JPH0225569A - Method for synthesizing hard-carbon film - Google Patents
Method for synthesizing hard-carbon filmInfo
- Publication number
- JPH0225569A JPH0225569A JP63174465A JP17446588A JPH0225569A JP H0225569 A JPH0225569 A JP H0225569A JP 63174465 A JP63174465 A JP 63174465A JP 17446588 A JP17446588 A JP 17446588A JP H0225569 A JPH0225569 A JP H0225569A
- Authority
- JP
- Japan
- Prior art keywords
- plasma discharge
- carbon film
- plasma
- film
- gas
- 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
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000006866 deterioration Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- MUJOIMFVNIBMKC-UHFFFAOYSA-N fludioxonil Chemical compound C=12OC(F)(F)OC2=CC=CC=1C1=CNC=C1C#N MUJOIMFVNIBMKC-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は硬質炭素膜の合成方法に係り、詳しくは、光デ
ィスク、磁気ヘッド、切削工具等のコーティング材料と
して用いられる膜質の優れた硬質炭素膜の合成方法に係
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for synthesizing a hard carbon film, and more specifically, to the synthesis of a hard carbon film with excellent film quality that is used as a coating material for optical disks, magnetic heads, cutting tools, etc. Regarding the method.
従 来 の 技 術
硬質炭素膜はアモルファス構造を持ち、高硬度、優れた
潤滑性・耐摩耗性・耐薬品性を有し、種々の用途に利用
できるコーティング材料として注目されている。−質炭
素躾の合成方法としてはイオンブレーティング法、スパ
ッタ法、プラズマｃｖｏ １等が知られている。イオン
ブレーティング法は成膜速度が遅（、膜形成可能な面積
が狭いため実用に適さないという欠点があり、また、ス
パッタ法は炭素膜中に金属や不活性ガス等の不純物を′
取り込み易いという欠点がある。Conventional technology Hard carbon films have an amorphous structure, high hardness, and excellent lubricity, wear resistance, and chemical resistance, and are attracting attention as coating materials that can be used for various purposes. Ion blating method, sputtering method, plasma CVO 1, etc. are known as methods for synthesizing carbon fibers. The ion blasting method has the disadvantage that it is not suitable for practical use because the film formation rate is slow (and the area where the film can be formed is small), and the sputtering method does not allow impurities such as metals and inert gases to enter the carbon film.
It has the disadvantage of being easy to incorporate.
プラズマＣｖＤ法は上記の如き欠点のない優れた方法で
ある。The plasma CVD method is an excellent method that does not have the above-mentioned drawbacks.
これは、例えば、ジャーナルオブアプライドフィジック
ス（Ｊ、 ＡＰＰＬ、 Ｐｈｙｓ、 ）第５２巻Ｐ６１
５１〜６１５７に記載された第２図に示される代表的な
プ。This is, for example, Journal of Applied Physics (J, APPL, Phys, ) Vol. 52, p. 61.
51-6157 and shown in FIG.
ラズマＣＶＤ装置を用い、炭化水素ガス１３を反応容器
６に導入し、高周波発振器１より出される高周波により
プラズマ分解し、基体５上に硬質炭素膜を形成させる方
法である。In this method, a hydrocarbon gas 13 is introduced into a reaction vessel 6 using a plasma CVD apparatus, and subjected to plasma decomposition by high frequency waves emitted from a high frequency oscillator 1, thereby forming a hard carbon film on the substrate 5.
しかし、プラズマＣｖＤ法の反応機構は解明されていな
い部分が多く、硬質炭素膜の合成においてもしばしば硬
度が低い、潤滑性がない等のＩＩＩ質の劣った膜が形成
するという問題があった。However, many parts of the reaction mechanism of the plasma CvD method have not been elucidated, and even in the synthesis of hard carbon films, there has been a problem in that films of inferior III quality, such as low hardness and lack of lubricity, are often formed.
以上要するに、現在までに提案されてきたプラズマＣＶ
Ｄ法による硬質炭素膜の合成方法ではプラズマＣＶＤの
反応機構が解明されていない部分が多いため、高硬質で
優れた潤滑性を有する炭素膜を再現性よく合成すること
は困難であり、プラズマＣＶＤ法による潰れた硬質炭素
膜の合成方法はよ（わかっていないのが現状である。In summary, the plasma CV that has been proposed to date
In the method of synthesizing a hard carbon film using the D method, the reaction mechanism of plasma CVD is largely unknown, so it is difficult to synthesize a carbon film with high hardness and excellent lubricity with good reproducibility. The method for synthesizing crushed hard carbon membranes by this method is currently unknown.
発明が解決しようとする課題
本発明は上記欠点の解決を目的とし、具体的には、プラ
ズマＣＶＤ法により高硬度で優れた潤滑性を有する炭素
膜が安定して得られる硬質炭素膜の合成方法を提案する
。Problems to be Solved by the Invention The present invention aims to solve the above-mentioned drawbacks, and specifically provides a method for synthesizing a hard carbon film that can stably obtain a carbon film with high hardness and excellent lubricity by plasma CVD method. propose.
課題を解決するための
手段ならびにその作用
すなわち、本発明は、炭化水素化合物を含む原料ガスを
プラズマ放電により分解し、基体上に硬質炭素膜を合成
する際に、前記プラズマ放電により形成されるプラズマ
放電空間ｗ４域中のアセチレンの濃度を１，０ｘｌＯ−
９ｓｏｊ／ｉ以下に調整することを特徴とする。Means for Solving the Problems and Their Effects That is, the present invention decomposes a raw material gas containing a hydrocarbon compound by plasma discharge, and when synthesizing a hard carbon film on a substrate, the plasma formed by the plasma discharge. The concentration of acetylene in the discharge space w4 region is set to 1,0xlO-
It is characterized by adjusting to 9 soj/i or less.
そこで、これらの手段たる構成ならびにその作用につい
て更に具体的に説明すると、次の通りである。Therefore, the structure of these means and their operation will be explained in more detail as follows.
本発明者等はプラズマＣＶＤ装置を用いて高硬度で潰れ
た潤滑性を有する硬質炭素膜を安定して基体上に得るた
め、プラズマＣＶＤ法による炭化水素ガスの気′相反応
機構を検討し、解析すると共に、合成膜との関係を研究
した結果、膜質の劣化に関してプラズマ放電により合成
されたアセチレンが重要な役割を果たすことがわかった
。更に進んで、硬質炭素膜の合成条件について研究し、
この研究結果に基づいて本発明は成立したものである。In order to stably obtain a hard carbon film with high hardness and crushed lubricity on a substrate using a plasma CVD device, the present inventors investigated the gas phase reaction mechanism of hydrocarbon gas by the plasma CVD method, and As a result of analysis and research on the relationship with synthetic membranes, it was found that acetylene synthesized by plasma discharge plays an important role in the deterioration of membrane quality. Going further, we researched the conditions for synthesizing hard carbon films.
The present invention was established based on the results of this research.
以下、第１図により本発明を更に詳しく説明する。The present invention will be explained in more detail below with reference to FIG.
なお、第１図は本発明を実施する際に用いられるプラズ
マｃｖｏ装置の一例の説明図であって、符号１は＾周波
発撮器、２はマツチングボックス、３．４は電極、５は
基体、６は反応容器、７は排気口、８．９％１０はバル
ブ、１１．１２はマスフローコントローラ、１３．１４
は原料ガス、１５はＦＴ・ＩＲ分析装置（Ｆｏｕｒｉｅ
ｒ Ｔｒａｎｓｆｏｒｍ Ｉｎｆｒａｒｅｄ ５ｐｅｃ
ｔｒｏｓｅｔｅｒ）、１６．１１はＺｎ５ｅの窓、１８
は赤外光、１９は制ｔＩｌ装置、２０は圧力調整弁を示
す。In addition, FIG. 1 is an explanatory diagram of an example of a plasma CVO device used when carrying out the present invention, in which reference numeral 1 is a frequency generator, 2 is a matching box, 3.4 is an electrode, and 5 is a Substrate, 6 is a reaction vessel, 7 is an exhaust port, 8.9% 10 is a valve, 11.12 is a mass flow controller, 13.14
is the raw material gas, 15 is the FT/IR analyzer (Fourie
r Transform Infrared 5pec
troseter), 16.11 is Zn5e window, 18
19 indicates an infrared light, 19 indicates a control device, and 20 indicates a pressure regulating valve.
まず、第１図において、プラズマＣＶＤ ＠置はプラズ
マ反応部と前記反応部に原料ガスを供給する原料供給機
構と前記反応部にエネルギーを供給するエネルギー供給
機構と前記反応部のプラズマ反応状態を検出し制御する
制御機構とからなる。First, in FIG. 1, a plasma CVD @ apparatus detects a plasma reaction section, a raw material supply mechanism that supplies raw material gas to the reaction section, an energy supply mechanism that supplies energy to the reaction section, and a plasma reaction state of the reaction section. It consists of a control mechanism that controls the
プラズマ反応部は反応容器６かうなり、この容器６内に
は上下方向相対位置にｌ！１ｆ１３．４と、前記反応容
器６の側部にプラズマ反応状況を検知するＺｎ５ｅの窓
１６．１７と前記反応容器６の下部に容器６内を減圧に
する真空装置（図示せず）に接続する排気ロアが設けら
れ、電極３上に基体５＃ｔｆｆｉされるようになってい
る。原料ガス供給ＲＭ４は原料ガス１３と添加ガス１４
をそれぞれ反応容器６内にそれぞれ供給するボンベ等の
貯槽とマスフローコントローラ１１．１２とバルブ８．
９．１０とから成り、原料ガスを所定量供給できるよう
にしたものである。The plasma reaction section is arranged in a reaction vessel 6, and inside this vessel 6 there is a relative position in the vertical direction. 1f13.4, a Zn5e window 16.17 on the side of the reaction vessel 6 for detecting the plasma reaction situation, and a vacuum device (not shown) for reducing the pressure inside the vessel 6 at the bottom of the reaction vessel 6. An exhaust lower is provided, and the base 5#tffi is mounted on the electrode 3. Raw material gas supply RM4 includes raw material gas 13 and additive gas 14.
into the reaction vessel 6, a storage tank such as a cylinder, a mass flow controller 11.12, and a valve 8.
9.10, and is capable of supplying a predetermined amount of raw material gas.
エネルギー供給機構は高周波発振器１とマツチングボッ
クス２とからなり、前記反応容器６内のｊ！権に高周波
電圧を印加するようにしたものである。制ａｍ構は「■
・ＩＲ分析装置１５．１５と制Ｗ装置１９と圧力調整弁
２０とからなり、このＦＴ・ＩＲ分析装ｒａ１５．１５
は反応容器６内部の放電空間中においてプラズマ反応に
より生成するアセチレンの濃度を測定することができる
ように反応容器６に対し、水平方向で反応容器６の外側
中央部の左右対応する位置に設け、更に、この分析１ｊ
ｉｌ１５．１５で検出したアセチレン濃度の測定値の出
力信号を制御装置１９に入力し、この制御Ｉ装［１９に
予め設定された設定値と比較して偏差を求め、この偏差
に応じて圧力調整弁２０を開閉して反応容器６内の圧力
を調整できるようにしたものである。また、更にマスフ
ローコントローラ、放電電源等を制画し、プラズマ条件
を調整することもできる。The energy supply mechanism consists of a high frequency oscillator 1 and a matching box 2, and includes j! in the reaction vessel 6. A high-frequency voltage is applied to the power source. The am structure is “■
・It consists of an IR analyzer 15.15, a W control device 19, and a pressure regulating valve 20, and this FT/IR analyzer ra15.15
are provided at horizontally corresponding positions on the left and right sides of the outer center of the reaction container 6, so as to be able to measure the concentration of acetylene generated by the plasma reaction in the discharge space inside the reaction container 6, Furthermore, this analysis 1j
The output signal of the measured value of the acetylene concentration detected by the control device 15 is input to the control device 19, and the deviation is determined by comparing it with the preset value in the control device 19, and the pressure is adjusted according to this deviation. The pressure inside the reaction vessel 6 can be adjusted by opening and closing the valve 20. Furthermore, it is also possible to design a mass flow controller, a discharge power source, etc., and adjust plasma conditions.
以上説明したプラズマＣＶＤ装置は本発明法を実施する
際に用いるＶＲｍの一例を示したにすぎず、本発明はこ
れにより拘束されるものではなく、同様の原理を用いた
ものであれば、本発明法を実施する際に用いることがで
きることは云うまでもない。The plasma CVD apparatus described above is merely an example of the VRm used when carrying out the method of the present invention, and the present invention is not limited thereto. Needless to say, it can be used when implementing the invented method.
以上のように構成された装置を用いて硬質炭素膜を基体
上に合成する方法は次の通りである。The method for synthesizing a hard carbon film on a substrate using the apparatus configured as described above is as follows.
反応容器６内の電極３上に基体を載置した債、反応容器
Ｇ内を真空装置を作動させて減圧状態とした債、この容
器６内に原料ガス及び添加ガス１３．１４をマスフロー
コントローラ１１．１２を介して導入する。The substrate is placed on the electrode 3 in the reaction vessel 6, the pressure inside the reaction vessel G is reduced by operating a vacuum device, and the raw material gas and additive gases 13 and 14 are introduced into the vessel 6 by the mass flow controller 11. Introduced via .12.
次に、高周波発振器１から出力した高周波電圧を電極３
に印加し、１１橿３．４間にプラズマ放電させ、反応容
器６内のプラズマ放電空間に存在するアセチレン濃度を
ＦＴ・ＩＲ分析装置１５．１５により測定し、この測定
値の出力信号を１８１１ｗ装置１９に入力し、所定のガ
ス圧力となるように制御Ｉ装［１９の出力信号により圧
力調整弁２０の調整を行なえば高硬度で潤滑性に優れた
硬質炭素膜が合成される。Next, the high frequency voltage output from the high frequency oscillator 1 is applied to the electrode 3.
was applied to generate a plasma discharge between 11 and 3.4 hours, and the acetylene concentration present in the plasma discharge space in the reaction vessel 6 was measured by the FT/IR analyzer 15.15, and the output signal of this measured value was sent to the 1811w device. 19 and adjusts the pressure regulating valve 20 according to the output signal of the control unit 19 so that a predetermined gas pressure is achieved, a hard carbon film with high hardness and excellent lubricity is synthesized.
更に、プラズマＣＶＤ法による硬質炭素膜の合成条件に
ついて説明する。Furthermore, conditions for synthesizing a hard carbon film by plasma CVD method will be explained.
本発明において用いる炭化水素化合物としては、例えば
、メタン、エタン、プロパン、ブタン等の飽和炭化水素
、エチレン、プロピレン等の三重結合炭素を持たない不
飽和炭化水素、シクロペンタン、アダマンタン、シクロ
ヘキサン等の脂環式炭化水素、ベンゼン、トルエン、ナ
フタレン等の芳香族炭化水素等の炭化水ＩＩＩｆ利用で
きるが、これらの中、取り扱いの容易な卓からメタン、
エタン等の炭素数の少ない飽和炭化水素が好ましい。Examples of the hydrocarbon compound used in the present invention include saturated hydrocarbons such as methane, ethane, propane, and butane; unsaturated hydrocarbons without triple bond carbons such as ethylene and propylene; and fats such as cyclopentane, adamantane, and cyclohexane. Hydrocarbons such as cyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and naphthalene can be used; among these, methane,
Saturated hydrocarbons with a small number of carbon atoms, such as ethane, are preferred.
上記炭化水素化合物に添加するガスとしては、例えば、
水素、アルゴン、ヘリウム等があげられ、これらの炭化
水素に対する添加ガスの比率はＯ〜１０００の範囲であ
り、好ましくは、０〜１００である。１０００［では炭
素膜が形成しないか、あるいは成膜速度が低いため実用
的ではない。なお、添加ガスの効果として水素を添加す
ると、膜中の水素含有量が減少し、アルゴン等の不活性
ガスを添加すると成膜速度が向上する。プラズマ放電は
公知のプラズマ放電形成手段を用いて作られる。プラズ
マ放電形成手段としては直流電場による電離、５０〜６
０Ｈ２の低周波数から１０４〜１０” Ｈｚの高周波の
交流電場による電離、１０９〜１０１２Ｈｚのマイクロ
波の電磁波による電離などがあげられる。これらの中で
本発明法に用いられるプラズマ放電を作る手段としては
高周波の交′ａ電場による電離が望ましい。この理由は
直流電場を用いると基体ｔｆ電荷を帯びてしまうこと、
また、マイクロ波は取り扱いｆｆ難かしいからである。Examples of the gas added to the hydrocarbon compound include:
Examples include hydrogen, argon, helium, etc., and the ratio of the additive gas to these hydrocarbons is in the range of 0 to 1000, preferably 0 to 100. 1000[ is not practical because a carbon film is not formed or the film formation rate is low. Note that as an effect of the additive gas, when hydrogen is added, the hydrogen content in the film is reduced, and when an inert gas such as argon is added, the film formation rate is increased. The plasma discharge is created using known plasma discharge forming means. As a plasma discharge forming means, ionization by a direct current electric field, 50-6
Ionization by an alternating current electric field with a low frequency of 0H2 to high frequency of 104 to 10" Hz, ionization by microwave electromagnetic waves of 109 to 1012 Hz, etc. Among these, the means for creating plasma discharge used in the method of the present invention include: Ionization by a high-frequency alternating electric field is desirable.The reason for this is that if a direct current electric field is used, the substrate will be charged with tf charge.
Further, microwaves are difficult to handle.
基体としてはプラズマ放電により分解されたり破屓した
りしないものが好ましく、例えば、シリコン、石英、炭
化ケイ素等のケイ素化合物、黒鉛、ダイヤモンド等の炭
素物質、鉄、モリブデン等の金属、サフアイヤ、アルミ
ナ等の酸化物などがあげられる。The substrate is preferably one that will not be decomposed or crushed by plasma discharge, such as silicon compounds such as silicon, quartz, and silicon carbide, carbon materials such as graphite and diamond, metals such as iron and molybdenum, saphire, alumina, etc. Examples include oxides of
ガス圧力は０．００１〜１００Ｔｏｒｒの範囲で使用で
き、好ましくは、０． Ｏ１〜１０Ｔｏｒｒである。
０．０ＩＴｏｒｒ未満では成膜速度は遅くなり、１０Ｔ
ｏｒｒ超では気相反応が主になり、硬質炭ＩＩ躾の合成
ｆｌかしくなる。ガス帽ト投入電力は装置構成等により
変わるため、特定することは困難である。The gas pressure can be used in the range of 0.001 to 100 Torr, preferably 0.00 Torr. O1 to 10 Torr.
Below 0.0ITorr, the deposition rate becomes slow, and at 10T
When the temperature exceeds orr, the gas phase reaction becomes dominant, and the synthesis of hard carbon II becomes difficult. The power input to the gas cap varies depending on the device configuration, etc., so it is difficult to specify.
本発明に５０では上記のような合成条件で硬質炭素膜を
合成するが、この場合、プラズマ放電空間領域（電極３
と電極４との間の空間領域）のアセチレン濃度を一定値
以下、すなわち、１．ＯＸ １ｏ−ｑｍｏ ／ ／１ｍ
’以下になるように、プラズマ条件を調整すると、アセ
チレンによる硬度の低下・潤滑性の低下等の膜質の劣化
を防止することができる。In 50 of the present invention, a hard carbon film is synthesized under the above synthesis conditions, but in this case, the plasma discharge space region (electrode 3
and the acetylene concentration in the space (between the electrode 4 and the electrode 4) below a certain value, that is, 1. OX 1o-qmo / /1m
If the plasma conditions are adjusted to the following, deterioration of film quality such as a decrease in hardness and lubricity due to acetylene can be prevented.
このアセチレンの、濃度として１，０Ｘ１０−’■０１
／ｉ以下であれば膜質の劣化を防止できるが、好ましく
は５．０ｘｌＯ−”ｖｏｌｎ以下である。このアセチレ
ンは前記したように、プラズマ放電空間中でプラズマ反
応により合成される。従って、プラズマ放電空間領域の
アセチレンの存在壇をＩＩＩＩＩｌするためには、ガス
圧力、ガス流量等のプラズマ条件を調整する必要がある
。第３図は瑛記の実施例において行なった試験結果であ
って、ガス圧力とアセチレン濃度、ｌ！ｉ！質の関係を
示すグラフであるが、この図よりアセチ１／ン濃度と膜
質との関係は明らかである。もちろん、他のプラズマ条
件においても同様の関係が得られる。The concentration of this acetylene is 1,0X10-'■01
If it is less than /i, deterioration of the film quality can be prevented, but it is preferably less than 5.0 In order to maximize the presence of acetylene in the spatial region, it is necessary to adjust plasma conditions such as gas pressure and gas flow rate. This is a graph showing the relationship between acetylene concentration and l!i! quality. From this graph, the relationship between acetylene concentration and film quality is clear. Of course, a similar relationship can be obtained under other plasma conditions.
また、アセチレン濃度の検出方法としては、赤外吸収分
析法が好ましいが、マススペクトル等地の方法を用いる
こともできる。ごれらの分析装置によりアセチレン濃度
を自動的に制御するには分析装置のアセチレン測定値の
出力信号を制ａ装置により処理し、原料ガス圧力弁、マ
スフローコントローラ、放電電源装置等をコントロール
することによりプラズマ条件を調整すればよい。Further, as a method for detecting the acetylene concentration, infrared absorption analysis is preferred, but methods such as mass spectroscopy can also be used. In order to automatically control the acetylene concentration using our analyzer, the output signal of the acetylene measurement value from the analyzer must be processed by a control device to control the raw gas pressure valve, mass flow controller, discharge power supply device, etc. The plasma conditions may be adjusted accordingly.
実施例 第１図に示すＩＩを用いて硬質炭素膜を合成した。Example A hard carbon film was synthesized using II shown in FIG.
原料ガス１３．１４としてメタン１００％を用い、反応
容器６内に５ＳＣＣＭで導入し、高面′！Ｉｔ発振器１
から１３．５６ＭＨｚの高周波によりプラズマ放電をお
こさせた。この時の投入電力は２００１で反応容器６内
のガス圧力は０．０８Ｔｏｒｒであった。反応容器６内
のアセチレン濃度す見るため、圧力を変化させ、プラズ
マ放電空間に存在するアセチレン濃度をＦＴ・ＩＲ分析
装置１５．１５により検出したところ、第３図のグラフ
に示す結果を得た。Using 100% methane as the raw material gas 13.14, it was introduced into the reaction vessel 6 at 5 SCCM, and the high surface '! It oscillator 1
Plasma discharge was caused by a high frequency of 13.56 MHz. At this time, the input power was 2001, and the gas pressure inside the reaction vessel 6 was 0.08 Torr. In order to check the acetylene concentration in the reaction vessel 6, the pressure was changed and the acetylene concentration present in the plasma discharge space was detected by the FT/IR analyzer 15.15, and the results shown in the graph of FIG. 3 were obtained.
そこで、成膜速度とプラズマの安定性を考慮して反応容
器６内の圧力を０．１５Ｔｏｒｒに設定し硬質炭素膜を
合成したところ、剥離のない高硬度で潤滑性の潰れた膜
がシリコン基体上に形成された。なお、口の場合のアセ
チレン濃度は２．５×１０−町ｎｏ ｌ ／ＣＩ’であ
った。Therefore, when we synthesized a hard carbon film by setting the pressure inside the reaction vessel 6 to 0.15 Torr in consideration of the film formation rate and plasma stability, we found that a highly hard and lubricating film with no peeling was formed on the silicon substrate. formed on top. Note that the acetylene concentration in the mouth was 2.5×10 −m /CI′.
比較のために反応容器Ｇ内のガス圧力を０．０７Ｔｏｒ
ｒに設定した以外は実施例と同様の条件で炭素膜を合成
した。For comparison, the gas pressure in reaction vessel G was set to 0.07 Tor.
A carbon film was synthesized under the same conditions as in the example except that r was set.
この時のアセチレン濃度は１，７ｘｌＯ−ｑｉｏｊ／ｊ
Ｖであった。実施例と比較例で得た炭素膜の成膜速度と
躾の物性値を第１表に示す。The acetylene concentration at this time is 1,7xlO-qioj/j
It was V. Table 1 shows the deposition rate and physical property values of the carbon films obtained in Examples and Comparative Examples.
第１表
第１表から明らかなように、実施例で合成した炭素膜に
比べて比較例で合成した炭素膜は物性１ｉ１ｔｆ大巾に
劣ることがわかる。Table 1 As is clear from Table 1, the carbon film synthesized in the comparative example is inferior to the carbon film synthesized in the example in physical properties 1i1tf width.
上記実施例では高周波の交流電界によるプラズマを用い
たが、これに限られるものではなく、どのような他のプ
ラズマであっても本発明法は有効に利用することができ
る利点がある。Although plasma generated by a high-frequency alternating electric field was used in the above embodiments, the invention is not limited to this, and the method of the present invention has the advantage that it can be effectively used with any other plasma.
〈発明の効果〉
以上説明したように、本発明は、炭化水素化合物を含む
原料ガスをプラズマ放電により分解し、基体上にＶ＃！
質炭素炭素膜成する際に、前記プラズマ放電により形成
されるプラズマ［！空Ｈ領ｌｊｌ 中（７） ７ ’ｃ
チレ＞ ’７） Ｊ ｒｌ ヲ１ 、ＯＸ １０−’
１１０１ ／ｃ１３以下に調整することを特徴とする
。<Effects of the Invention> As explained above, the present invention decomposes a raw material gas containing a hydrocarbon compound by plasma discharge and deposits V#! on a substrate.
When forming a carbon film, the plasma formed by the plasma discharge [! Sky H area ljl Medium (7) 7 'c
Chile>'7) J rl wo1, OX 10-'
It is characterized by adjusting to 1101/c13 or less.
本発明によれば、従来、硬質炭零躾合成時に問題であっ
た炭素膜の膜質の劣化を防ぐことができ、高硬度で潤滑
性に優れ、安定した品質の硬質炭素膜が常に供給するこ
とが可能になった。According to the present invention, it is possible to prevent the deterioration of the film quality of the carbon film, which has conventionally been a problem during the synthesis of hard carbon, and to constantly supply a hard carbon film with high hardness, excellent lubricity, and stable quality. is now possible.
これによる工業的１ＩｉＷｉは大きい。The industrial 1IiWi resulting from this is large.
第１図は本発明法を実施する際に用いられる装置の一例
を示す説明図、第２図は従来例の装置の説明図、第３図
はガス圧力とアセチレン濃度及び膜質の関係を示すグラ
フである。
符号１・・・・・・高周波発振器
２・・・・・・マツチングボックス
３．４・・・・・・電極 ５・・・・・・基体６
・・・・・・反応容器 ７・・・・・・排気口８．
９．１０・・・・・・バルブ
１１、 Ｔ２・・・・・・マスフローコントローラ１３
．１４・・・・・・原料ガス
１５・・・・・・ＦＴ・ＩＲ分析装置
１６．１７・・・・・・１ｎＳｅ窓 １８・・・・・
・赤外光１９・・・・・・制御装置 ２０・・・・
・・圧力調整弁第２図
第３
図
０．０５
０．１
ガ′ス瓜力 （丁ｏｒｒ）
０．１５Fig. 1 is an explanatory diagram showing an example of an apparatus used in carrying out the method of the present invention, Fig. 2 is an explanatory diagram of a conventional apparatus, and Fig. 3 is a graph showing the relationship between gas pressure, acetylene concentration, and film quality. It is. Code 1...High frequency oscillator 2...Matching box 3.4...Electrode 5...Base 6
...Reaction container 7...Exhaust port 8.
9.10... Valve 11, T2... Mass flow controller 13
．． 14... Raw material gas 15...FT/IR analyzer 16.17...1nSe window 18...
・Infrared light 19...Control device 20...
...Pressure regulating valve Fig. 2 Fig. 3 0.05 0.1 Gas pressure 0.15
Claims (1)
り分解し、基体上に硬質炭素膜を合成する際に、前記プ
ラズマ放電により形成されるプラズマ放電空間領域中の
アセチレンの濃度を１．０×１０＾−＾９ｍｏｌ／ｃｍ
＾３以下に調整することを特徴とする硬質炭素膜の合成
方法。1) When a raw material gas containing a hydrocarbon compound is decomposed by plasma discharge and a hard carbon film is synthesized on a substrate, the concentration of acetylene in the plasma discharge space region formed by the plasma discharge is set to 1.0×10 ^-^9mol/cm
A method for synthesizing a hard carbon film characterized by adjusting the carbon film to ^3 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174465A JPH0225569A (en) | 1988-07-13 | 1988-07-13 | Method for synthesizing hard-carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174465A JPH0225569A (en) | 1988-07-13 | 1988-07-13 | Method for synthesizing hard-carbon film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0225569A true JPH0225569A (en) | 1990-01-29 |
Family
ID=15978959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63174465A Pending JPH0225569A (en) | 1988-07-13 | 1988-07-13 | Method for synthesizing hard-carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0225569A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1132504A1 (en) * | 2000-02-28 | 2001-09-12 | Horiba, Ltd. | Thin film depositing process and device, ftir gas analyzer used in the thin film depositing process, and mixed gas supplying device used in the thin film depositing process |
| JP2005298286A (en) * | 2004-04-13 | 2005-10-27 | Japan Science & Technology Agency | Apparatus and method of decomposing hydrocarbon |
| JP2007262514A (en) * | 2006-03-29 | 2007-10-11 | Sumitomo Electric Ind Ltd | Chemical vapor deposition system |
-
1988
- 1988-07-13 JP JP63174465A patent/JPH0225569A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1132504A1 (en) * | 2000-02-28 | 2001-09-12 | Horiba, Ltd. | Thin film depositing process and device, ftir gas analyzer used in the thin film depositing process, and mixed gas supplying device used in the thin film depositing process |
| US7485189B2 (en) | 2000-02-28 | 2009-02-03 | Horiba, Ltd. | Thin film deposition device using an FTIR gas analyzer for mixed gas supply |
| JP2005298286A (en) * | 2004-04-13 | 2005-10-27 | Japan Science & Technology Agency | Apparatus and method of decomposing hydrocarbon |
| JP2007262514A (en) * | 2006-03-29 | 2007-10-11 | Sumitomo Electric Ind Ltd | Chemical vapor deposition system |
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