JPS61170570A - Formation of conductive graphite film - Google Patents
Formation of conductive graphite filmInfo
- Publication number
- JPS61170570A JPS61170570A JP1076385A JP1076385A JPS61170570A JP S61170570 A JPS61170570 A JP S61170570A JP 1076385 A JP1076385 A JP 1076385A JP 1076385 A JP1076385 A JP 1076385A JP S61170570 A JPS61170570 A JP S61170570A
- Authority
- JP
- Japan
- Prior art keywords
- graphite film
- film
- base material
- carbon film
- conductive graphite
- 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導電性グラファイト
膜の形成方法に関する
〔従来の技術〕
従来、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（例えば、
大釜ら“炭素化工学の基礎１９８０年、オーム社発行）
（方法ｌ）。これら炭素質は、大きく三種類に分類され
、第１表のように示される（長油ら、「炭素材料入門」
１９７９年、炭素材料学会Ｉり。これらの常温におげろ
電導度は、＆５〜５ Ｘ １０ ” Ｓ／ｃｍである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for forming a conductive graphite film having excellent electrical conductivity [Prior Art] Conventionally, the method for obtaining graphitizable carbon has been Thermal decomposition method is common. This method thermally decomposes hydrocarbons and generates carbonaceous substances by heating the reaction system to high temperatures in an atmosphere of hydrocarbons as raw materials (for example,
Ohkama et al., “Fundamentals of Carbonization Engineering, 1980, published by Ohmsha”
(Method l). These carbon materials are broadly classified into three types, as shown in Table 1 (Nagayu et al., "Introduction to Carbon Materials")
1979, Carbon Materials Society I. The electrical conductivity of these materials at room temperature is &5 to 5 x 10''S/cm.
第 １ 表
グラファイトの 製造温度１℃ 主な性質更に
、上記方法で得られる炭素質を例えば３０００．・℃の
高温で熱処理して、グラファイト化することも知られて
いる。Table 1: Production temperature of graphite: 1°C Main properties Furthermore, the carbonaceous material obtained by the above method is, for example, 3,000°C.・It is also known that graphite can be formed by heat treatment at high temperatures of ℃.
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、石英板あるいはソ
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（ Ｈ，ＭＡＴＳＵＳ）（ＩＭＡ ａｔ ａｌＪ−Ａ
ＰＰＬ−ＰＨＹＳ、 Ｖａｔ、 ２２ （Ｎｎ５ ）
、 ８８８（１９８３） ）（方法２）。Plasma polymerization of benzene is performed using high-frequency discharge at a lower temperature (1000°C) than the above method to obtain a carbon thin film on a quartz plate or soric wafer (H, MATSUS) (IMA at alJ-A).
PPL-PHYS, Vat, 22 (Nn5)
, 888 (1983) ) (Method 2).
しかし乍ら、上記方法１においては、易黒鉛化性炭素を
得る１つの条件として１２００℃以上の熱分解温度が必
要である。このような温度では基材の種類も限定され、
またエネルギーの損失も大きい。従ってより低温での易
黒鉛化性炭素合成法が望まれる。However, in the method 1 described above, a thermal decomposition temperature of 1200° C. or higher is required as one condition for obtaining graphitizable carbon. At such temperatures, the types of substrates are limited,
There is also a large loss of energy. Therefore, a method for synthesizing easily graphitizable carbon at lower temperatures is desired.
方法２では、電導度が１０”Ｓ／ａｎ未満であり、また
、炭素質生長速度が０．０５２μｍ／ｍ ｉ ｎと、方
法ｌ及び２の熱分解法における炭素質生長速度（１，７
＋−１７μｍ／ｍ ｉ ｎ ）に比較して、著しく低い
。In method 2, the electrical conductivity is less than 10"S/an, and the carbonaceous growth rate is 0.052 μm/min, which is the carbonaceous growth rate (1,7
+-17 μm/min).
■
（〔問題点を解決するための手段〕
この発明は、上記従来技術の問題点に鑑み方法ｌの様に
、炭素膜を形成する基材の種類が余り制限されずに、父
方法２から得た炭素質よりも導電性′に優れたグラファ
イト膜が形成される方法を提供子る。その要旨とすると
ころは、炭化水素ガスを歎料として、７００°Ｃ以上に
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
せた後、２０００℃以上の温度で熱処理を行なうことを
特徴とする導電性グラファイト膜の形成方法にある。(Means for Solving the Problems) In view of the above-mentioned problems of the prior art, the present invention is based on the parent method 2, without limiting the type of base material on which the carbon film is formed, as in method 1. The present invention provides a method for forming a graphite film with better conductivity than the obtained carbonaceous material.The gist of the method is to form a graphite film on a substrate heated to 700°C or higher using hydrocarbon gas as a feedstock. The method of forming a conductive graphite film is characterized in that a carbon film is formed by plasma discharge, and then heat treatment is performed at a temperature of 2000° C. or higher.
この発明において、原料となる炭化水素として、ガスと
なり得る物質、例えば、メタン、エタン、プロパン等の
脂肪族化合物ＣｎＨｔｎ−１−ｓ、アルケン、アルキン
等の不飽和誘導体すなわち１つ以上の二重結合あるいは
三重結合を有するもの、ベンゼン、ナフタレン、アント
ラセン、ピレン等の芳香族化合物が用いられ、特に１ａ
ａＨｇ程度で容易に蒸気を生ずる炭化水素が適している
。In this invention, the raw material hydrocarbons include substances that can become gases, such as aliphatic compounds such as methane, ethane, and propane, CnHtn-1-s, unsaturated derivatives such as alkenes and alkynes, that is, one or more double bonds. Alternatively, those having a triple bond, aromatic compounds such as benzene, naphthalene, anthracene, and pyrene are used, especially 1a
Hydrocarbons that easily generate steam at about aHg are 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、コバルラス、シ
リコン、七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、カーボンシート（例えば
、カーボンファイバ織布）、グラフフィトファイバ、グ
ラファイト板（例えば、ＨＯＰＧ ）を用いることがで
きる。上記基材のうち特に遷移金属を含む基材が、グラ
ファイト化反応の触媒物質として作用するので、好まし
い。In the present invention, materials other than metals such as iron, covar lath, silicon, and heptaramic may be used as the base material. Furthermore, carbon fibers, carbon sheets (eg, carbon fiber woven fabric), graphite fibers, graphite plates (eg, HOPG) can be used. Among the above-mentioned base materials, a base material containing a transition metal is particularly preferable because it acts as a catalyst substance for the graphitization reaction.
基材は、７００℃以上の温度に加熱すると、特に、炭素
膜の形成に効果的である。Heating the base material to a temperature of 700° C. or higher is particularly effective in forming a carbon film.
この発明においては、基材上に炭素膜を形成した後Ｋ、
更に、２０００℃以上の温度で熱処理が行なわれる。熱
処理は、基材から剥離した炭素膜に対して行なってもよ
く、基材と共に行なってもよい。基材が融点２０００°
Ｃ未満の物質からなる基材を用いた場合、基材と共に熱
処理を行なうと基材が融解、揮散等によって除去され、
熱処理と同時にグラファイト膜のみを分離することがで
きる。In this invention, after forming a carbon film on a base material, K,
Furthermore, heat treatment is performed at a temperature of 2000° C. or higher. The heat treatment may be performed on the carbon film peeled from the base material, or may be performed together with the base material. Base material has a melting point of 2000°
When using a base material made of a substance with less than C, if heat treatment is performed together with the base material, the base material will be removed by melting, volatilization, etc.
Only the graphite film can be separated at the same time as heat treatment.
以上の方法により、高導電性のグラファイト膜を形成す
ることができるが、上記熱処理の後Ｋ、得られたグラフ
ァイト膜に適当なドーパントをドＩＣＩＢ、ＩＢｒ）、
Ｌ６ｗｉ ｓ酸、プロトン酸（例えば、ＰＦ、。A highly conductive graphite film can be formed by the above method. After the above heat treatment, the obtained graphite film is doped with an appropriate dopant (ICIB, IBr),
L6wis acids, protic acids (e.g. PF,.
ＡｓＦ５．５ｂＦｓ 、ＡｇＣｌＯ４，ＡｇＢＦ４ 、
ＢＦｌｌ 、ＢＣｌ ｇ ＊ＢＢｒＢ 。AsF5.5bFs, AgClO4, AgBF4,
BFll , BCl g *BBrB .
ＦＳＯｇＯＯ３ＣｈＦ 、ＣＮＯ＊ Ｘ５ｂＦａ ）
、（Ｎｏ）ＳｂＣ１δ、（Ｎｏ！ＸＢＦ番）。FSOgOO3ChF, CNO*X5bFa)
, (No) SbC1δ, (No! XBF number).
Ｓｏ ＠ 、ＴｉＦ ４ 、ＮｂＦ ５ ＋ＴａＦ ＠
＋ＮｂＣ１＠ 、ＴａＣｌ Ｂ 、ＭｎＣ１！ 、Ｍ
ＯＣｌ ４１ＭｏＣ１ｓｌＭｏＯＣｌ ４ ＋ＮｉＣ１
＠ 、ＺｎＣ１＠ 、Ｃｒ０ＩＣ１Ｂ 、ＦｅＣｌ Ｂ
、ＣｄＣｌ ！ 。So @ , TiF 4 , NbF 5 +TaF @
+NbC1@, TaCl B, MnC1! ,M
OCl 41MoC1slMoOCl4+NiC1
@ , ZnC1@ , Cr0IC1B , FeCl B
, CdCl! .
ＡｕＣ１ａ 、ＣｒＣ１＠ ｌＡｌＣｌ Ｓ 、ＡｌＢ
ｒ ８ 、ＧａＢｒ ｌｌ 、ｐｔｃｔ ４．５ｂＣ１
Ｂ ＋ＵＣＩ ｓ 、５ＯＣＩ ｓ 、ＸｅＦ ｅ １
ＨｓＳＯ４、）ｔｃ１０４ 、ＨＮＣ）１ 、ＦＳＯＢ
Ｈ９ＣＦｓＳＯｓＨ）及び電子供与性試薬Ｌｉ、Ｎａ＋
に、Ｒｈ＋Ｃｓ等が使用される。AuC1a, CrC1@lAlClS, AlB
r 8 , GaBr ll , ptct 4.5bC1
B +UCI s , 5OCI s , XeF e 1
HsSO4, )tc104, HNC)1, FSOB
H9CFsSOsH) and electron donating reagents Li, Na+
For example, Rh+Cs is used.
実施例ｌ
５ＵＳ ３０４からなるシート状の基材（厚み０．２
ｔｍ ）、を合成室内に静置して、基材を９５０°Ｃに
加熱した後、ベンゼン蒸気を合成室内に導入し、圧力１
．０ ｍｍＨｇ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 Sheet-like base material made of 5US 304 (thickness 0.2
tm) was placed in the synthesis chamber and the base material was heated to 950°C, then benzene vapor was introduced into the synthesis chamber and the pressure was increased to 1.
．． It was maintained at 0 mmHg. After that, a high frequency electric field (13
, 56 MHz, output 40 W) 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.
然る後、基材の温度を室温まで下げて、炭素膜を基材か
ら剥離した。次いで、この炭素膜を３２００℃で熱処理
し、グラファイト膜を得た。Thereafter, the temperature of the substrate was lowered to room temperature, and the carbon film was peeled off from the substrate. Next, this carbon film was heat-treated at 3200°C to obtain a graphite film.
得られたグラファイト膜について、電導塵を測定した結
果、１．２ ｘ １０’ Ｓ／ａｎの導電性を示し、熱
処理前の炭素膜の電導塵ｆＬ２Ｘ１０’ｓ／ａｎに比べ
著しく増加した。また、Ｘ線回折の結果から、シャープ
な（００２） 、（００４）、（００６）回折線が観測
され、グラファイト化が進行したものであることが判っ
た。また、グラファイト膜は、ｄ−３，３５５人の面間
隔を持ち、天然黒鉛の面間隔 ｄ−３，３５４λに極め
て近いものテ、アった。Ｅのことは、得られたグラファ
イト膜−一が結晶性の高いものであることを示し、従っ
て電導塵以外のデータでも、本方法の有効性を示してい
る。As a result of measuring conductive dust on the obtained graphite film, it was found that the conductivity was 1.2 x 10'S/an, which was significantly increased compared to the conductive dust fL2X10's/an of the carbon film before heat treatment. Further, from the results of X-ray diffraction, sharp (002), (004), and (006) diffraction lines were observed, indicating that graphitization had progressed. Furthermore, the graphite film has a lattice spacing of d-3,355, which is extremely close to the lattice spacing of natural graphite, d-3,354λ. E indicates that the obtained graphite film-1 has high crystallinity, and data other than conductive dust also indicate the effectiveness of this method.
実施例２
実施例１において得られたグラファイトＩＩ１．ＫＡｓ
Ｆ、をドープした。ドーピング条件は、室温、７．９８
Ｘ１０’Ｐａである。得られたグラファイト膜の電導塵
は１．Ｉ Ｘ １０’ Ｓ／龜であった。Example 2 Graphite II1. obtained in Example 1. KAs
Doped with F. Doping conditions were room temperature, 7.98
X10'Pa. The conductive dust of the obtained graphite film is 1. It was I x 10' S/head.
実施例３
実施例１より得られたグラファイト膜を、発煙硝酸上に
２１．５時間静置し、ドーピングを行なった。Example 3 The graphite film obtained in Example 1 was left standing on fuming nitric acid for 21.5 hours to perform doping.
ドーピング条件は、室温、１気圧である。得られたグラ
ファイト膜の電導塵は７．８ Ｘ １０ ’ Ｓ／ｃｍ
であった。The doping conditions were room temperature and 1 atm. The conductive dust of the obtained graphite film was 7.8 x 10' S/cm
Met.
実施例４
実施例１により得られたグラファイト膜を、発絆硫酸上
に５分間静置し、ドープした。ドーピング条件は、室温
、１気圧である。得られたグラファイト膜の電導塵は２
．１ ｘ １０ ’ Ｓ／ｃｍであった。Example 4 The graphite film obtained in Example 1 was left standing on sulfuric acid for 5 minutes to be doped. The doping conditions were room temperature and 1 atm. The conductive dust of the obtained graphite film is 2
．． It was 1 x 10' S/cm.
温度２０００℃で熱処理を行ないグラファイト膜を得た
。得られたグラファイト膜の電導塵は５．０ＸＩＯ”シ
ーであった。A graphite film was obtained by heat treatment at a temperature of 2000°C. The conductive dust of the obtained graphite film was 5.0XIO''.
この発明は、上述の様になされる導電性グラファイト膜
の製造方法であるから、以下の効果を有する。Since the present invention is a method for manufacturing a conductive graphite film as described above, it has the following effects.
（１）従来の熱分解法を用いて得られたグラファイト膜
に比較して、導電性に優れたものであり、更にドーパン
トをドープすることにより、一層導電性を向上すること
ができる。(1) It has superior conductivity compared to graphite films obtained using conventional thermal decomposition methods, and the conductivity can be further improved by doping with a dopant.
（１１）炭素膜合成法がプラズマ重合法であるので、熱
分解法に較べて、厚み、形状、サイズ等に富むグラファ
イト膜を得ることができる。(11) Since the carbon film synthesis method is a plasma polymerization method, it is possible to obtain a graphite film with greater thickness, shape, size, etc., compared to a thermal decomposition method.
０ｉｉ１炭素膜を形成する温度は熱分解法と比較して低
いので、その分、融点の低い材料を基材として用いるこ
とができる。従って、用いられる材料の選択範囲が広い
。Since the temperature at which the carbon film is formed is lower than that in the thermal decomposition method, a material with a lower melting point can be used as the base material. Therefore, there is a wide range of materials to choose from.
Claims (4)
された基材上にプラズマ放電により炭素膜を形成させた
後、２０００℃以上の温度で熱処理を行なうことを特徴
とする導電性グラファイト膜の形成方法。(1) A conductive graphite film characterized in that a carbon film is formed by plasma discharge on a base material heated to 700°C or higher using hydrocarbon gas as a raw material, and then heat-treated at a temperature of 2000°C or higher. How to form.
求の範囲第（１）項記載の導電性グラファイト膜の形成
方法。(2) The method for forming a conductive graphite film according to claim (1), wherein the base material contains a transition metal.
された基材上にプラズマ放電により炭素膜を形成させた
後、２０００℃以上の温度で熱処理を行ない、次いで、
ドーパントをドープすることを特徴とする導電性グラフ
ァイト膜の形成方法。(3) Using hydrocarbon gas as a raw material, a carbon film is formed by plasma discharge on a substrate heated to 700°C or higher, followed by heat treatment at a temperature of 2000°C or higher, and then
A method for forming a conductive graphite film characterized by doping with a dopant.
求の範囲第（３）項記載の導電性グラファイト膜の形成
方法(4) A method for forming a conductive graphite film according to claim (3), wherein the base material contains a transition metal.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076385A JPS61170570A (en) | 1985-01-25 | 1985-01-25 | Formation of conductive graphite film |
| US06/822,244 US4645713A (en) | 1985-01-25 | 1986-01-27 | Method for forming conductive graphite film and film formed thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076385A JPS61170570A (en) | 1985-01-25 | 1985-01-25 | Formation of conductive graphite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61170570A true JPS61170570A (en) | 1986-08-01 |
| JPH0362791B2 JPH0362791B2 (en) | 1991-09-27 |
Family
ID=11759369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1076385A Granted JPS61170570A (en) | 1985-01-25 | 1985-01-25 | Formation of conductive graphite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61170570A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62124273A (en) * | 1985-11-22 | 1987-06-05 | Agency Of Ind Science & Technol | Formation of electrically conductive graphite film |
| JPS63293163A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
| JPS63293164A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
| US4795656A (en) * | 1986-08-26 | 1989-01-03 | Kozo Iizuka, Director-General, Agency Of Industrial Science And Technology | Cluster ion plating method for producing electrically conductive carbon film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49127893A (en) * | 1973-04-12 | 1974-12-06 |
-
1985
- 1985-01-25 JP JP1076385A patent/JPS61170570A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49127893A (en) * | 1973-04-12 | 1974-12-06 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62124273A (en) * | 1985-11-22 | 1987-06-05 | Agency Of Ind Science & Technol | Formation of electrically conductive graphite film |
| US4795656A (en) * | 1986-08-26 | 1989-01-03 | Kozo Iizuka, Director-General, Agency Of Industrial Science And Technology | Cluster ion plating method for producing electrically conductive carbon film |
| JPS63293163A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
| JPS63293164A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
| JPH0232354B2 (en) * | 1987-05-27 | 1990-07-19 | Kogyo Gijutsuin | |
| JPH0258352B2 (en) * | 1987-05-27 | 1990-12-07 | Kogyo Gijutsuin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0362791B2 (en) | 1991-09-27 |
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