JPS62174379A - Formation of thin hard carbon film - Google Patents
Formation of thin hard carbon filmInfo
- Publication number
- JPS62174379A JPS62174379A JP61015097A JP1509786A JPS62174379A JP S62174379 A JPS62174379 A JP S62174379A JP 61015097 A JP61015097 A JP 61015097A JP 1509786 A JP1509786 A JP 1509786A JP S62174379 A JPS62174379 A JP S62174379A
- Authority
- JP
- Japan
- Prior art keywords
- film
- thin film
- thin
- carbon film
- forming
- 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.)
- Expired - Lifetime
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 2
- 239000003701 inert diluent Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 26
- 239000010408 film Substances 0.000 abstract description 24
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 229910002804 graphite Inorganic materials 0.000 abstract description 12
- 239000010439 graphite Substances 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052786 argon Inorganic materials 0.000 abstract description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 2
- 229910052754 neon Inorganic materials 0.000 abstract description 2
- 239000001294 propane Substances 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の技術的分野）
本発明は、硬質炭素薄膜の形成方法に関し、さらに詳し
くは、プラズマＣＶＤプロレスによるアモルファスカー
ボン等の炭素薄膜の形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a method for forming a hard carbon thin film, and more particularly to a method for forming a carbon thin film such as amorphous carbon by plasma CVD processing.
（発明の技術的背景ならびにその問題点）近年、エレク
トロニクス材料、光学材料などべの応用が期待されてい
る硬質炭素薄膜に苅する関心が高まっている。(Technical background of the invention and its problems) In recent years, there has been increasing interest in hard carbon thin films, which are expected to be applied to electronic materials, optical materials, and other fields.
炭素薄膜に関連するものとしては、プラズマプロセスに
よって有機上ツマ−から合成される有機重合性薄膜がす
でに知られている。この有機重合性薄膜は、一般に、ア
モルファスポリマーと称されているものであって、架橋
性の高分子でおる。Related to carbon thin films, organic polymerizable thin films synthesized from organic polymers by a plasma process are already known. This organic polymerizable thin film is generally called an amorphous polymer, and is made of a crosslinkable polymer.
ところが、有機上ツマ−を反応原料とする場合でも、七
ツマ−の種類やプラズマ教電の条イ（１によっては、ダ
イヤモンド状、またはアモルファスカーボンなどの硬質
炭素薄膜が得られることか見出されたことから、有機上
ツマ−を用いるプラズマＣＶＤプロセスが新たな関心を
集めでいる。However, it has been found that even when organic carbon dioxide is used as a reaction raw material, a hard carbon thin film such as diamond-like or amorphous carbon can be obtained depending on the type of carbon fiber and the method of plasma education. As a result, plasma CVD processes using organic materials are attracting renewed interest.
これらの硬質炭素薄膜としては、ダイヤモンド、アモル
ファスカーボン、グラファイト等の１工々な膜１構造が
考えられる。As these hard carbon thin films, elaborate film structures such as diamond, amorphous carbon, graphite, etc. can be considered.
しかしながら、薄膜の構造、その生成のプ［１しスと放
電条件との関係については、いまだ充分に明らかにされ
ていないのか現状である。特に、低カス圧下てのプラズ
マＣＶＤ法の場合には、有機上ツマーカスと不活性希釈
カスとの反応により、硬質炭素薄膜を形成する際に、薄
膜中にグラフフィトの生成か避けられず、炭素膜の膜質
が不均等となり、Ｘ線マスク用薄膜、半導体基板用絶縁
膜、必るいは、ラングミュアブロジェット（ＬＢ）膜用
基板として有用なアモルファスカーボンの薄膜等として
は好ましいものではなかった。また、このグラファイト
の生成を抑制する方法も見出されていなかった。However, the relationship between the structure of the thin film, its formation process, and discharge conditions has not yet been fully clarified. In particular, in the case of the plasma CVD method under a low scum pressure, when a hard carbon thin film is formed due to the reaction between the organic topmarker and the inert diluted scum, the formation of graphite in the thin film is unavoidable. The quality of the film was non-uniform, and it was not preferable as an amorphous carbon thin film useful as a thin film for an X-ray mask, an insulating film for a semiconductor substrate, or a substrate for a Langmuir-Blodgett (LB) film. Furthermore, no method has been found to suppress the production of graphite.
グラフフィトの生成は、薄膜の光透過性が低いため、Ｘ
線マスク用などに用いるためには好ましくなく、このた
め、このような問題のないアモルファスカーボン等の硬
質炭素薄膜の形成方法を確立することと、そのためのプ
ラズマＣＶＤプロレスの条件を選択することが強く望ま
れていた。The generation of graphite is due to the low light transmittance of the thin film.
It is not preferable for use in line masks, etc. Therefore, it is strongly recommended to establish a method for forming a hard carbon thin film such as amorphous carbon that does not have such problems, and to select conditions for plasma CVD wrestling for that purpose. It was wanted.
（発明の目的）
本発明１ユ、上記のような従来技術に伴なう問題点を解
決しようとづるものであり、プラズマＣＶＤプロレスに
より、グラフフィトの生成を抑制した硬質炭素薄膜、特
にアモルファスカーボン薄膜を形成する方法を提供する
ことを目的としている。(Objective of the Invention) The present invention 1 is aimed at solving the problems associated with the above-mentioned conventional techniques, and it is a hard carbon thin film, especially amorphous carbon, that suppresses the generation of graphite by plasma CVD processing. The purpose is to provide a method for forming thin films.
また、本発明は、薄膜の機能特性としての透光性に優れ
た炭素薄膜を形成する方法を提供することを目的として
いる。Another object of the present invention is to provide a method for forming a carbon thin film having excellent light transmittance as a functional property of the thin film.
（発明の概要）
本発明に係る硬質炭素薄膜の形成方法は、プラズマＣＶ
Ｄプロセスによって、有機上ツマ−と不活性希釈ガスと
により炭素薄膜を形成するにあたり、反応ガス系に酸素
ガスを添加することを特徴としている。(Summary of the Invention) The method for forming a hard carbon thin film according to the present invention includes plasma CV
When a carbon thin film is formed by the D process using an organic layer and an inert diluent gas, oxygen gas is added to the reaction gas system.
この方法によって得られる硬質炭素薄膜、特にアモルフ
ァスカーボン薄膜は、Ｘ線マスク用として、あるいは半
導体基板用絶縁物などの広い範囲の機能材料として応用
が期待されるものでおる。The hard carbon thin film, especially the amorphous carbon thin film obtained by this method, is expected to be applied as a wide range of functional materials such as X-ray masks and insulators for semiconductor substrates.
（発明の詳細な説明）
本発明のプラズマＣＶＤプロセスに用いる装置について
は、平行平板電極による方法、高周波励起による方法な
どの、プラズマプロセスに使用することのできる適宜の
ものを用いることができる。(Detailed Description of the Invention) As for the apparatus used in the plasma CVD process of the present invention, any suitable apparatus that can be used in a plasma process, such as a method using parallel plate electrodes or a method using high frequency excitation, can be used.
また、硬質炭素薄膜形成用の基板については、３ｉウエ
ハー、ガラス基板、金属、プラスチックなとの任意のも
のが使用できる。Further, as for the substrate for forming the hard carbon thin film, any substrate such as a 3i wafer, a glass substrate, metal, or plastic can be used.
薄膜形成のための反応には、成膜分子で必る有機モノマ
ーと、不活性の希釈ガス、及び添加成分としての酸素カ
スを用いる。右は七ツマ−については、メタン、エタン
、プロパン、エチレンなどの炭化水素をはじめとする有
機上ツマ−を適宜に選択することができる。また、不活
性の希釈ガスとしては、アルゴン（Ａｒ＞、ネオン（Ｎ
ｅ＞などを使用する。The reaction for forming a thin film uses organic monomers necessary for film-forming molecules, an inert diluent gas, and oxygen residue as an additive component. As for the seven-layer compound shown on the right, an organic compound including hydrocarbons such as methane, ethane, propane, and ethylene can be appropriately selected. In addition, as inert diluent gases, argon (Ar>, neon (N
Use e> etc.
プラズマＣＶＤの反応系に導入づるこれらのガス成分の
υ１合は、所望とする炭素薄膜の性状、膜厚、反応容器
、カス圧によって変わってくるが、たとえば、約１０．
１！の反応容器ではその流量は、右）幾モノマーが５０
−０．１ｓｅｃｍ、希釈ガスか１００〜０．１ ｓｅｃ
ｍ、 酸素が５０−０．．０１ｓｅｃｍで必って、成分
の相対比は、有機モノマーに大して希釈ガスが５０〜１
、酸素か５０〜０．１の範囲とする。反応系のカス圧力
は１〜０゜０１”’ｒｏｒｒとするのが好ましい。The ratio υ1 of these gas components introduced into the plasma CVD reaction system varies depending on the desired properties of the carbon thin film, film thickness, reaction vessel, and gas pressure, but is, for example, about 10.
1! In the reaction vessel, the flow rate is 50
-0.1sec, diluent gas or 100~0.1sec
m, oxygen is 50-0. ．． At 0.01 sec, the relative ratio of the components is approximately 50 to 1 of the diluent gas to the organic monomer.
, oxygen is in the range of 50 to 0.1. The scum pressure in the reaction system is preferably 1 to 0.01'''rorr.
なお、酸素ガスの添加は、硬質炭素薄膜中へのグラファ
イトの存在が許容される程度に応じて、適宜にその添加
徂を調整すればよい。Note that the addition range of oxygen gas may be adjusted as appropriate depending on the extent to which graphite is allowed to exist in the hard carbon thin film.
ざらに、プロセスの放電電力、放電時間についても、使
用する装置、薄膜の膜厚によって適宜に選択することが
できる。たとえば、平行平板電極による装置を用いる場
合には、放電電力は５００〜’ＩＯＷの範囲が選択でき
る。In general, the discharge power and discharge time of the process can be appropriately selected depending on the equipment used and the thickness of the thin film. For example, when using a device using parallel plate electrodes, the discharge power can be selected from a range of 500 to 'IOW.
以上のプロセスの諸条件の選択によって、プラズマＣＶ
Ｄプロセスの反応系への酸素ガスの添加効果は顕著なも
のとなり、グラフフィトの生成か抑制され、炭素薄膜の
光透過度は著しく向上する。By selecting the above process conditions, plasma CV
The effect of adding oxygen gas to the reaction system in process D is significant, the generation of graphite is suppressed, and the light transmittance of the carbon thin film is significantly improved.
アモルファスカーボン薄膜として優れた膜質のものか得
られる。An amorphous carbon thin film with excellent film quality can be obtained.
このような本発明による効果は、これまでのプラズマＣ
ＶＤプロセス技術からは全く予期しえないものである。The effects of the present invention are as follows:
This is completely unexpected from VD process technology.
以下、本発明の具体的な実施例を説明する。Hereinafter, specific examples of the present invention will be described.
実施例
炭素薄膜の形成は、平行平板電（車を有するプラズマＣ
ＶＤ装置（ＣＰＤ−１１０８，ＵＬＶＡＣ）を用いて、
１３．５６Ｍ１−１２、約０．１Ｔｏｒｒのガス圧力、
０．６〜１．６Ｗ／ｒｍの放電の条件において行なった
。Example Carbon thin film formation was performed using a parallel plate electrode (plasma C with a wheel).
Using a VD device (CPD-1108, ULVAC),
13.56M1-12, gas pressure of about 0.1 Torr,
The test was carried out under conditions of discharge of 0.6 to 1.6 W/rm.
基板としては、Ｓｉウェハー、ガラス基板等を用いた。As the substrate, a Si wafer, a glass substrate, etc. were used.
プラズマ診断には、分光器と、マスフィルタ型ガス分析
計を用いた。また、炭素薄膜の評価は、ＩＲ，ＥＳＣＡ
等によって行なった。A spectrometer and a mass filter type gas analyzer were used for plasma diagnosis. In addition, evaluation of carbon thin film is performed by IR, ESCA
etc.
（１）まず、酸素ガスを添加しないで、メタンとアルゴ
ンとの反応によって炭素薄膜を生成させた。(1) First, a carbon thin film was generated by a reaction between methane and argon without adding oxygen gas.
メタン流１５ ｓ ｅ ｃｍ、アルゴン流５５ Ｑ ｓ
ｃｃｍとし、放電カス圧力的Ｑ、 １Ｔｏｒｒの条
件で、２００ｗと４００ｗの放電電力で、各々２時間放
電した。Methane flow 15 sec cm, argon flow 55 Q s
ccm, discharge scum pressure Q, 1 Torr, and discharge power of 200 W and 400 W for 2 hours each.
２００Ｗの放電の場合には、１１７ａｏＡの膜厚の薄膜
が得られた（基礎圧力０．０１１Ｔｏｒｒ、放電ガス圧
力０．１０１Ｔｏｒｒ、基板温度４０ ’Ｃ）。また、
４０Ｑｗの放電の場合には、２回の放電で、各々１８１
００人及び、１６５００Ａの膜厚の薄膜が（ｑられだ（
基礎圧力０．０３３ＴＯｒｒ、Ｍ電カス圧力０．０９６
Ｔｏｒｒ、１板温度７３ ’Ｃ）。In the case of 200 W discharge, a thin film with a film thickness of 117 aoA was obtained (base pressure 0.011 Torr, discharge gas pressure 0.101 Torr, substrate temperature 40'C). Also,
In the case of 40Qw discharge, two discharges each yield 181
00 people and a thin film with a film thickness of 16500A (qreda(
Base pressure 0.033 TOrr, M electric gas pressure 0.096
Torr, 1 plate temperature 73'C).
ＩＲスペクトルによると、２００ｗの場合には、Ｃ−Ｈ
結合に起因する吸収が見られた。有機重合膜の構造が存
在するものと考えられる。According to the IR spectrum, at 200w, C-H
Absorption due to binding was observed. It is thought that the structure of an organic polymer film exists.
また、薄膜の外観は、２００Ｗの場合にはこげ茶色であ
るものの、放電電力を４００ｗにした場合はすみ状の黒
色であった。Further, the appearance of the thin film was dark brown when the discharge power was 200 W, but it was black with corners when the discharge power was 400 W.
放電電力を増大させて４００ｗとする時には、膜成長速
度も増大し、完全に炭素薄膜になっているものの、グラ
ファイトが多辺に生成するということができる。When the discharge power is increased to 400 W, the film growth rate also increases, and although the film becomes a completely thin carbon film, it can be said that graphite is formed on many sides.
（２）次に、反応系に酸素カスを添加して薄膜を形成し
た。(2) Next, oxygen residue was added to the reaction system to form a thin film.
前述と同様のメタンとアルゴンの流Ｆｆｇ （５Ｓ Ｃ
ｃｍと５Ｑｓｃｃｍ）で、４００ｗの放電電力で２時間
放電を行なった。The same methane and argon flow Ffg (5S C
cm and 5Qsccm), and discharge was performed for 2 hours at a discharge power of 400W.
反応系に、酸素ガスを１０１０５ｅ添加した。10105e of oxygen gas was added to the reaction system.
基礎圧力０．０３３ＴＯｒｒ、放電ガス圧力０゜１１０
Ｔｏｒｒ、基板温度７３°Ｃで、２回の放電によって、
各々膜厚が１４６００Ａ、及び１３７００への薄膜が得
られた。Base pressure 0.033 TOrr, discharge gas pressure 0°110
Torr, substrate temperature 73°C, by two discharges,
Thin films with film thicknesses of 14,600 A and 13,700 A were obtained, respectively.
この薄膜の外観は、透明度の大きい黒紫色の鏡面であっ
た。The appearance of this thin film was a black-purple mirror with high transparency.
酸素の添加によって膜成長速度は、酸素を添加しない場
合よりも１０％程度減少するものの、グラファイト成分
の生成が抑えられた炭素膜が生成する。このことは、酸
素添加量が解離水素量に比して著しく多いので、気相に
おいて炭素まで酸化除去することになり、このため膜成
長速度が減少することになり、逆に、グラファイト成分
が除去されて、アモルファスカーボンが堆積しやすくな
るものと考えられる。Although the addition of oxygen reduces the film growth rate by about 10% compared to when no oxygen is added, a carbon film is produced in which the production of graphite components is suppressed. This means that since the amount of oxygen added is significantly larger than the amount of dissociated hydrogen, even carbon is oxidized and removed in the gas phase, which reduces the film growth rate, and conversely, graphite components are removed. It is thought that this makes it easier for amorphous carbon to accumulate.
Claims (4)
不活性希釈ガスの存在下に反応させて硬質炭素薄膜を形
成するにあたり、反応系に酸素を添加することを特徴と
する硬質炭素薄膜の形成方法。(1) A method for forming a hard carbon thin film, which comprises adding oxygen to the reaction system when forming a hard carbon thin film by reacting an organic monomer in the presence of an inert diluent gas by a plasma CVD process.
（１）項に記載の方法。(2) The method according to claim (1), wherein the organic monomer is a hydrocarbon.
第（１）項に記載の方法。(3) The method according to claim (1), wherein the hard carbon thin film is a transparent thin film.
特許請求の範囲第（１）項ないし第（３）項に記載の方
法。(4) The method according to claims (1) to (3), wherein the hard carbon thin film is an amorphous carbon thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61015097A JPS62174379A (en) | 1986-01-27 | 1986-01-27 | Formation of thin hard carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61015097A JPS62174379A (en) | 1986-01-27 | 1986-01-27 | Formation of thin hard carbon film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62174379A true JPS62174379A (en) | 1987-07-31 |
Family
ID=11879337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61015097A Expired - Lifetime JPS62174379A (en) | 1986-01-27 | 1986-01-27 | Formation of thin hard carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62174379A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01246115A (en) * | 1988-03-26 | 1989-10-02 | Semiconductor Energy Lab Co Ltd | Method for forming coating film of carbon or material composed mainly of carbon |
-
1986
- 1986-01-27 JP JP61015097A patent/JPS62174379A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01246115A (en) * | 1988-03-26 | 1989-10-02 | Semiconductor Energy Lab Co Ltd | Method for forming coating film of carbon or material composed mainly of carbon |
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