JPS62124272A - Formation of electrically conductive carbon film - Google Patents
Formation of electrically conductive carbon filmInfo
- Publication number
- JPS62124272A JPS62124272A JP60261382A JP26138285A JPS62124272A JP S62124272 A JPS62124272 A JP S62124272A JP 60261382 A JP60261382 A JP 60261382A JP 26138285 A JP26138285 A JP 26138285A JP S62124272 A JPS62124272 A JP S62124272A
- Authority
- JP
- Japan
- Prior art keywords
- carbon film
- substrate
- conductive carbon
- electrically conductive
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、優れた導電性を有する易黒鉛化性炭素膜の
形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming a graphitizable carbon film having excellent electrical conductivity.
従来、このような易黒鉛化性炭素を得る方法はいわゆる
熱分解法が一般的である。この方法は原料であるメタン
、エタン、プロパン、ベンゼン等の脂肪族または芳香族
炭化水素の雰囲気中で反応系を高温に加熱することによ
り炭化水素を熱分解し、炭素質を生成するものである。Conventionally, a so-called pyrolysis method has been commonly used to obtain such graphitizable carbon. This method thermally decomposes hydrocarbons by heating the reaction system to high temperatures in an atmosphere of aliphatic or aromatic hydrocarbons such as methane, ethane, propane, and benzene, which are raw materials, to generate carbonaceous substances. .
（例えば大釜ら“炭素化工学の基礎” １９８０ オ
ーム社）生成した炭素質の特性は加熱温度に大きく依存
し、２０００’Ｃを越える加熱温度でないと良好な炭素
質は得られない。（方法１）
上記方法よりも低温（１０００℃）で、高周波放電によ
りベンゼンのプラズマ重合を行ない、石英板あるいはシ
リコンウェハー上に炭素薄膜を得ることも行なわれてい
る（エッチ、マツシマら、ジャーナルオブアプライドフ
イジックス、２２巻（５号）、８８８ （１９８３）
） （Ｈ，ＭＡＴＳＵＳＨＩＭＡｅｔ ａｌ Ｊ、
ＡＰＰＬ、ＰＨＹＳ、Ｖｏｌ、２２（ｔｌｈ５）、８８
８（１９８３）） （方法２）
〔発明が解決しようとする問題〕
しかしながら上記方法１においては、高価な高温のエネ
ルギーを多消費するという問題があり、方法２では得ら
れた炭素質の電導塵が低く、生成速度も低いという問題
がある。(For example, Ohkama et al., "Fundamentals of Carbonization Engineering," 1980, Ohm Publishing) The properties of the produced carbonaceous material depend largely on the heating temperature, and good carbonaceous material cannot be obtained unless the heating temperature exceeds 2000'C. (Method 1) Plasma polymerization of benzene is carried out using high-frequency discharge at a lower temperature (1000°C) than the above method, and carbon thin films are also obtained on quartz plates or silicon wafers (Etchi, Matsushima et al., Journal of Applied Physics, Volume 22 (No. 5), 888 (1983)
) (H, MATSUSHIMAet al J,
APPL, PHYS, Vol, 22 (tlh5), 88
8 (1983)) (Method 2) [Problem to be solved by the invention] However, in the above method 1, there is a problem that a large amount of expensive high-temperature energy is consumed, and in method 2, the obtained carbonaceous conductive dust There is a problem that the production rate is low and the production rate is also low.
この発明は、上記従来技術の問題点に鑑み、方法１の様
に高価な熱エネルギーを多消費せず、父方法２から得た
炭素質よりも導電性に優れた品位の高い炭素膜が形成さ
れる方法を提供するものである。In view of the problems of the prior art described above, this invention does not consume a large amount of expensive thermal energy like Method 1, and forms a high-grade carbon film with better conductivity than the carbon material obtained from Method 2. This method provides a method for
その要旨とするところは゛ヘテロ原子を含有する炭化水
素ガスを原料として、９５０℃を越える温度に加熱され
た基材上にプラズマ放電により炭素膜を形成させること
を特徴とする導電性炭素膜形成方法にある。The gist is ``A conductive carbon film forming method characterized by forming a carbon film by plasma discharge on a substrate heated to a temperature exceeding 950°C using a hydrocarbon gas containing heteroatoms as a raw material. It is in.
この発明において原料となるヘテロ原子を含有する炭化
水素としては、例えばメチルアミン、プロピルアミン、
アクリロニトリル、アミノアクリロニトリル、プロピル
メルカプタン、四基化炭ロニトリル、チオフェンはきわ
めて適している。In this invention, examples of the hydrocarbon containing a heteroatom that can be used as a raw material include methylamine, propylamine,
Acrylonitrile, aminoacrylonitrile, propylmercaptan, tetracarbonitrile, thiophene are highly suitable.
プラズマ放電により基板上に炭素膜を形成する方法は、
反応容器中を原料である炭化水素蒸気で所定の圧力に充
満させ、高周波電界を印加することによって基材上に炭
素膜を形成する。The method of forming a carbon film on a substrate by plasma discharge is as follows:
A carbon film is formed on the substrate by filling the reaction vessel with hydrocarbon vapor as a raw material to a predetermined pressure and applying a high-frequency electric field.
この発明において、基材としては、鉄、コバルト、ニッ
ケル等の金属、或はステンレス等の合金からなる板、シ
ート、フィルム、その他の成形品を使用することができ
、ファイバ状のもの及びその織布も使用することができ
る。また、石英、ガラス、シリコン、セラミックからな
る金属以外のものを用いても良い。更にカーボンファイ
バ、カーホンシート（例えば、カーボンファイバ織布）
、グラファイトファイバ、グラファイト板（例えばＨＯ
ＰＧ ）を用いることができる。上記基材のうち特シζ
遷移金属を含む基材が好ましい。In this invention, plates, sheets, films, and other molded products made of metals such as iron, cobalt, and nickel, or alloys such as stainless steel can be used as the base material, and fiber-like materials and woven products thereof can be used. Cloth can also be used. Moreover, materials other than metals such as quartz, glass, silicon, and ceramic may be used. Furthermore, carbon fiber, carphone sheet (e.g. carbon fiber woven fabric)
, graphite fiber, graphite plate (e.g. HO
PG) can be used. Among the above base materials, special
Substrates containing transition metals are preferred.
基材は、９５０℃を越える温度に加熱すると、特に、炭
素膜の形成に効果的である。Heating the substrate to a temperature above 950°C is particularly effective in forming a carbon film.
（実施例１）
導入し、圧力１．０ｍｍＨｇに保持した。然る後、高周
波電界（１３，５６ＭＨｚ 出力４０Ｗ）を印加し、
プラズマ反応を行ない、基材上に金属光沢を有する膜厚
２０〜２２μｍの炭素膜を形成せしめた。(Example 1) The pressure was maintained at 1.0 mmHg. After that, a high frequency electric field (13,56MHz output 40W) was applied,
A plasma reaction was carried out to form a carbon film having a metallic luster and a thickness of 20 to 22 μm on the substrate.
得られた炭素膜のグラファイト層間隔はｄ＝３．３６６
Ａとなりかなりグラファイト化が進行している事が判っ
た。The graphite layer spacing of the obtained carbon film is d=3.366
The result was A, indicating that graphitization had progressed considerably.
（実施例２）
ＳＵＳ３０４からなるシート状の基材（厚み０．２ ｍ
ｍ ）を合成室内に静置して、基材を１１００’ｃ、１
０５０’Ｃ及び１０００℃に加熱した後、チオフェン蒸
気ヲ合成室内に導入し、圧力１．０ｍｍＨｇに保持した
。然る後、高周波電界（１３，５６ＭＨｚ 出力４０
Ｗ）を印加し、プラズマ反応を行ない、基材上に金属光
沢を有する膜厚２０〜２２μｍの炭素膜を形成せしめた
。(Example 2) A sheet-like base material made of SUS304 (thickness 0.2 m
m) was left still in the synthesis chamber, and the base material was heated at 1100'c, 1
After heating to 050'C and 1000C, thiophene vapor was introduced into the synthesis chamber and maintained at a pressure of 1.0 mmHg. After that, high frequency electric field (13,56MHz output 40
W) was applied to perform a plasma reaction to form a carbon film having a thickness of 20 to 22 μm and having metallic luster on the substrate.
得られた炭素薄膜の電導塵は基材温度の高い順序で、各
々１．４Ｘ１０３，８００．７００５／ｃｍであった。The conductive dust of the obtained carbon thin film was 1.4×10 3 and 800.7005/cm, respectively, in descending order of substrate temperature.
（比較例１）
ＳＵＳ３０４からなるシート状の基材（厚み０．２・Ｍ
）を合成室内に静置して基材を１０００℃に加熱し、ベ
ンゼン蒸気を合成室内に導入、圧力ｌｍｍＨｇに保持し
、熱分解反応を行なわしめ、基材上に炭素質を形成せし
めた。炭素質の形状は繊維状であった。(Comparative Example 1) Sheet-like base material made of SUS304 (thickness 0.2 M
) was allowed to stand still in a synthesis chamber and the substrate was heated to 1000° C., and benzene vapor was introduced into the synthesis chamber and maintained at a pressure of 1 mmHg to carry out a thermal decomposition reaction to form carbonaceous material on the substrate. The shape of the carbonaceous material was fibrous.
得られた炭素質のＸ線回折の結果よりグラファイト層間
隔はｄ＝３．４６２Ａとなり、グラファイト化が進行し
ていない炭素質である事が判った。As a result of X-ray diffraction of the obtained carbonaceous material, the graphite layer spacing was d=3.462A, and it was found that the carbonaceous material had not undergone graphitization.
（比較例２）
ＳＵＳ３０４からなるシート状の基材（厚み０．２Ｍ）
を合成室内に静置して、基材を１０００℃に加熱した後
、ベンゼン蒸気を合成室内に導入し、圧力１．０１１１
１ｎＨｇに保持した。然る後、高周波電界（１３，５６
ＭＨｚ出力４０Ｗ）を印加し、プラズマ反応を行ない、
基材上に金属光沢を有する膜厚２０〜２２μｍ の炭素
膜を形成せしめた。(Comparative Example 2) Sheet-like base material made of SUS304 (thickness 0.2M)
was left still in the synthesis chamber and the base material was heated to 1000°C, then benzene vapor was introduced into the synthesis chamber and the pressure was increased to 1.0111℃.
It was maintained at 1 nHg. After that, a high frequency electric field (13,56
MHz output of 40 W) was applied to perform a plasma reaction,
A carbon film having a thickness of 20 to 22 μm and having metallic luster was formed on the base material.
得られた炭素膜のグラファイト層間隔はｄ＝３．４４２
Ａ となり、わずかにグラファイト化がすすんでいる
事が判った。The graphite layer spacing of the obtained carbon film is d=3.442
It was found that graphitization was progressing slightly.
（比較例３）
ＳＵＳ３０４からなるシート状の基材（厚み０．２Ｍ）
を合成室内に静置して、基材を１１００℃ に加熱した
後、ベンゼン蒸気を合成室内に導入し、を形成せしめ六
〇
得られた炭素膜の電導度は６００５／ａｎであった。(Comparative Example 3) Sheet-like base material made of SUS304 (thickness 0.2M)
was allowed to stand still in a synthesis chamber and the substrate was heated to 1100° C., and then benzene vapor was introduced into the synthesis chamber to form 60. The conductivity of the obtained carbon film was 6005/an.
（比較例４）
ＳＵＳ ３０４からなるシート状の基材（厚み０．２ｍ
ｍ）を合成室内に静置して、基材を９５０℃に加熱した
後、チオフェン蒸気を合成室内に導入し、圧力１．Ｏｍ
ｍＨｇに保持した。然る後、高周波電界（１３，５６Ｍ
Ｈｚ 出力４０Ｗ ）を印加し、プラズマ反応を行な
い、基材上に膜厚２０〜２２μｍの炭素膜を形成せしめ
な。(Comparative Example 4) Sheet-like base material made of SUS 304 (thickness 0.2 m
m) was left still in the synthesis chamber and the base material was heated to 950°C, then thiophene vapor was introduced into the synthesis chamber and the pressure was increased to 1. Om
Maintained at mHg. After that, a high frequency electric field (13,56M
Hz and output power of 40 W) to conduct a plasma reaction and form a carbon film with a thickness of 20 to 22 μm on the substrate.
得られた炭素薄膜の電導度は３００５／ｃｍであった。The electrical conductivity of the obtained carbon thin film was 3005/cm.
（比較例５）
シリコンからなる基材（厚み０．２ ｍ ） を合成
室内に静置して、基材を１１００℃に加熱した後、ベン
ゼン蒸気を合成室内に導入し、圧力１．ＯａｎＨｇに保
持した。然る後、高周波電界（１３，５６ＭＨｚ出力４
０Ｗ）を印加し、プラズマ反応を行ない、基材上に膜厚
２０〜２２μｍの炭素膜を形成せしめた。(Comparative Example 5) A base material made of silicon (thickness: 0.2 m) was placed in a synthesis chamber, and after heating the base material to 1100°C, benzene vapor was introduced into the synthesis chamber and the pressure was increased to 1. It was maintained at OanHg. After that, high frequency electric field (13,56MHz output 4
0 W) was applied to perform a plasma reaction to form a carbon film with a thickness of 20 to 22 μm on the substrate.
得られた炭素膜の電導度は３００Ｓ／ａｎであった。The electrical conductivity of the obtained carbon film was 300 S/an.
この発明によって提案されたヘテロ原子を含有する炭化
水素を原料として、プラズマＣＶＤにて炭素膜を合成す
る方法によって、これまでより低温で高品位な炭素質を
得ることが出来る。By the method proposed by this invention of synthesizing a carbon film by plasma CVD using a hydrocarbon containing heteroatoms as a raw material, it is possible to obtain high-quality carbon at a lower temperature than ever before.
Claims (4)
０℃を越える温度に加熱された基材上にプラズマ放電に
より炭素膜を形成させることを特徴とする導電性炭素膜
の形成方法。(1) 95 using a hydrocarbon containing a heteroatom as a raw material
A method for forming a conductive carbon film, which comprises forming a carbon film by plasma discharge on a substrate heated to a temperature exceeding 0°C.
窒素を含有する炭化水素であることを特徴とする特許請
求の範囲第１項記載の導電性炭素膜の形成方法。(2) The method for forming a conductive carbon film according to claim 1, wherein the hydrocarbon containing a heteroatom is a hydrocarbon containing sulfur or nitrogen.
ェンあるいはアクリロニトリルであることを特徴とする
特許請求の範囲第２項記載の導電性炭素膜の形成方法。(3) The method for forming a conductive carbon film according to claim 2, wherein the hydrocarbon containing sulfur or nitrogen is thiophene or acrylonitrile.
求の範囲第１項、第２項または第３項記載の導電性炭素
膜の形成方法。(4) The method for forming a conductive carbon film according to claim 1, 2, or 3, wherein the base material contains a transition metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60261382A JPS62124272A (en) | 1985-11-22 | 1985-11-22 | Formation of electrically conductive carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60261382A JPS62124272A (en) | 1985-11-22 | 1985-11-22 | Formation of electrically conductive carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62124272A true JPS62124272A (en) | 1987-06-05 |
| JPS6248754B2 JPS6248754B2 (en) | 1987-10-15 |
Family
ID=17361070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60261382A Granted JPS62124272A (en) | 1985-11-22 | 1985-11-22 | Formation of electrically conductive carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62124272A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63293164A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6455542U (en) * | 1987-09-30 | 1989-04-06 |
-
1985
- 1985-11-22 JP JP60261382A patent/JPS62124272A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63293164A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
| JPH0258352B2 (en) * | 1987-05-27 | 1990-12-07 | Kogyo Gijutsuin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6248754B2 (en) | 1987-10-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |