波エネルギを加え、１５０分間膜形成を行
い、第１の層を形成した。次に第１の層の上に、メタン
に対する高周波エネルギが１５０Ｗである以外は第１の
層と同じ条件で実施し第２の層を形成した。そして第２
の層上に、高周波エネルギを３００Ｗにして６０分間成
膜する以外は第１の層と同一条件で実施した。その結
果、２２００Kg/mm2、３８００Kg/mm2、５０００Kg/m
m2、のビッカース硬度を有する第１の層、第２の層、第
３の層からなる炭素膜を形成させることができた。この
炭素膜は表面の硬度が５０００Kg/mm2とダイヤモンド類
似の硬さを有し、耐摩耗性、高熱伝導性、高平滑性に優
れたものであった。Example 2 Hydrogen-added methane was introduced into a reaction system on which a substrate having a surface to be formed was placed at a flow rate of 100 SCCM, the pressure was kept at 0/03 torr, and the methane was adjusted to 5 methane.
A high frequency energy of 0 W was applied to form a film for 150 minutes to form a first layer. Next, a second layer was formed on the first layer under the same conditions as the first layer except that the high frequency energy for methane was 150 W. And the second
It was carried out under the same conditions as those for the first layer except that the high frequency energy was set to 300 W and the film was formed on the layer for 60 minutes. As a result, 2200Kg / mm 2 , 3800Kg / mm 2 , 5000Kg / m
A carbon film having a Vickers hardness of m 2 and composed of a first layer, a second layer, and a third layer could be formed. This carbon film had a surface hardness of 5000 kg / mm 2 and a hardness similar to diamond, and was excellent in wear resistance, high thermal conductivity and high smoothness.
【００２０】本実施例においては高周波エネルギの出力
のみを増加させることにより炭素膜の硬度を大きくした
が、反応圧力のみを減少させても同様な効果が得られる
ことは前述した通りである。また本実施例では各炭素膜
の層を一つの反応室を用いて作成したが、反応室を複数
接続させることにより各層をそれぞれ異なる反応室で形
成させても良い。In the present embodiment, the hardness of the carbon film is increased by increasing only the output of high frequency energy, but the same effect can be obtained by decreasing only the reaction pressure, as described above. Further, in the present embodiment, each carbon film layer was formed using one reaction chamber, but each layer may be formed in a different reaction chamber by connecting a plurality of reaction chambers.
【００２１】〔実施例３〕本実施例においては、被形成
面上に硬度の異なる層を積層させるのではなく、高周波
エネルギを連続的に増加させることにより硬度が連続的
に変化している炭素膜を形成させた。先ず、実施例１の
第１の層を形成させるのと同一の条件で膜形成を開始
し、その後高周波エネルギを0.７〜２W/min の上昇率で
３００Ｗになるまで増加させることにより被形成面上に
炭素膜を形成させた。形成させた炭素膜は、表面におい
て４０００Kg/mm2のビッカース硬度を有する、耐摩耗
性、高熱伝導性、高平滑性に優れたものであった。[Embodiment 3] In the present embodiment, carbon whose hardness is continuously changed by continuously increasing high-frequency energy is not formed by laminating layers having different hardness on the formation surface. A film was formed. First, the film formation is started under the same conditions as the formation of the first layer of Example 1, and then the high frequency energy is increased at an increase rate of 0.7 to 2 W / min until it reaches 300 W. A carbon film was formed on the surface. The formed carbon film had a Vickers hardness of 4000 kg / mm 2 on the surface and was excellent in wear resistance, high thermal conductivity and high smoothness.
【００２２】本実施例では高周波エネルギのみを連続的
に大きくさせたが、反応圧力のみを連続的に減少させて
も良く、また高周波エネルギを連続的に大きくさせると
共に反応圧力を連続的に減少させても良い。また反応性
気体に添加する添加物の量を連続的に変化させても良
く、添加物の変化と高周波エネルギの増加若しくは反応
圧力の減少とを組み合わせても本発明の方法を実施する
ことはできる。Although only the high frequency energy is continuously increased in this embodiment, only the reaction pressure may be continuously decreased. Alternatively, the high frequency energy may be continuously increased and the reaction pressure may be continuously decreased. May be. Further, the amount of the additive added to the reactive gas may be continuously changed, and the method of the present invention can be carried out by combining the change of the additive and the increase of the high frequency energy or the decrease of the reaction pressure. .
【００２３】〔実施例４〕本実施例は、被形成面上に炭
素膜を形成する前に、プラズマ活性にした不活性気体ま
たは水素の雰囲気に被形成面を配設することにより被形
成面の酸化物、炭化物または窒化物等の汚染物または異
物を除去した後に炭素膜を形成させた。不活性気体また
は水素をプラズマ化するための手段は、0.1 〜100MHZ
の高周波や1 〜10GHZ のマイクロ波を用い、加えるエネ
ルギーは10〜1000W で十分である。プラズマ化に際して
の反応系の圧力は10-3torr以上、代表的には0.01〜200t
orr 好ましくは1 〜10torrである。以上のような条件の
下で不活性気体または水素をプラズマ活性にし、その活
性化した水素または不活性気体により被形成面上の酸化
物、汚物、水酸化物、さらにまたはこれらの局部性によ
る表面張力、物理吸着力を除去した。このような処理を
した後被形成面上に実施例１、実施例２若しくは実施例
３に従って炭素膜を形成した。得られた炭素膜は被形成
面との密着性に優れたものであった。[Embodiment 4] In this embodiment, the surface to be formed is arranged by forming the surface to be formed in an atmosphere of plasma-activated inert gas or hydrogen before forming the carbon film on the surface to be formed. After removing contaminants such as oxides, carbides, or nitrides or foreign substances, the carbon film was formed. Means for plasma of inert gas or hydrogen, 0.1 ~100MH Z
Using a microwave frequency and 1 ~10GH Z, energy applied is sufficient 10～1000W. The pressure of the reaction system during plasmaization is 10 -3 torr or more, typically 0.01 to 200 t
orr It is preferably 1 to 10 torr. Under the above conditions, the inert gas or hydrogen is plasma-activated, and the activated hydrogen or inert gas causes oxides, dirt, or hydroxides on the surface to be formed, and / or the surface due to locality of these. The tension and physical adsorption force were removed. After such treatment, a carbon film was formed on the surface to be formed according to Example 1, Example 2 or Example 3. The obtained carbon film had excellent adhesion to the formation surface.
【００２４】[0024]
【発明の効果】以上の如く本発明の方法により作製した
炭素または炭素を主成分とする被膜は被形成面上に密接
した炭素または炭素を主成分とする被膜は、被形成面に
損傷を与えない程度のセルフバイアスで作り得る硬さの
炭素または炭素を主成分とする被膜にしておき、徐々に
硬度を上げた膜を積層させて、表面には所望の硬度を有
した炭素または炭素を主成分とする被膜を形成している
ため、被形成面との密着性に優れたダイヤモンドに類似
の硬さを有するものであり、磁気ヘッドや磁気ディスク
等一部に異種材料がその表面ををこすって走行する電気
用部材にきわめて有効であった。As described above, the carbon or the coating containing carbon as the main component, which is produced by the method of the present invention, is closely adhered to the surface to be formed. A carbon film with a hardness that can be produced with a self-bias of a certain degree or a coating film containing carbon as the main component is deposited, and films with gradually increasing hardness are laminated, and carbon or carbon with the desired hardness is mainly formed on the surface. Since it has a coating film as a component, it has a hardness similar to that of diamond, which has excellent adhesion to the surface to be formed. It was extremely effective as an electric component that runs on the road.
【００２５】特に得られる炭素または炭素を主成分とす
る被膜は熱伝導率が2.5W/cm deg 以上、代表的には4.0
〜6.0W/cm deg とダイヤモンドの60W/cm deg に近いた
め摩擦によって生じる熱を全体に均一に逃すことが可能
であり、更に耐摩耗性、高熱伝導性、炭素膜特有の高平
滑性等の特性を有するものであった。Particularly, the obtained carbon or a coating film containing carbon as a main component has a thermal conductivity of 2.5 W / cm deg or more, typically 4.0
Since it is close to ~ 6.0W / cm deg and 60W / cm deg of diamond, it is possible to dissipate the heat generated by friction evenly throughout, and further wear resistance, high thermal conductivity, high smoothness peculiar to carbon film, etc. It had characteristics.
【００２６】また本発明の方法は、有機樹脂、ガラス、
磁性体、金属、セラミックまたは半導体等を被形成面と
して実施することができるため、その反応は計り知れな
いものである。Further, the method of the present invention comprises an organic resin, glass,
The reaction is immeasurable since it can be carried out using a magnetic material, metal, ceramic, semiconductor or the like as the surface to be formed.
【図１】 本発明に使用する装置の概要を示す図。FIG. 1 is a diagram showing an outline of an apparatus used in the present invention.
【図２】 炭素膜の膜質を示す図。FIG. 2 is a diagram showing the film quality of a carbon film.
【図３】 高周波エネルギの出力と成膜速度及びビッカ
ース硬度を示す図。FIG. 3 is a diagram showing an output of high-frequency energy, a film formation rate, and Vickers hardness.
【図４】 反応圧力と成膜速度及びビッカース硬度を示
す図。FIG. 4 is a diagram showing reaction pressure, film formation rate, and Vickers hardness.
【図５】 高周波エネルギと反応圧力及びセルフバイア
スとの関係を示した図。FIG. 5 is a diagram showing the relationship between high-frequency energy, reaction pressure, and self-bias.
【図６】 炭素膜の膜厚と硬度の関係を示す図。FIG. 6 is a diagram showing the relationship between the film thickness and the hardness of a carbon film.
１・・・ドーピング系 ６・・・バルブ ７・・・流量計 ８・・・反応系 ９・・・ノズル １０・・・マイクロ波エネルギ １１・・・第１の電極 １２・・・第２の電極 １３・・・高周波電源 １４・・・マッチングトランス １５・・・直流バイアス電源 １６・・・排気系 １７・・・圧力調整バルブ １８・・・ターボ分子ポンプ １９・・・ロータリーポンプ ２０・・・反応空間 DESCRIPTION OF SYMBOLS 1 ... Doping system 6 ... Valve 7 ... Flow meter 8 ... Reaction system 9 ... Nozzle 10 ... Microwave energy 11 ... First electrode 12 ... Second Electrode 13 ... High frequency power supply 14 ... Matching transformer 15 ... DC bias power supply 16 ... Exhaust system 17 ... Pressure control valve 18 ... Turbo molecular pump 19 ... Rotary pump 20 ... Reaction space
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ３０Ｂ 29/04 8216−4Ｇ Ｚ 8216−4Ｇ Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // C30B 29/04 8216-4G Z 8216-4G
Claims (2)
る被膜であって、 前記被膜はその表面に向かって連続的に硬度が高められ
ていることを特徴とする炭素または炭素を主成分とする
被膜。1. A coating containing carbon as a main component formed on a surface to be formed, wherein the coating has a hardness continuously increased toward the surface thereof. A coating that is the main component.
る被膜であって、 前記被膜はその表面に向かって段階的に硬度が高められ
ていることを特徴とする炭素または炭素を主成分とする
被膜。2. A coating containing carbon as a main component formed on a surface to be formed, wherein the coating has a hardness gradually increased toward the surface. A coating that is the main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6197516A JP2990220B2 (en) | 1994-07-30 | 1994-07-30 | Carbon or carbon-based coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6197516A JP2990220B2 (en) | 1994-07-30 | 1994-07-30 | Carbon or carbon-based coating |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63050397A Division JP2610469B2 (en) | 1988-02-26 | 1988-03-02 | Method for forming carbon or carbon-based coating |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22757097A Division JP3192109B2 (en) | 1997-08-07 | 1997-08-07 | Electrical components |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07102377A true JPH07102377A (en) | 1995-04-18 |
| JP2990220B2 JP2990220B2 (en) | 1999-12-13 |
Family
ID=16375769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6197516A Expired - Lifetime JP2990220B2 (en) | 1994-07-30 | 1994-07-30 | Carbon or carbon-based coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2990220B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6330013B1 (en) | 1997-02-07 | 2001-12-11 | Fuji Photo Fim Co., Ltd. | Thermal head and method of manufacturing the same |
| JP2007324353A (en) * | 2006-05-31 | 2007-12-13 | Tocalo Co Ltd | Member for semiconductor machining device and manufacturing method therefor |
| JP2008081630A (en) * | 2006-09-28 | 2008-04-10 | Brother Ind Ltd | Sliding member |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184681A (en) * | 1984-03-02 | 1985-09-20 | Sharp Corp | Amorphous silicon carbide film for coating |
| JPS6173882A (en) * | 1984-09-17 | 1986-04-16 | Sumitomo Electric Ind Ltd | Material coated with very hard layer |
-
1994
- 1994-07-30 JP JP6197516A patent/JP2990220B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184681A (en) * | 1984-03-02 | 1985-09-20 | Sharp Corp | Amorphous silicon carbide film for coating |
| JPS6173882A (en) * | 1984-09-17 | 1986-04-16 | Sumitomo Electric Ind Ltd | Material coated with very hard layer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6330013B1 (en) | 1997-02-07 | 2001-12-11 | Fuji Photo Fim Co., Ltd. | Thermal head and method of manufacturing the same |
| JP2007324353A (en) * | 2006-05-31 | 2007-12-13 | Tocalo Co Ltd | Member for semiconductor machining device and manufacturing method therefor |
| JP4563966B2 (en) * | 2006-05-31 | 2010-10-20 | トーカロ株式会社 | Semiconductor processing apparatus member and method for manufacturing the same |
| JP2008081630A (en) * | 2006-09-28 | 2008-04-10 | Brother Ind Ltd | Sliding member |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2990220B2 (en) | 1999-12-13 |
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