JPH05140744A - Formation of dlc-si film - Google Patents
Formation of dlc-si filmInfo
- Publication number
- JPH05140744A JPH05140744A JP3300649A JP30064991A JPH05140744A JP H05140744 A JPH05140744 A JP H05140744A JP 3300649 A JP3300649 A JP 3300649A JP 30064991 A JP30064991 A JP 30064991A JP H05140744 A JPH05140744 A JP H05140744A
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- substrate
- film
- dlc
- plasma
- chamber
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- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は低摩擦係数を有し密着力
の優れたａ−ＤＬＣ（ダイヤモンド・ライク・カーボ
ン）−Ｓｉ膜の形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an a-DLC (diamond-like carbon) -Si film having a low coefficient of friction and excellent adhesion.
【０００２】[0002]
【従来の技術】ダイヤモンドの気相合成法は、炭化水素
と水素との混合ガスを反応ガスとし、数１０Ｔｏｒｒに
保った反応槽の中で、熱、マイクロ波または高周波等を
用いて反応ガスを励起し、６００〜１０００℃に加熱さ
れた基板上に導いて、炭化水素の熱分解と活性化した水
素の作用により、ダイヤモンド構造の炭素を基板上に析
出させるものである。2. Description of the Related Art The vapor phase synthesis method of diamond uses a mixed gas of hydrocarbon and hydrogen as a reaction gas, and heat, microwave or high frequency is used to generate the reaction gas in a reaction tank kept at several tens Torr. It is excited and guided onto a substrate heated to 600 to 1000 ° C., and the carbon of diamond structure is deposited on the substrate by the thermal decomposition of hydrocarbon and the action of activated hydrogen.
【０００３】このダイヤモンド気相合成法には、主とし
てＣＶＤ法（気相化学反応蒸着法）が用いられるが、Ｃ
ＶＤ法としては熱フィラメント法、マイクロ波プラズマ
法、電子衝撃ＣＶＤ法、直流プラズマ法等がある。例え
ば、マイクロ波プラズマ法では、マイクロ波を励起源と
して、基板周囲にメタン−水素混合ガスを励起したプラ
ズマを発生させ、基板はマイクロ波の吸収とプラズマに
よる衝撃によって加熱され、圧力数Ｔｏｒｒ〜３００Ｔ
ｏｒｒ、基板温度７００〜１０００℃の範囲でダイヤモ
ンドが合成される。In this diamond vapor phase synthesis method, a CVD method (vapor phase chemical reaction vapor deposition method) is mainly used.
Examples of the VD method include a hot filament method, a microwave plasma method, an electron impact CVD method, a direct current plasma method and the like. For example, in the microwave plasma method, plasma is generated by exciting a methane-hydrogen mixed gas around a substrate using microwaves as an excitation source, the substrate is heated by the absorption of the microwave and the impact of the plasma, and the pressure is several Torr to 300T.
Diamond is synthesized in the range of orr and substrate temperature of 700 to 1000 ° C.
【０００４】しかしながら、これらＣＶＤ法では２０〜
２００Ｔｏｒｒの比較的高圧で反応が行われるため、反
応領域または析出範囲に限度があり、広い領域に均一に
ダイヤモンドを析出させることが困難である。この問題
は、反応圧力を低下することによって解決される。何故
ならば、反応圧力を下げることにより、電子の平均自由
工程が長くなり、磁界を使用して広い領域で容易にプラ
ズマ密度を増加することができるからである。However, in these CVD methods,
Since the reaction is performed at a relatively high pressure of 200 Torr, there is a limit in the reaction region or deposition range, and it is difficult to deposit diamond uniformly in a wide region. This problem is solved by lowering the reaction pressure. This is because by lowering the reaction pressure, the mean free path of electrons becomes longer, and the magnetic field can be used to easily increase the plasma density in a wide region.
【０００５】然るに、最近は磁界とマイクロ波エネルギ
ーを用い、電子サイクロトン共鳴（Ｅｌｅｃｔｒｏｎ
Ｃｙｃｌｏｔｒｏｎ Ｒｅｓｏｎａｎｃｅ、以下ＥＣＲ
という）と呼ばれる現象を利用したプラズマ生成法が、
低ガス圧、高活性、高イオン化率等の特徴を有すること
から、プラズマ加工技術として注目され、プラズマＣＶ
Ｄとしても実用化されている。However, recently, electron cyclotron resonance (Electron Resonance) has been used by using magnetic field and microwave energy.
Cyclotron Resonance, ECR
A plasma generation method using a phenomenon called
Because of its features such as low gas pressure, high activity, and high ionization rate, it has attracted attention as a plasma processing technology, and plasma CV
It has been put to practical use as D.
【０００６】ＥＣＲプラズマＣＶＤ装置の基本構成を図
１に従って説明すると、マイクロ波１６は矩形導波管７
を利用してプラズマ室１７へ導入される。マイクロ波と
しては、通常工業周波数である２．４５ＧＨｚが利用さ
れる。プラズマ室１７の周囲には励磁コイル４が配置さ
れ、マイクロ波導入部から反応室１４方向に徐々に磁界
強度が弱くなる発散磁界構成となっており、プラズマ室
内の適当な領域でＥＣＲ条件を満たす磁界を発生させ
る。反応ガス導入管６によってプラズマ室１７に導入さ
れた反応ガスは、プラズマ室１７内で励起され、磁界に
沿ってプラズマ流１８の形で基板１１に供給される。The basic structure of the ECR plasma CVD apparatus will be described with reference to FIG.
Is introduced into the plasma chamber 17 by utilizing. 2.45 GHz, which is an industrial frequency, is usually used as the microwave. The exciting coil 4 is arranged around the plasma chamber 17 and has a divergent magnetic field structure in which the magnetic field strength gradually decreases from the microwave introduction portion toward the reaction chamber 14, and the ECR condition is satisfied in an appropriate region of the plasma chamber. Generate a magnetic field. The reaction gas introduced into the plasma chamber 17 by the reaction gas introduction pipe 6 is excited in the plasma chamber 17 and supplied to the substrate 11 in the form of a plasma flow 18 along the magnetic field.
【０００７】このＥＣＲプラズマＣＶＤ装置を用いて、
ダイヤモンド膜を形成した報告が鈴木等によってなされ
ており（Ｊａｐａｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａ
ｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｖｏｌ．２８，Ｎｏ．
２，１９８９，ｐｐ．Ｌ２８１−Ｌ２８３）、この報告
によると、ＥＣＲ条件の設定により基板周辺で１×１０
11ｃｍ-3の高密度プラズマが得られ、ＣＯ／Ｈ2ガスを
用い、０．１Ｔｏｏｒの低圧で、６００℃の温度で、ダ
イヤモンド膜が得られている。また、このダイヤモンド
膜をラマン光により分析したところ、ダイヤモンドの結
晶質部分とその粒界に析出した非晶質の炭素層とからな
る（通常、ダイヤモンド・ライク・カーボンと称され
る。）ことが確認されている。Using this ECR plasma CVD apparatus,
A report of forming a diamond film has been made by Suzuki et al. (Japane Journal of A
applied Physics Vol. 28, No.
2, 1989, pp. L281-L283), according to this report, depending on the setting of ECR conditions, 1 × 10 around the substrate.
A high density plasma of 11 cm −3 was obtained, and a diamond film was obtained using CO / H 2 gas at a low pressure of 0.1 Toor and a temperature of 600 ° C. When the diamond film was analyzed by Raman light, it was found to consist of a crystalline portion of diamond and an amorphous carbon layer deposited at the grain boundaries (usually called diamond-like carbon). It has been confirmed.
【０００８】一方、これらＥＣＲプラズマＣＶＤ法にお
いて、反応ガスにＳｉの塩化物または水素化物ガスを混
入することにより、ＤＬＣとＳｉの混合膜（ａ−ＤＬＣ
−Ｓｉ）が得られる。このａ−ＤＬＣ−Ｓｉ膜は摩擦係
数が極めて低く、図３に荷重１ｋｇｆ、速度０．４ｍ／
ｓで測定したＣ濃度と摩擦係数の関係を示すが、その摩
擦係数は、Ｃ濃度６５〜９０原子％において、０．０５
と非常に小さい。On the other hand, in these ECR plasma CVD methods, a mixed film of DLC and Si (a-DLC) is obtained by mixing Si chloride or hydride gas into the reaction gas.
-Si) is obtained. This a-DLC-Si film has an extremely low coefficient of friction, and a load of 1 kgf and a speed of 0.4 m /
The relationship between the C concentration measured in s and the friction coefficient is shown. The friction coefficient is 0.05 at a C concentration of 65 to 90 atom%.
And very small.
【０００９】[0009]
【発明が解決しようとする課題】しかしながら、このａ
−ＤＬＣ−Ｓｉ膜は、プラズマＣＶＤ法による低温形成
のアモルファス膜ということで、基板に対する密着性に
劣っている。例えば、従来法で形成されたＣ濃度８０原
子％のａ−ＤＬＣ−Ｓｉ膜の付着力を引っかき法で測定
した結果は、僅か３×１０8ｄｙｎ／ｃｍ2にしかならな
い。However, this a
Since the -DLC-Si film is an amorphous film formed at a low temperature by the plasma CVD method, it has poor adhesion to the substrate. For example, the result of measuring the adhesion force of the a-DLC-Si film having a C concentration of 80 atomic% formed by the conventional method by the scratch method is only 3 × 10 8 dyn / cm 2 .
【００１０】本発明は、ＥＣＲプラズマＣＶＤ法により
低圧かつ低温度で形成されるａ−ＤＬＣ−Ｓｉ膜が密着
性に劣るという前記のごとき問題点を解決するためにな
されたものであって、基板に対する付着力に優れた低摩
擦係数のａ−ＤＬＣ−Ｓｉ膜の形成方法を提供すること
を目的とする。The present invention has been made in order to solve the above-mentioned problem that the a-DLC-Si film formed by the ECR plasma CVD method at a low pressure and a low temperature has poor adhesion. It is an object of the present invention to provide a method for forming an a-DLC-Si film having a low friction coefficient and excellent adhesion to the.
【００１１】[0011]
【課題を解決するための手段】ＥＣＲプラズマＰＶＤ法
は、他のプラズマＣＶＤ法と比べて低圧で、１０-4〜１
０-6Ｔｏｒｒ程度のガス圧で反応が行われる。そこで、
発明者はこのＥＣＲプラズマＰＶＤ法と密着力に優れた
真空蒸着を組み合わせることを着想し、鋭意研究を重ね
た結果、レーザＰＶＤ法とを組み合わせると、付着力に
優れたａ−ＤＬＣ−Ｓｉ膜が得られることを新たに知見
し本発明を完成した。The ECR plasma PVD method is 10 -4 to 1 at a low pressure as compared with other plasma CVD methods.
The reaction is carried out at a gas pressure of about 0 -6 Torr. Therefore,
The inventor has conceived to combine this ECR plasma PVD method with vacuum deposition having excellent adhesiveness, and as a result of earnest research, as a result, when combined with the laser PVD method, an a-DLC-Si film having excellent adhesion was obtained. The inventors have newly found that they can be obtained and completed the present invention.
【００１２】本発明のａ−ＤＬＣ−Ｓｉ膜の形成方法
は、基板を、反応室内において、マイクロ波矩形導波管
と磁気コイルを具備したＥＣＲプラズマ室に対面して斜
めに設置し、前記基板に対向して反応室内にＳｉターゲ
ットを配置し、前記ＥＣＲプラズマ室に反応ガスを導入
してＥＣＲプラズマＣＶＤにより前記基板にＤＬＣ（ダ
イヤモンド・ライク・カーボン）膜を形成するととも
に、前記反応室に設けた入射窓を介してレーザ光をＳｉ
ターゲットに照射してレーザＰＶＤにより前記基板にＳ
ｉを蒸着させ、前記基板上にａ−ＤＬＣ−Ｓｉ膜を形成
することを要旨とする。In the method of forming an a-DLC-Si film of the present invention, the substrate is obliquely installed in the reaction chamber so as to face an ECR plasma chamber equipped with a microwave rectangular waveguide and a magnetic coil. A Si target in the reaction chamber facing the substrate, a reaction gas is introduced into the ECR plasma chamber to form a DLC (diamond-like carbon) film on the substrate by ECR plasma CVD, and the Si target is provided in the reaction chamber. Laser light through the incident window
The target is irradiated and S is applied to the substrate by laser PVD.
The gist is to evaporate i and form an a-DLC-Si film on the substrate.
【００１３】ＥＣＲプラズマＣＶＤは、マイクロ波波長
２．４５ＧＨｚ、磁場８７５ガウスの条件のもとで、マ
イクロ波パワー８００〜１２００Ｗ、ガス圧力０．０１
〜０．１Ｔｏｒｒの間で、プラズマを安定して起こすこ
とができる。ECR plasma CVD uses a microwave power of 800 to 1200 W and a gas pressure of 0.01 under the conditions of a microwave wavelength of 2.45 GHz and a magnetic field of 875 Gauss.
Plasma can be stably generated between 0.1 Torr and 0.1 Torr.
【００１４】Ｈ2で希釈される反応ガスのＣＨ4濃度は、
０．１〜６％とすることが好ましい。ＣＨ4濃度が０．
１％未満ではダイヤモンドの析出速度が極めて遅く殆ど
析出しないからであり、６％を越えるとＣが煤として析
出し、ＤＬＣが形成されないからである。The CH 4 concentration of the reaction gas diluted with H 2 is
It is preferably 0.1 to 6%. CH 4 concentration is 0.
This is because if it is less than 1%, the deposition rate of diamond is extremely slow and hardly deposits, and if it exceeds 6%, C is deposited as soot and DLC is not formed.
【００１５】レーザＰＶＤの条件範囲は、レーザパワ
ー：１〜１５０Ｗ、パルスエネルギー：５０〜４００ｍ
Ｊ、エネルギー密度：０．５〜２００ＫＪ／ｍ2、レー
ザ波長：２４８ｎｍである。なお、レーザ波長はこれ以
外でも可能であって、例えば波長１９３、３０８、３５
１ｎｍのエキシマレーザ、波長１．０６μｍのＹＡＧレ
ーザでも良い。The condition range of the laser PVD is as follows: laser power: 1-150 W, pulse energy: 50-400 m
J, energy density: 0.5 to 200 KJ / m 2 , laser wavelength: 248 nm. The laser wavelength may be other than this, for example, the wavelengths 193, 308, 35.
A 1 nm excimer laser or a YAG laser having a wavelength of 1.06 μm may be used.
【００１６】エネルギー密度を０．５〜２００ＫＪ／ｍ
2としたのは、レーザパワー、パルスエネルギー、スポ
ット径から算出されるエネルギー密度が０．５ＫＪ／ｍ
2よりも小さいと、スパッタ現象が起きないからであ
り、上限値は現在のエキシマレーザの最高値であり、こ
れより大きな値でも差支えない。Energy density of 0.5 to 200 KJ / m
2 means that the energy density calculated from laser power, pulse energy, and spot diameter is 0.5 KJ / m.
This is because if it is smaller than 2 , the spattering phenomenon does not occur, and the upper limit value is the maximum value of the current excimer laser, and a value larger than this value is also acceptable.
【００１７】ダイヤモンドの生成が可能な基板には、モ
リブデン、タングステン、金、銅、ジルコニウム、シリ
コンなどの単体、超硬合金、シリカガラス、サファイヤ
などの化合物のほか、炭化珪素、炭化チタン、窒化ホウ
素、窒化珪素などのセラミックスがある。Substrates capable of producing diamond include simple substances such as molybdenum, tungsten, gold, copper, zirconium and silicon, cemented carbide, silica glass, sapphire and other compounds, as well as silicon carbide, titanium carbide and boron nitride. Ceramics such as silicon nitride.
【００１８】[0018]
【作用】マイクロ波１６は矩形導波管７を利用してプラ
ズマ室１７へ導入される。プラズマ室１７の周囲には励
磁コイル４が配置され、マイクロ波導入部から反応室１
４方向に徐々に磁界強度が弱くなる発散磁界構成となっ
ており、プラズマ室内の適当な領域でＥＣＲ条件を満た
す磁界を発生させる。The microwave 16 is introduced into the plasma chamber 17 using the rectangular waveguide 7. The exciting coil 4 is arranged around the plasma chamber 17, and the reaction chamber
It has a divergent magnetic field structure in which the magnetic field strength gradually weakens in four directions, and a magnetic field that satisfies the ECR condition is generated in an appropriate region in the plasma chamber.
【００１９】ＥＣＲプラズマはその共鳴現象により、電
子が効率良くマイクロ波のエネルギーを吸収し運動エネ
ルギーに変換する。このマイクロ波エネルギーを吸収し
た電子はさらに気体分子に衝突し、低ガス圧で高密度・
高活性なプラズマを発生させる。反応ガス導入管６によ
ってプラズマ室１７に導入された反応ガスは、プラズマ
室１７内で励起され、発散磁界によりプラズマ流１８の
形で基板１１に供給されるので、基板１１の上にＤＬＣ
膜が生成する。In the ECR plasma, due to its resonance phenomenon, electrons efficiently absorb the microwave energy and convert it into kinetic energy. The electrons that have absorbed this microwave energy further collide with gas molecules, resulting in high density and low gas pressure.
Generates highly active plasma. The reaction gas introduced into the plasma chamber 17 by the reaction gas introduction pipe 6 is excited in the plasma chamber 17 and supplied to the substrate 11 in the form of a plasma flow 18 by the divergent magnetic field.
A film forms.
【００２０】一方、これと同時にレーザ光１がレンズ２
で集光されて入射窓３を通して反応室１４内に設置され
たＳｉターゲット１０に照射される。レーザ光１がＳｉ
ターゲット１０に照射されると、ターゲット１０の表面
がアブソレーションを起こし、ターゲット１０から放出
されるＳｉ蒸発粒子が対向して置かれた基板上にＤＬＣ
膜とともに堆積する。この蒸発粒子は非常に高いエネル
ギーを持っているので、基板１１上に密着性に優れたａ
−ＤＬＣ−Ｓｉ膜が形成される。On the other hand, at the same time, the laser light 1 is reflected by the lens 2
Then, the Si target 10 is focused and is irradiated through the entrance window 3 to the Si target 10 installed in the reaction chamber 14. Laser light 1 is Si
When the target 10 is irradiated, the surface of the target 10 is ablated, and Si vaporized particles emitted from the target 10 are placed on the substrate facing each other by DLC.
Deposit with the film. Since these evaporated particles have very high energy, they have excellent adhesion on the substrate 11.
A -DLC-Si film is formed.
【００２１】[0021]
【実施例】本発明の実施例を従来例と比較して説明し、
本発明の効果を明らかにする。図１は本発明方法の実施
に用いた装置の概略断面図である。反応室１４は基板１
１およびターゲット１０が設置される真空室であって、
底面には排気管１５が設けられ真空排気されている。ま
た、反応室１４の上面はプラズマ室１７と連通してお
り、側面には入射窓３が設けられている。EXAMPLES Examples of the present invention will be described in comparison with conventional examples,
The effect of the present invention will be clarified. FIG. 1 is a schematic sectional view of an apparatus used for carrying out the method of the present invention. The reaction chamber 14 is the substrate 1
1 and a vacuum chamber in which the target 10 is installed,
An exhaust pipe 15 is provided on the bottom surface for vacuum exhaust. The upper surface of the reaction chamber 14 communicates with the plasma chamber 17, and the entrance window 3 is provided on the side surface.
【００２２】プラズマ室１７の外周にはウオータージャ
ケットが設けられ冷却水５によって冷却されており、さ
らにその周囲には励磁コイル４が配置されている。ま
た、プラズマ室１７の上面には矩形導波管７が取り付け
られ、マイクロ波１６がプラズマ室１７へ導入される。
さらに、プラズマ室１７には反応ガス導入管６が取り付
けられ水素で希釈されたメタンガスが反応ガスとして供
給される。A water jacket is provided on the outer periphery of the plasma chamber 17 and is cooled by cooling water 5, and an exciting coil 4 is arranged around the water jacket. Further, the rectangular waveguide 7 is attached to the upper surface of the plasma chamber 17, and the microwave 16 is introduced into the plasma chamber 17.
Further, a reaction gas introduction pipe 6 is attached to the plasma chamber 17, and methane gas diluted with hydrogen is supplied as a reaction gas.
【００２３】一方、反応室１４内のプラズマ室８に対面
する位置には、基板ホルダー１２に固定された基板１１
が配置されており、さらにこの基板１１に対向し、かつ
側面の入射窓３から臨む位置には、ターゲットホルダー
９に支持されたＳｉターゲット１０がレーザ光１に４５
°の角度をなして設置されている。On the other hand, at a position facing the plasma chamber 8 in the reaction chamber 14, the substrate 11 fixed to the substrate holder 12 is provided.
Is arranged. Further, at a position facing the substrate 11 and facing the incident window 3 on the side surface, the Si target 10 supported by the target holder 9 is exposed to the laser light 1 45.
It is installed at an angle of °.
【００２４】この装置の作動について説明すると、２．
４５ＧＨｚのマイクロ波１６は矩形導波管７を利用して
プラズマ室１７へ導入される。プラズマ室１７の周囲に
配置されたは励磁コイル４は、マイクロ波導入部から反
応室１４方向に徐々に磁界強度が弱くなる発散磁界構成
となっており、８７５ＧのＥＣＲ条件によって、プラズ
マ８を発生させる。The operation of this device will be described below.
The 45 GHz microwave 16 is introduced into the plasma chamber 17 using the rectangular waveguide 7. The excitation coil 4 arranged around the plasma chamber 17 has a divergent magnetic field structure in which the magnetic field strength gradually decreases from the microwave introduction part toward the reaction chamber 14, and the plasma 8 is generated according to the ECR condition of 875G. Let
【００２５】ＥＣＲプラズマはその共鳴現象により、電
子が効率良くマイクロ波のエネルギーを吸収し運動エネ
ルギーに変換する。このマイクロ波エネルギーを吸収し
た電子はさらに気体分子に衝突し、低ガス圧で高密度・
高活性なプラズマを発生させる。そこで、反応ガス導入
管６によってプラズマ室１７に導入された反応ガスは、
プラズマ室１７内で励起され、発散磁界によりプラズマ
流１８の形で基板１１に供給されるので、基板１１の上
にＤＬＣ膜が生成する。Due to the resonance phenomenon of ECR plasma, electrons efficiently absorb microwave energy and convert it into kinetic energy. The electrons that have absorbed this microwave energy further collide with gas molecules, resulting in high density and low gas pressure.
Generates highly active plasma. Therefore, the reaction gas introduced into the plasma chamber 17 by the reaction gas introduction pipe 6 is
A DLC film is formed on the substrate 11 as it is excited in the plasma chamber 17 and supplied to the substrate 11 in the form of a plasma stream 18 by a divergent magnetic field.
【００２６】一方、これと同時にレーザ光１がレンズ２
で集光されて入射窓３を通して反応室１４内に設置され
たＳｉターゲット１０に照射される。レーザ光１がＳｉ
ターゲット１０に照射されると、ターゲット１０の表面
がアブソレーションを起こし、ターゲット１０から放出
されるＳｉ蒸発粒子が対向して置かれた基板上にＤＬＣ
膜とともに堆積するので、基板１１上に密着性に優れた
ａ−ＤＬＣ−Ｓｉ膜が形成される。On the other hand, at the same time, the laser light 1 is reflected by the lens 2
Then, the Si target 10 is focused and is irradiated through the entrance window 3 to the Si target 10 installed in the reaction chamber 14. Laser light 1 is Si
When the target 10 is irradiated, the surface of the target 10 is ablated, and Si vaporized particles emitted from the target 10 are placed on the substrate facing each other by DLC.
Since it is deposited together with the film, an a-DLC-Si film having excellent adhesion is formed on the substrate 11.
【００２７】（実施例１）この装置を用い、本発明方法
により下記の条件によりａ−ＤＬＣ−Ｓｉ膜を形成した
ところ、Ｃ濃度８０原子％のａ−ＤＬＣ−Ｓｉ膜を得
た。 レーザパルスエネルギー ２００ｍＪ レーザパワー ２０Ｗ レーザの繰り返し発振回数 １００ｐｐｓ ターゲット上のスポット径 ２ｍｍ×７ｍｍの楕円形 エネルギー密度 １４ＫＪ／ｍ2 反応ガス ＣＨ4：１％、Ｈ2：９９％ 真空度 ０．０２Ｔｏｒｒ マイクロ波パワー １０００Ｗ 基板温度 ８００℃Example 1 Using this apparatus, an a-DLC-Si film was formed by the method of the present invention under the following conditions, and an a-DLC-Si film having a C concentration of 80 atomic% was obtained. Laser pulse energy 200 mJ Laser power 20 W Repetitive oscillation frequency of laser 100 pps Spot diameter 2 mm × 7 mm on target Elliptical energy density 14 KJ / m 2 Reactive gas CH 4 : 1%, H 2 : 99% Vacuum degree 0.02 Torr microwave Power 1000W Substrate temperature 800 ℃
【００２８】比較のために、従来の直流プラズマＣＶＤ
法により、下記の条件でａ−ＤＬＣ−Ｓｉ膜を形成した
ところ、Ｃ濃度８０原子％のａ−ＤＬＣ−Ｓｉ膜を得
た。 反応ガス ＣＨ4：４％、ＳｉＣｌ4：０．３％ Ｈ2：５８％、Ａｒ：３７．７％ 真空度 ４Ｔｏｒｒ ＤＣ電圧 ４００Ｖ 基板温度 ５５０℃For comparison, conventional DC plasma CVD
When an a-DLC-Si film was formed by the method under the following conditions, an a-DLC-Si film having a C concentration of 80 atomic% was obtained. Reaction gas CH 4: 4%, SiCl 4 : 0.3% H 2: 58%, Ar: 37.7% vacuum 4 Torr DC voltage 400V substrate temperature 550 ° C.
【００２９】得られた本発明例と従来例のａ−ＤＬＣ−
Ｓｉ膜について、その付着力を評価した。付着力は引っ
かき法で測定したものであって、この引っかき法は硬い
針を薄膜に垂直に押し付けて、荷重をかけて動かし、引
っかきによって薄膜が基板から引き剥がす方法である。
得られた結果は図２にまとめて示した。The obtained a-DLC-of the present invention and the conventional example
The adhesive force of the Si film was evaluated. The adhesive force is measured by a scratching method, and the scratching method is a method in which a hard needle is vertically pressed against a thin film, a load is moved, and the thin film is peeled from a substrate by scratching.
The obtained results are summarized in FIG.
【００３０】図２から明らかなように、従来例で形成さ
れたのａ−ＤＬＣ−Ｓｉ膜は付着力が僅かに３×１０8
ｄｙｎ／ｃｍ2であったが、本発明方法で成膜したもの
では、５０×１０8ｄｙｎ／ｃｍ2の高い付着力を示し、
本発明の効果が確認された。なお、ここではエキシマレ
ーザを用いており、エキシマレーザスパッタによって飛
び出してくる蒸発粒子は、非常に高いエネルギーを持っ
ているので、膜の密着力をこのように高くすることが可
能である。As is apparent from FIG. 2, the a-DLC-Si film formed in the conventional example has an adhesive force of only 3 × 10 8.
Although it was dyn / cm 2 , the film formed by the method of the present invention shows a high adhesive force of 50 × 10 8 dyn / cm 2 ,
The effect of the present invention was confirmed. Note that an excimer laser is used here, and the vaporized particles ejected by the excimer laser sputtering have extremely high energy, so that the adhesion of the film can be increased in this way.
【００３１】（実施例２）図１の装置を用い、本発明方
法により、表１に示す条件でａ−ＤＬＣ−Ｓｉ膜を形成
したところ、表１に示すＣ濃度％の膜が得られた。な
お、ＥＣＲ条件は１０００Ｗ、レーザ条件は２００ｍ
Ｊ、ターゲット上のスポット径：２ｍｍ×７ｍｍの楕円
で、それぞれ一定とした。得られた膜について、ボール
オンディスク方式の摩擦摩耗試験機（相手材：直径６．
３５ｍｍ（１／４インチ）ＳＵＪ２ボール）を用い摩擦
係数を測定し、得られた結果を図３に示した。(Example 2) When an a-DLC-Si film was formed under the conditions shown in Table 1 by the method of the present invention using the apparatus shown in FIG. 1, a film having a C concentration% shown in Table 1 was obtained. .. ECR condition is 1000 W, laser condition is 200 m
J, spot diameter on target: ellipse of 2 mm × 7 mm, which was constant. For the obtained film, a ball-on-disk type friction wear tester (counterpart material: diameter 6.
The friction coefficient was measured using a 35 mm (1/4 inch) SUJ2 ball), and the obtained results are shown in FIG.
【００３２】[0032]
【表１】 なお、表中のｐｐｓは１秒間当たりの発振回数。[Table 1] Note that pps in the table is the number of oscillations per second.
【００３３】表１に示したように、本発明方法によれ
ば、レーザ繰り返し周波数、マイクロ波パワー等を変え
ることにより、ａ−ＤＬＣ−Ｓｉ膜中のＤＬＣとＳｉの
割合を自由に変えることができる。また、図３から明ら
かなように、Ｃ濃度６５〜９５％において、形成された
膜の摩擦係数は０．０５と非常に小さな値を示した。As shown in Table 1, according to the method of the present invention, the ratio of DLC and Si in the a-DLC-Si film can be freely changed by changing the laser repetition frequency, the microwave power and the like. it can. Further, as is clear from FIG. 3, the friction coefficient of the formed film showed a very small value of 0.05 at a C concentration of 65 to 95%.
【００３４】[0034]
【発明の効果】本発明のａ−ＤＬＣ−Ｓｉ膜の形成方法
は以上詳述したように、基板を、反応室内において、Ｅ
ＣＲプラズマ室に対面して斜めに設置し、ＥＣＲプラズ
マ室に反応ガスを導入してＥＣＲプラズマＣＶＤにより
基板にＤＬＣ（ダイヤモンド・ライク・カーボン）膜を
形成するとともに、基板に対向して反応室内に配置した
Ｓｉターゲットにレーザを照射してレーザＰＶＤにより
基板にＳｉを蒸着させ、基板上にａ−ＤＬＣ−Ｓｉ膜を
形成するものであって、プラズマ室に導入された反応ガ
スは、プラズマ室内で励起され、発散磁界によりプラズ
マ流の形で基板に供給されるので、基板の上にＤＬＣ膜
が生成するとともに、レーザＰＶＤにより高いエネルギ
ーのＳｉ蒸発粒子が蒸着するので、密着性の優れたａ−
ＤＬＣ−Ｓｉ膜が形成される。As described above in detail, the method for forming an a-DLC-Si film of the present invention is performed by using the substrate in a reaction chamber to remove E
It is installed diagonally so as to face the CR plasma chamber, and a reaction gas is introduced into the ECR plasma chamber to form a DLC (diamond-like carbon) film on the substrate by ECR plasma CVD, while facing the substrate and inside the reaction chamber. The arranged Si target is irradiated with a laser to deposit Si on the substrate by laser PVD to form an a-DLC-Si film on the substrate, and the reaction gas introduced into the plasma chamber is in the plasma chamber. Since it is excited and supplied to the substrate in the form of a plasma flow by a divergent magnetic field, a DLC film is formed on the substrate, and high energy Si vaporized particles are deposited by the laser PVD.
A DLC-Si film is formed.
【図１】本発明を実施するための装置の概略側断面図で
ある。1 is a schematic side sectional view of an apparatus for practicing the present invention.
【図２】本発明方法により形成された膜と従来方法によ
り形成された膜の付着力を示す図である。FIG. 2 is a diagram showing the adhesive force between a film formed by the method of the present invention and a film formed by a conventional method.
【図３】本発明方法により形成されたａ−ＤＬＣ−Ｓｉ
膜の摩擦係数とＣ濃度との関係を示す線図である。FIG. 3 is a-DLC-Si formed by the method of the present invention.
It is a diagram showing the relationship between the friction coefficient of the film and the C concentration.
１ レーザ光 ３ 入射窓 ４ 励磁コイル ６ 反応ガス導入
管 ７ 矩形導波管 ８ プラズマ １０ ターゲット １１ 基板 １３ 蒸発粒子 １４ 反応室 １６ マイクロ波 １７ ブラズマ室 １８ プラズマ流1 Laser Light 3 Incident Window 4 Excitation Coil 6 Reactive Gas Introducing Tube 7 Rectangular Waveguide 8 Plasma 10 Target 11 Substrate 13 Evaporated Particles 14 Reaction Chamber 16 Microwave 17 Plasma Chamber 18 Plasma Flow
Claims (1)
矩形導波管と磁気コイルを具備したＥＣＲプラズマ室に
対面して斜めに設置し、前記基板に対向して反応室内に
Ｓｉターゲットを配置し、前記ＥＣＲプラズマ室に反応
ガスを導入してＥＣＲプラズマＣＶＤにより前記基板に
ＤＬＣ（ダイヤモンド・ライク・カーボン）膜を形成す
るとともに、前記反応室に設けた入射窓を介してレーザ
光をＳｉターゲットに照射してレーザＰＶＤにより前記
基板にＳｉを蒸着させ、前記基板上にａ−ＤＬＣ−Ｓｉ
膜を形成することを特徴とするａ−ＤＬＣ−Ｓｉ膜の形
成方法。1. A substrate is diagonally installed in a reaction chamber so as to face an ECR plasma chamber equipped with a microwave rectangular waveguide and a magnetic coil, and a Si target is arranged in the reaction chamber facing the substrate. A reaction gas is introduced into the ECR plasma chamber to form a DLC (diamond-like carbon) film on the substrate by ECR plasma CVD, and laser light is directed to a Si target through an entrance window provided in the reaction chamber. Irradiation is performed to deposit Si on the substrate by laser PVD, and a-DLC-Si is deposited on the substrate.
A method for forming an a-DLC-Si film, which comprises forming a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03300649A JP3082979B2 (en) | 1991-11-15 | 1991-11-15 | Method for forming a-DLC-Si film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03300649A JP3082979B2 (en) | 1991-11-15 | 1991-11-15 | Method for forming a-DLC-Si film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05140744A true JPH05140744A (en) | 1993-06-08 |
| JP3082979B2 JP3082979B2 (en) | 2000-09-04 |
Family
ID=17887401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03300649A Expired - Fee Related JP3082979B2 (en) | 1991-11-15 | 1991-11-15 | Method for forming a-DLC-Si film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3082979B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005001972A (en) * | 2003-06-10 | 2005-01-06 | Kansai Tlo Kk | Method and base material for forming diamond film |
| KR100545719B1 (en) * | 1998-09-25 | 2006-03-31 | 학교법인연세대학교 | Protective coating layer material for AC plasma display panel device |
| CN100336935C (en) * | 2004-02-03 | 2007-09-12 | 旺宏电子股份有限公司 | Physical gaseous phase deposition technology and its equipment |
| KR101412070B1 (en) * | 2013-12-05 | 2014-07-01 | 송길용 | Scriber fixing pin for evaporation a diamond-like carbon thin film method and apparatus, using this scriber fixing pin |
| JP2015081358A (en) * | 2013-10-22 | 2015-04-27 | 三井造船株式会社 | Coating film formation apparatus and method of forming coating film |
| KR20210144446A (en) * | 2020-05-22 | 2021-11-30 | (주)아이네쓰 | Thin film depostion apparatus and DLC thin film coating methos using the appartus |
Families Citing this family (1)
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| PL223008B1 (en) | 2012-03-15 | 2016-09-30 | Borowski Józef Przedsiębiorstwo Produkcyjno Usługowo Handlowe Medgal | Method for producing the silicon-containing carbon layer on medical implants |
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1991
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100545719B1 (en) * | 1998-09-25 | 2006-03-31 | 학교법인연세대학교 | Protective coating layer material for AC plasma display panel device |
| JP2005001972A (en) * | 2003-06-10 | 2005-01-06 | Kansai Tlo Kk | Method and base material for forming diamond film |
| CN100336935C (en) * | 2004-02-03 | 2007-09-12 | 旺宏电子股份有限公司 | Physical gaseous phase deposition technology and its equipment |
| JP2015081358A (en) * | 2013-10-22 | 2015-04-27 | 三井造船株式会社 | Coating film formation apparatus and method of forming coating film |
| KR101412070B1 (en) * | 2013-12-05 | 2014-07-01 | 송길용 | Scriber fixing pin for evaporation a diamond-like carbon thin film method and apparatus, using this scriber fixing pin |
| KR20210144446A (en) * | 2020-05-22 | 2021-11-30 | (주)아이네쓰 | Thin film depostion apparatus and DLC thin film coating methos using the appartus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3082979B2 (en) | 2000-09-04 |
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