JPH02274876A - Formation of thin hard carbon film - Google Patents
Formation of thin hard carbon filmInfo
- Publication number
- JPH02274876A JPH02274876A JP9576189A JP9576189A JPH02274876A JP H02274876 A JPH02274876 A JP H02274876A JP 9576189 A JP9576189 A JP 9576189A JP 9576189 A JP9576189 A JP 9576189A JP H02274876 A JPH02274876 A JP H02274876A
- Authority
- JP
- Japan
- Prior art keywords
- film
- film formation
- acceleration voltage
- substrate
- voltage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 230000001133 acceleration Effects 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 107
- 238000000034 method Methods 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- -1 carbon ions Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract 2
- 230000001419 dependent effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は硬質炭素薄膜の形成法に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to a method of forming a hard carbon thin film.
従来の技術
従来より、工具等の耐摩耗表面保護にはＳＩＣやＴＩＮ
等の炭化物、窒化物をはじめとして多くの硬質薄膜が用
いられてきた。しかし、最近、さらに耐摩耗性を有する
ダイヤモンド状炭素薄膜（旧ａｍｏｎｄ口ｋｅ Ｃａｒ
ｂｏｎ：Ｄ Ｌ Ｃ＋以下ＤＬＣ膜という）が注目をあ
びている。ＤＬＣ膜は非晶質であるが、物性がダイヤモ
ンドに近いため、電気的や光学的にも多方面への応用展
開の可能性を有している。ＤＬＣ膜の硬度が条件により
ヌープ硬度で５０００Ｋｇ／ａｍ”以上にもなることや
、酸等の薬品に対する化学的安定性、耐腐食性も備わっ
ていることから保護膜としてはもっとも適した材料であ
る。Conventional technology Traditionally, SIC and TIN have been used to protect the wear-resistant surfaces of tools, etc.
Many hard thin films including carbides and nitrides have been used. However, recently, diamond-like carbon thin films (formerly known as diamond-like carbon films), which have even more wear resistance, have been developed.
bon:DLC+ (hereinafter referred to as DLC film) is attracting attention. Although the DLC film is amorphous, its physical properties are close to those of diamond, so it has the potential to be applied in many electrical and optical fields. It is the most suitable material for a protective film because the hardness of the DLC film can exceed 5,000 Kg/am on the Knoop hardness depending on the conditions, and it also has chemical stability against chemicals such as acids and corrosion resistance. .
ＤＬＣ膜の代表的な形成法にイオンのもつ運動エネルギ
ーを膜形成に利用したイオンビーム法がある。これは、
真空中で炭素源をイオン化して、電界で加速し、基体に
成膜するものである。この方法によると、低温でも容易
にＤＬＣが成膜できるのが特徴である。ところが、ＤＬ
Ｃ膜は一般に基体との付着性が弱いためその実用化も遅
れている。これはダイヤモンド結合を有するＤＬＣ膜が
基体との界面で化学結合あるいは原子の拡散が行なわれ
にクク、そのために基体界面における結合力が弱いとい
うＤＬＣ自身の欠点がある。特に、工具等、局部に負荷
のかかるようなものの表面に被覆した場合には、容易に
基体からの剥離を生ずる。A typical method for forming a DLC film is an ion beam method that utilizes the kinetic energy of ions for film formation. this is,
A carbon source is ionized in a vacuum, accelerated by an electric field, and then deposited on a substrate. This method is characterized in that DLC can be easily formed even at low temperatures. However, DL
Since C films generally have weak adhesion to substrates, their practical application has been delayed. This is because the DLC film having diamond bonds does not undergo chemical bonding or atomic diffusion at the interface with the substrate, and as a result, the bonding force at the substrate interface is weak, which is a drawback of DLC itself. Particularly, when the coating is applied to the surface of an object such as a tool that is subjected to local loads, it easily peels off from the substrate.
そこで、基体との付着強度を強化する方法として多くの
試みがなされている。たとえば、特開昭８２−４１４８
０公報では基体と保護層の間に中間層を設ける等多層膜
形成することで膜の付着力を向上している。しかし、こ
のような方法は実用化を考慮した場合、成膜プロセスの
複雑化につながるため、あまり望ましいものとはいえな
い。Therefore, many attempts have been made to improve the adhesive strength with the substrate. For example, JP-A-82-4148
In Publication No. 0, the adhesion of the film is improved by forming a multilayer film such as providing an intermediate layer between the substrate and the protective layer. However, such a method is not very desirable when considering practical use because it leads to a complicated film formation process.
発明が解決しようとする課題
ＤＬＣ膜の内部には成膜中に内部応力が存在しており、
基体界面の付着強度の弱さもあいまって、膜の剥離ある
いはクラックを生じさせる原因となる。また、膜厚の増
加によって、内部応力も増大するので、膜が厚くできな
いといった問題がある。Problems to be Solved by the Invention Internal stress exists inside the DLC film during film formation.
Combined with the weak adhesion strength at the substrate interface, this causes peeling or cracking of the film. Furthermore, as the film thickness increases, internal stress also increases, so there is a problem that the film cannot be made thicker.
したがって、簡単なプロヤスで内部応力を低減し、膜の
付着性を向上し、かつ厚いＤＬＣ膜を実現することか困
難であった。Therefore, it has been difficult to reduce internal stress, improve film adhesion, and realize a thick DLC film using a simple process.
本発明は、このような従来技術の課題を解決することを
目的とする。The present invention aims to solve the problems of the prior art.
課題を解決するための手段
本発明は、成膜初期にはイオンの加速電圧を高い状態に
して成膜を行い、その後、成膜しながら電圧を連続的に
減少させ、再び電圧を一定に保持して成膜するものであ
る。Means for Solving the Problems The present invention performs film formation with a high ion accelerating voltage in the initial stage of film formation, then continuously decreases the voltage while forming the film, and then holds the voltage constant again. The film is formed by
作用
成膜されるＤＬＣ膜の膜質（内部応力、硬度）はイオン
の加速電圧に強く依存する。イオンは自身がもつ電荷と
反応系内の電極との間に生じるクーロン力によって加速
される。加速されたイオンはその電圧が大きいほど高エ
ネルギーをもって基板に衝突する。したがって、これら
のイオンは基板表面に到達し、マイグレーシロンによっ
て膜が形成されるとともにに膜に損傷を与えることにな
る。本発明においては膜硬度はイオンの加速電圧に対し
ては数百ボルトの低電圧で最大となっており、高電圧で
は硬度は低下する。内部応力は高電圧はど低減されて基
板との付着性が向上するという傾向がある。ＤＬＣ膜の
硬度と内部応力はイオンの加速電圧に対して相反する性
質があり、成膜中にこの加速電圧を適時制御することに
よって、基体界面近傍と表面近傍でおのおのを最適な条
件を溝たして成膜すればよい。The film quality (internal stress, hardness) of the DLC film that is formed depends strongly on the ion accelerating voltage. Ions are accelerated by the Coulomb force generated between their own charges and the electrodes in the reaction system. The accelerated ions collide with the substrate with higher energy as the voltage increases. Therefore, these ions reach the substrate surface, form a film due to migration, and damage the film. In the present invention, the film hardness is maximum at a low voltage of several hundred volts with respect to the ion accelerating voltage, and the hardness decreases at a high voltage. Internal stresses tend to be reduced at high voltages and adhesion to the substrate is improved. The hardness and internal stress of the DLC film have contradictory properties with respect to the ion accelerating voltage, and by controlling this accelerating voltage appropriately during film formation, it is possible to achieve the optimum conditions for each near the substrate interface and near the surface. The film may be formed by
すなわち、ＤＬＣ膜の界面から膜厚方向に内部応力を低
減した膜層を成膜することによりもっとも剥離が生じや
すい界面付近で、基板との付着性を強くすることができ
る。′内部応力低減のためのイオンの加速電圧は３００
０Ｖ以上の高電圧が望ましい。That is, by forming a film layer with reduced internal stress in the film thickness direction from the interface of the DLC film, it is possible to strengthen the adhesion with the substrate near the interface where peeling is most likely to occur. 'Ion acceleration voltage to reduce internal stress is 300
A high voltage of 0V or higher is desirable.
その後、加速電圧を連続的に徐々に減少していき膜内部
の内部応力、硬度を膜厚方向に微視的な範囲で徐徐に変
化させつつ、成膜を続行する。成膜終了段階で所定の加
速電圧に到達して、表面近傍に硬質膜層を形成し、成膜
を終了する。硬質膜層を形成するための加速電圧は望ま
しくは１００〜ｔｏｏｏｖの低い電圧の範囲あるのがよ
い。このように連続的にイオンの加速電圧を制御するプ
ロセスを導入することにより、基板とＤＬＣ膜の付着性
を保ちつつ、膜の硬質化を実現することができる。Thereafter, the accelerating voltage is continuously and gradually reduced to gradually change the internal stress and hardness inside the film in a microscopic range in the film thickness direction, and film formation is continued. At the end stage of film formation, a predetermined acceleration voltage is reached, a hard film layer is formed near the surface, and film formation is completed. The accelerating voltage for forming the hard film layer is preferably in the low voltage range of 100 to tooov. By introducing a process of continuously controlling the ion accelerating voltage in this way, it is possible to harden the film while maintaining the adhesion between the substrate and the DLC film.
実施例
以下に、本発明の実施例について図面を参照しながら説
明する。Examples Examples of the present invention will be described below with reference to the drawings.
第１図は本発明に用いたＤＬＣ膜形成装置の概略を示す
構造図である。炭素薄膜の成膜はガス導入口１から原料
ガスのメタンあるいはベンゼンを導入し、管内圧力０．
００５Ｔｏｒｒに保つ。内証のフィラメント２から放出
される熱電子と衝突分解電離を繰り返した原料ガス分子
が炭素イオンを生成する。FIG. 1 is a structural diagram schematically showing a DLC film forming apparatus used in the present invention. To form a carbon thin film, methane or benzene as a raw material gas is introduced from the gas inlet 1, and the pressure inside the tube is 0.
Maintain at 0.005 Torr. Raw material gas molecules that undergo repeated collision decomposition and ionization with thermoelectrons emitted from the internal filament 2 generate carbon ions.
イオン化室３の外周にはコイル４を設置して、磁場によ
りイオン化率を高めた。本発明で述べているイオンの加
速電圧は基板５に印加する負電圧により決定される。ま
た、成膜速度はイオンの加速電圧に無関係に一定である
ことから、成膜膜厚は成膜時間によってモニターできる
。基板にはシリコンを用いた。A coil 4 was installed around the outer periphery of the ionization chamber 3, and the ionization rate was increased by a magnetic field. The ion acceleration voltage described in the present invention is determined by the negative voltage applied to the substrate 5. Furthermore, since the film formation rate is constant regardless of the ion accelerating voltage, the film thickness can be monitored by the film formation time. Silicon was used for the substrate.
第２図は前記方法において成膜したＤＬＣ膜のヌープ硬
度とイオンの加速電圧の関係を示したグラフである。原
料ガスをメタンにした場合。イオ７（７）加速電圧２０
０〜３ＱＯＶＴ！最高硬度３０００〜４０００Ｋｇ／■
２を示す。印加電圧の増加によって膜硬度は軟質化した
。これはイオンのもつ運動エネルギーが大きい程膜内部
にダイヤモンド結合の生成が困難になると考えられる。FIG. 2 is a graph showing the relationship between the Knoop hardness of the DLC film formed by the method described above and the ion acceleration voltage. When the raw material gas is methane. Io7 (7) acceleration voltage 20
0~3QOVT! Maximum hardness 3000-4000Kg/■
2 is shown. The film hardness softened as the applied voltage increased. This is thought to be because the greater the kinetic energy of the ions, the more difficult it is to form diamond bonds within the film.
ベンゼンを原料にもちいた場合も７００Ｖ付近で硬度が
５０００−８０００Ｋｇ／ａｍ”の最大値を示し、電圧
の増加によって硬度は低下する傾向を示す。ただし、ベ
ンゼンの場合、１分子あたり含有する炭素数がメタンに
比べて多いため、１炭素原子がもつエネルギーは小さく
、膜自体におよぼす損傷も小さくてすむ。したがって、
ベンゼンのほうが硬質のＤＬＣ膜が実現できる。これら
の試料の膜厚はすべて約１μｍとした。Even when benzene is used as a raw material, the hardness shows a maximum value of 5000-8000 Kg/am'' around 700V, and the hardness tends to decrease as the voltage increases.However, in the case of benzene, the number of carbons contained per molecule Since there are more carbon atoms than methane, each carbon atom has less energy and less damage to the film itself.Therefore,
Benzene can produce a harder DLC film. The film thickness of all of these samples was approximately 1 μm.
第３図はＤＬＣ膜の内部応力とイオンの加速電圧の関係
を示したグラフである。原料の種類によらずイオンの加
速電圧ｔｏｏｏｖ以下で約５００にｇｅｍｓ２の内部応
力が膜内部に生ずる。加速電圧の増加によって内部応力
は減少し、４０００Ｖで１００Ｋｇ／ａｍ”以下にまで
低減される。FIG. 3 is a graph showing the relationship between the internal stress of the DLC film and the ion acceleration voltage. Regardless of the type of raw material, an internal stress of about 500 gems2 is generated inside the film when the ion acceleration voltage is tooov or less. The internal stress is reduced by increasing the accelerating voltage, and is reduced to less than 100 Kg/am'' at 4000V.
以下の実施例では、成膜中に、ＤＬＣ膜の硬質化に適す
る加速電圧と内部応力低減に適する加速電圧を組合せ、
基板と付着性の良い硬質ＤＬＣ膜を得たものを述べる。In the following examples, during film formation, an accelerating voltage suitable for hardening the DLC film and an accelerating voltage suitable for reducing internal stress are combined,
A hard DLC film with good adhesion to the substrate will be described.
まず、第１の実施例として原料ガスにメタンを用いた場
合について述べる。第４図（イ）〜（ニ）は成膜時、イ
オンの加速電圧を減少する操作を成膜時間に対して示し
た成膜プロセスを示す図である。前述のように、管内圧
力を一定に保ち、以下に示す４通りの条件で加速電圧を
変えＤＬＣ膜を成膜した。First, a case where methane is used as the raw material gas will be described as a first example. FIGS. 4(A) to 4(D) are diagrams showing a film forming process in which the operation of reducing the ion accelerating voltage during film forming is shown with respect to the film forming time. As described above, the DLC film was formed by keeping the pressure inside the tube constant and changing the accelerating voltage under the following four conditions.
（イ）成膜中、加速電圧３００ｖの一定で３０分行なっ
た場合である（（イ）図参照）。(A) This is the case where film formation was carried out for 30 minutes at a constant acceleration voltage of 300 V (see figure (A)).
（ロ）成膜中、加速電圧３０００Ｖの一定で３０分行な
った場合である（（ロ）図参照）。(B) This is the case where film formation was carried out for 30 minutes at a constant acceleration voltage of 3000 V (see figure (B)).
（ハ）成膜開始１０分間（膜厚的０．３４μｍまで）３
０００Ｖの一定とし、その後１０分間（膜厚的０．６８
μｍまで）で徐々に減少して３００Ｖとし、１０分間こ
れを保持して終了する（（ハ）図参照）。(c) 10 minutes from the start of film formation (up to 0.34 μm in film thickness) 3
000V for 10 minutes (film thickness: 0.68
(up to μm) gradually decrease to 300V, hold this for 10 minutes, and finish (see figure (c)).
（ニ）成膜開始１０分間（膜厚的０．３４μｍまで）３
０００Ｖの一定とし、その後１００分間（膜厚的３．７
μｍまで）で徐々に減少して３００Ｖとし１０分間これ
を保持しトータルの成膜時間２時間で終了する（（ニ）
図参照）。(d) 10 minutes from the start of film formation (up to 0.34 μm in film thickness) 3
000V for 100 minutes (film thickness: 3.7
μm) gradually decreases to 300V and holds it for 10 minutes, completing the film formation in 2 hours ((d)
(see figure).
これらの条件で得た膜について、試料をヌープ硬度計で
評価した結果を第１表に示す。Table 1 shows the results of evaluating the samples using a Knoop hardness tester for the films obtained under these conditions.
第１表
（イ）、（ロ）、（ハ）の条件で得た膜厚は、いずれも
約１μｍであった。 （イ）の条件で成膜した場合、膜
の一部に剥離を生じ、表面には多くのクラックがみられ
硬度の測定は不可能であった。The film thicknesses obtained under the conditions shown in Table 1 (a), (b), and (c) were all approximately 1 μm. When the film was formed under the conditions (a), part of the film peeled off and many cracks were observed on the surface, making it impossible to measure the hardness.
また、 （ロ）の方法ではヌープ硬度が２０００Ｋｇ／
ｇｍ”であり、ＤＬＣ膜の硬度としては低い。これらに
くらべて、 （ハ）の条件によると、硬度は３Ｇ（１０
〜４０００Ｋｇ／ｖ＋＋”を示し、付着性の良い硬質の
ＤＬＣ膜が得られた。さらに、これらの試料をエメリー
ペーパーで擦ると（イ）は完全に剥離し、 （ロ）には
傷がついた。−（ハ）に異常はなかった。また、（ニ）
の条件で得た膜については、ヌープ硬度は３０００〜４
０００Ｋｇ／ａｓ’と（ハ）のものと同等であるが、内
部応力が低減されて、膜厚的４μｍのものでも剥離はな
かった。In addition, in method (b), the Knoop hardness is 2000 kg/
gm”, which is low as the hardness of DLC film.Compared to these, according to the condition (c), the hardness is 3G (10
〜4000Kg/v++'', and a hard DLC film with good adhesion was obtained.Furthermore, when these samples were rubbed with emery paper, (a) was completely peeled off, and (b) was scratched. - There was no abnormality in (c).Also, (d)
For the film obtained under the conditions, the Knoop hardness is 3000-4
000 Kg/as', which is equivalent to (c), but the internal stress was reduced and there was no peeling even with a film thickness of 4 μm.
次に第２の実施例として原料ガスにベンゼンを用いた場
合を示す。第５図には成膜時間に対する加速電圧の変化
を示す。第１の実施例の場合と同様条件を以下の４通り
に設定した。Next, as a second example, a case where benzene is used as the raw material gas will be shown. FIG. 5 shows changes in accelerating voltage with respect to film formation time. Similar to the case of the first example, the following four conditions were set.
（イ）成膜中加速電圧は７００ｖの一定で３０分行なう
（（イ）図参照）。(a) During film formation, the acceleration voltage was kept constant at 700 V for 30 minutes (see figure (a)).
（ロ）成膜中加速電圧は３０００Ｖの一定で３０分行な
う（（ロ）図参照）。(B) During film formation, the acceleration voltage was kept constant at 3000 V for 30 minutes (see figure (B)).
（ハ）成膜開始１０分間（Ｍ厚約０．５μｍまで）３０
００ｖの一定とし、その後１０分間で（膜厚的１．０μ
ｍまで）徐々に減少して７００ｖとじ１０分間これを保
持して終了する（（ハ）図参照）。(c) 10 minutes from the start of film formation (up to M thickness of approximately 0.5 μm) 30
00V constant, then for 10 minutes (film thickness 1.0μ
m) gradually decrease to 700V and hold this for 10 minutes to finish (see figure (C)).
（ニ）成膜開始１０分間（膜厚的０．５μｍまで）３０
００ｖの一定とし、その後１００分間で（膜厚的５．５
μｍまで）徐々に減少して７００ｖとし１０分間これを
保持してトータルの成膜時間２時間で終了する（（ニ）
図参照）。結果を第２表に示す。(d) 10 minutes from the start of film formation (up to 0.5 μm in film thickness) 30 minutes
00v constant, then for 100 minutes (film thickness 5.5
μm) gradually decrease to 700V and hold it for 10 minutes, completing the film formation in 2 hours ((d)
(see figure). The results are shown in Table 2.
第２表
（ホ）の条件では膜が剥離し、硬度の測定は不可能であ
った。 （へ）の条件では、ヌープ硬度３０００〜４０
００にｇ／ｍｍ２でありメタンの場合と同等の硬い膜が
得られている。 （ト）の条件ではヌープ硬度は５００
０〜Ｂ０００にｇ／ｅｍ”と非常に硬い膜が得られてお
り、しかも基板との付着性もよい。 （チ）の条件で成
膜時間を延長して、膜厚６μｍのＤＬＣを成膜したが剥
離も見られず、硬度も５０００〜ｆｆ０００Ｋｇ／ＩＩ
ｍ”を示した。Under the conditions shown in Table 2 (e), the film peeled off, making it impossible to measure the hardness. Under the conditions (to), Knoop hardness is 3000 to 40
00g/mm2, and a hard film equivalent to that of methane was obtained. Under the conditions (g), the Knoop hardness is 500
A very hard film of 0 to B000 g/em" was obtained, and the adhesion to the substrate was also good. The film forming time was extended under the condition (H) to form a DLC film with a thickness of 6 μm. However, no peeling was observed, and the hardness was 5000 to ff000Kg/II.
m” was shown.
発明の効果
本発明は、成膜中に、成膜膜厚に応じてイオンの加速電
圧を減少していくことにより、基板材料と付着性を保ち
つつ、硬質の炭素薄膜が形成できる。また、初期の加速
電圧を少なくとも３０００ｖ以上にすることにより、さ
らに膜内部の応力を低減して基体との付着性を向上し、
膜を厚く成膜できる。Effects of the Invention According to the present invention, a hard carbon thin film can be formed while maintaining adhesion to the substrate material by decreasing the ion accelerating voltage according to the film thickness during film formation. In addition, by setting the initial accelerating voltage to at least 3000 V, the stress inside the film is further reduced and the adhesion to the substrate is improved.
A thick film can be formed.
このようなことから、本発明は耐摩耗性ＤＬＣ膜被覆方
法としての工業的価値の高いものである。For these reasons, the present invention has high industrial value as a method for coating a wear-resistant DLC film.
第１図は本発明の一実施例の硬質炭素薄膜の形成法に用
いた炭素薄膜の成膜装置の概略構造図、第２図は同実施
例におけるイオンの加速電圧と膜硬度の関係を示すグラ
フ、第３図は同実施例におけるイオンの加速電圧と膜の
内部応力の関係を示すグラフ、第４図は同実施例を行な
った成膜条件のプロセスを示すグラフ、第６図は第２の
実施例を行なった成膜条件のプロセスを示す図である。
１・・・ガス導入口、２・・・フィラメント、３・・・
イオン化室、 ４・・・コイル、５・・・基板。
代理人の氏名 弁理士 粟野重孝はか１名第１図
第
図
第
因
イオンのＰ遭ノ１工ｆｌ／１
イオンのＪｆｆ遣電、ＬＣｖ＋
第
図
へ噴２時り■（分）
第
図
へ侯ｆｆ間（分）
へ＊ｖｆ間（分）
へ暁時間（分）
六喚吟間（分）Fig. 1 is a schematic structural diagram of a carbon thin film forming apparatus used in the method of forming a hard carbon thin film according to an embodiment of the present invention, and Fig. 2 shows the relationship between ion acceleration voltage and film hardness in the same embodiment. Graphs, Figure 3 is a graph showing the relationship between ion acceleration voltage and internal stress of the film in the same example, Figure 4 is a graph showing the process of film formation conditions under which the same example was carried out, and Figure 6 is a graph showing the relationship between the ion acceleration voltage and the internal stress of the film in the same example. FIG. 3 is a diagram showing the process of film forming conditions under which the example was carried out. 1... Gas inlet, 2... Filament, 3...
Ionization chamber, 4... Coil, 5... Substrate. Name of agent: Patent attorney Shigetaka Awano (1 person) Figure 1 Figure Figure 1 Ion's P encounter 1 engineering fl/1 Ion's Jff power dispatch, LCv+ Figure 2 2 o'clock ■ (minutes) Figure 1 Hou ff interval (minutes) To*Vf interval (minutes) To Akatsuki time (minutes) Rokukangin interval (minutes)
Claims (3)
０＾−＾２〜１０＾−＾４Ｔｏｒｒの減圧でイオン化し
、前記イオンを基板方向に加速しつつ、膜厚に応じて、
前記イオンの加速電圧を減少させながら成膜することを
特徴とする硬質炭素薄膜の形成法。(1) A gas containing at least carbon as a constituent element is
Ionize under reduced pressure of 0^-^2 to 10^-^4 Torr, and while accelerating the ions toward the substrate, depending on the film thickness,
A method for forming a hard carbon thin film, characterized in that the film is formed while decreasing the acceleration voltage of the ions.
あることを特徴とする請求項１記載の硬質炭素薄膜の形
成法。(2) The method for forming a hard carbon thin film according to claim 1, wherein the ion acceleration voltage at the initial stage of film formation is 3000 V or more.
０Ｖの範囲にあることを特徴とする請求項１記載の硬質
炭素薄膜の形成法。(3) Ion acceleration voltage at the end of film formation is 100 to 100
2. The method of forming a hard carbon thin film according to claim 1, wherein the voltage is in the range of 0V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9576189A JP2676903B2 (en) | 1989-04-14 | 1989-04-14 | Method of forming hard carbon thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9576189A JP2676903B2 (en) | 1989-04-14 | 1989-04-14 | Method of forming hard carbon thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02274876A true JPH02274876A (en) | 1990-11-09 |
| JP2676903B2 JP2676903B2 (en) | 1997-11-17 |
Family
ID=14146472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9576189A Expired - Fee Related JP2676903B2 (en) | 1989-04-14 | 1989-04-14 | Method of forming hard carbon thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2676903B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370292A (en) * | 1990-08-29 | 1994-12-06 | Matsushita Electric Industrial Co., Ltd. | Magnetic tape driving mechanism having a capstan with a surface made of carbon film including diamond-bonded carbons |
| US5378285A (en) * | 1993-02-10 | 1995-01-03 | Matsushita Electric Industrial Co., Ltd. | Apparatus for forming a diamond-like thin film |
| US5455081A (en) * | 1990-09-25 | 1995-10-03 | Nippon Steel Corporation | Process for coating diamond-like carbon film and coated thin strip |
-
1989
- 1989-04-14 JP JP9576189A patent/JP2676903B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5370292A (en) * | 1990-08-29 | 1994-12-06 | Matsushita Electric Industrial Co., Ltd. | Magnetic tape driving mechanism having a capstan with a surface made of carbon film including diamond-bonded carbons |
| US5455081A (en) * | 1990-09-25 | 1995-10-03 | Nippon Steel Corporation | Process for coating diamond-like carbon film and coated thin strip |
| US5378285A (en) * | 1993-02-10 | 1995-01-03 | Matsushita Electric Industrial Co., Ltd. | Apparatus for forming a diamond-like thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2676903B2 (en) | 1997-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5314652A (en) | Method for making free-standing diamond film | |
| JP2002541604A (en) | Method and apparatus for depositing a diamond-like carbon coating from a Hall current ion source | |
| EP2383366B1 (en) | Method for producing diamond-like carbon membrane | |
| CA2846434C (en) | Stripping process for hard carbon coatings | |
| JPH04374A (en) | Production of hardened protective film on surface of plastic substrate | |
| JPH02274876A (en) | Formation of thin hard carbon film | |
| JP3187487B2 (en) | Article with diamond-like thin film protective film | |
| JP3034241B1 (en) | Method of forming high hardness and high adhesion DLC film | |
| JP3355892B2 (en) | Method of forming carbon film | |
| JPH0784642B2 (en) | Method for forming a film on the surface of an object to be treated | |
| JP3205363B2 (en) | Mold with diamond-like protective film | |
| US5869390A (en) | Method for forming electrode on diamond for electronic devices | |
| JP2008174790A (en) | Surface treatment method for metal fiber textile, and article obtained thereby | |
| JP3130094B2 (en) | Mold with diamond-like protective film | |
| JP2852380B2 (en) | Method for forming carbon or carbon-based coating | |
| EP0651385A2 (en) | Method for producing diamond-like carbon film and tape driving apparatus | |
| JPH10265955A (en) | Formation of carbonaceous highly functional material thin film by electron beam-excited plasma cvd | |
| JP3056827B2 (en) | Article having a diamond-like carbon protective film and method for producing the same | |
| Ugolini et al. | Direct ion beam deposition of polymeric styrene films and in situ characterization by electron spectroscopy | |
| JPH08309100A (en) | Iron and its production | |
| WO2023105894A1 (en) | Silicon nitride film forming method, film forming device, and silicon nitride film | |
| JP2001107246A (en) | Deposition of carbon film or film composed essentially of carbon | |
| JP2775263B2 (en) | Member covered with carbon film | |
| JP2752225B2 (en) | Method for synthesizing hard carbon film | |
| US20140224768A1 (en) | Method for removing hard carbon layers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070725 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080725 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |