JPH0362791B2 - - Google Patents
Info
- Publication number
- JPH0362791B2 JPH0362791B2 JP60010763A JP1076385A JPH0362791B2 JP H0362791 B2 JPH0362791 B2 JP H0362791B2 JP 60010763 A JP60010763 A JP 60010763A JP 1076385 A JP1076385 A JP 1076385A JP H0362791 B2 JPH0362791 B2 JP H0362791B2
- Authority
- JP
- Japan
- Prior art keywords
- graphite film
- base material
- film
- carbon
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- 239000010439 graphite Substances 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- -1 Cl 2 Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910017049 AsF5 Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910019929 CrO2Cl2 Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910005258 GaBr3 Inorganic materials 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910015218 MoCl4 Inorganic materials 0.000 description 1
- 229910015221 MoCl5 Inorganic materials 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- 229910019787 NbF5 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910004537 TaCl5 Inorganic materials 0.000 description 1
- 229910004546 TaF5 Inorganic materials 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Description
〔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
フア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、単価水素を熱分解し、炭素質を生
成するものである（例えば、大谷ら“炭素化工学
の基礎”1980年、オーム社発行）（方法１）。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（長沖ら、「炭素材料入門」1979
年、炭素材料学会編）。これらの常温における電
導度は、2.5〜５×103S／cmである。
[Industrial Field of Application] The present invention relates to a method for forming a conductive graphite film having excellent conductivity. [Prior Art] Conventionally, a so-called pyrolysis method has been commonly used to obtain graphitizable carbon. This method heats the reaction system to a high temperature in an atmosphere of raw material hydrocarbons to thermally decompose unit hydrogen and generate carbonaceous material (for example, Otani et al. ”1980, published by Ohmsha) (Method 1). These carbon materials are broadly classified into three types, as shown in Table 1 (Nagaoki et al., "Introduction to Carbon Materials" 1979
(edited by the Carbon Materials Society). The electrical conductivity of these materials at room temperature is 2.5 to 5×10 3 S/cm.
しかし乍ら、上記方法１においては、易個鉛化
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。従つてより低温での易黒鉛化性炭素合成法が
望まれる。
方法２では、電導度が103S／cm未満であり、ま
た、炭素質生長速度が0.052μｍ／minと、方法１
及び２の熱分解法における炭素質生長速度（1.7
〜17μｍ／min）に比較して、著しく低い。
〔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
１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、又方法２から得た炭素質よりも導電
性に優れたグラフアイト膜が形成される方法を提
供する。その要旨とするところは炭化水素ガスを
原料として、700℃以上に加熱された基材上に高
周波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
する導電性グラフアイト膜の形成方法にある。
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CnH2o+2、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１mmHg程度で容易
に蒸気を生ずる炭化水素が適している。
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
とによつて基材上に炭素膜を形成する。
この発明において、基材としては、鉄、コバル
ト、ニツケル等の金属、或はステンレス等の合金
からなる板、シート、フイルム、その他の成形品
を使用することができ、フア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、セラミツクからなる金属以外の
ものを用いても良い。更にカーボンフアイバ、カ
ーボンシート（例えば、カーボンフアイバ織布）、
グラフアイトフアイバ、グラフアイト板（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特性が、グラフアイト
化反応の触媒物質として作用するので、好まし
い。
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。
この発明においては、基材上に炭素膜を形成し
た後に、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
して行なつてもよく、基材と共に行なつてもよ
い。基材が融点2000℃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、揮散等によつて除去され、熱処理と同時に
グラフアイト膜のみを分離することができる。
以上の方法により、高導電性のグラフアイト膜
を形成することができるが、上記熱処理の後に、
得られたグラフアイト膜に適当なドーパントをド
ープすることによつて、更に導電性を増すことが
できる。
適当なドーパントとしては、電子受容性試薬の
例として、ハロゲン（例えば、Cl2、Br2、I2、
ICI、Ｉ、ICI3IBr）、Lewis酸、プロトン酸（例
えば、PF5、AsF5、SbF5、AgClO4、AgBF4、
BF3、BCl3B、Br3、FSO2OOSO2F、（NO2）
（SbF6）、（NO）SbCl6、（NO2）（BF4）、SO3、
TiF4、NbF5、TaF5、NbCl5、TaCl5、MnCl2、
MoCl4、MoCl5、MoOCL4、NiCl2、ZnCL2、
CrO2Cl2、FeCl3、CdCl2、AuCl3、CrCl3、
AlCl3、AlBr3、GaBr3、PtCl4、SbCl5、UCl5、
SOCl2、XeF6、H2SO4、HClO4、HNO3、
FSO3H、CF3SO3H）及び電子供与性試薬Li、
Na、Ｋ、Rb、Cs等が使用される。
〔実施例〕
実施例 １
SUS304からなるシート状の基材（厚み0.2mm）、
を合成室内に静置して、基材を950℃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、高周波数電界
（13.56MHz出力4.0W）を印加し、プラズマ反応
を行ない。基材上に金属光沢を有する膜厚20−
22μｍの炭素膜を形成せしめた。
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、グラフアイト膜を得た。
得られたグラフアイト膜について、電導度を測
定した結果、1.2×104S／cmの導電性を示し、熱
処理前の炭素膜の電導度2.2×103S／cmに比べ著
しく増加した。また、Ｘ線回折の結果から、シヨ
ープな（002）、（004）、（006）回折線が観測され、
グラフアイト化が進行したものであることが判つ
た。また、グラフアイト膜は、ｄ＝3.355Åの面
間隔を持ち、天然黒煙の面間隔２＝3.354Åに極
めて近いものであつた。このことは、得られたグ
ラフアイト膜が結晶性の高いものであることを示
し、従つて電導度以外のデータでも、本方法の有
効性を示している。
実施例 ２
実施例１において得られたグラフアイト膜に
AsF5のドープした。ドーピング条件は、室温、
7.98×104Paである。得られたグラフアイト膜の
電導度は1.1×105S／cmであつた。
実施例 ３
実施例１より得られたグラフアイト膜を、発煙
硝酸上に21.5時間静置し、ドーピングを行なつ
た。ドーピング条件は、室温、１気圧である。得
られたグラフアイト膜の電導度は7.8×104S／cm
であつた。
実施例 ４
実施例１により得られたグラフアイト膜を、発
煙硫酸上に５分間芻置し、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
アイト膜の電導度は2.1×104S／cmであつた。
実施例 ５
実施例１と同様の条件で炭素膜を形成し、次い
で、温度2000℃で熱処理を行ないグラフアイト膜
を得た。得られたグラフアイト膜の電導度は5.0
×103S／cmであつた。
〔発明の効果〕
この発明は、上述の様になされる導電性グラフ
アイト膜の製造方法であるから、以下の効果を有
する。
() 従来の熱分解法を用いて得られたグラフア
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。
() 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
に富むグラフアイト膜を得ることができる。
() 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。従つて、用いられる
材料の選択範囲が広い。
However, in the above method 1, a thermal decomposition temperature of 1200° C. or higher is required as one condition for obtaining easily plugitizable carbon. At such temperatures, the types of base materials are limited and energy loss is also large. Therefore, a method for synthesizing easily graphitizable carbon at lower temperatures is desired. Method 2 has an electrical conductivity of less than 10 3 S/cm and a carbonaceous growth rate of 0.052 μm/min.
and the carbonaceous growth rate in the pyrolysis method of 2 (1.7
~17 μm/min). [Means for Solving the Problems] In view of the above-mentioned problems of the prior art, the present invention provides that, unlike Method 1, the type of base material on which a carbon film is formed is not so limited, and that Provided is a method for forming a graphite film that has better conductivity than carbonaceous materials. The gist of this is that a carbon film is formed using high-frequency plasma discharge on a substrate heated to over 700°C using hydrocarbon gas as a raw material.
The present invention provides a method for forming a conductive graphite film characterized by performing heat treatment at a temperature of 2000°C or higher. In this invention, the hydrocarbons used as raw materials include substances that can become gases, such as aliphatic compounds such as methane, ethane, and propane, CnH 2o+2 , unsaturated derivatives such as alkenes and alkynes, ie, one or more double bonds, Those having a triple bond, aromatic compounds such as benzene, naphthalene, anthracene, and pyrene are used, and hydrocarbons that easily generate steam at about 1 mmHg are particularly suitable. The method of forming a carbon film on a substrate by plasma discharge involves filling a reaction vessel with raw material hydrocarbon vapor to a predetermined pressure, and forming a carbon film on the substrate by applying a high-frequency electric field. . 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 materials 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, carbon sheet (e.g. carbon fiber woven fabric),
Graphite fibers and graphite plates (eg, HOPG) can be used. Among the above-mentioned base materials, those containing transition metals are particularly preferable because they act as catalysts for the graphitization reaction. In particular, when the substrate is heated to a temperature of 700°C or higher,
Effective in forming a carbon film. In this invention, after the carbon film is formed on the base material, heat treatment is further 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. When a base material made of a substance with a melting point of less than 2000°C is used, if heat treatment is performed together with the base material, the base material will be removed by melting, volatilization, etc., and it may be difficult to separate only the graphite film at the same time as the heat treatment. can. A highly conductive graphite film can be formed by the above method, but after the above heat treatment,
The electrical conductivity can be further increased by doping the obtained graphite film with a suitable dopant. Suitable dopants include halogens (e.g. Cl 2 , Br 2 , I 2 ,
ICI, I, ICI 3 IBr), Lewis acids, protic acids (e.g. PF 5 , AsF 5 , SbF 5 , AgClO 4 , AgBF 4 ,
BF3 , BCl3B , Br3 , FSO2OOSO2F , ( NO2 )
(SbF 6 ), (NO)SbCl 6 , (NO 2 )(BF 4 ), SO 3 ,
TiF4 , NbF5 , TaF5 , NbCl5 , TaCl5 , MnCl2 ,
MoCl4 , MoCl5 , MoOCL4 , NiCl2 , ZnCL2 ,
CrO2Cl2 , FeCl3 , CdCl2 , AuCl3 , CrCl3 ,
AlCl3 , AlBr3 , GaBr3 , PtCl4 , SbCl5 , UCl5 ,
SOCl 2 , XeF 6 , H 2 SO 4 , HClO 4 , HNO 3 ,
FSO 3 H, CF 3 SO 3 H) and electron donating reagent Li,
Na, K, Rb, Cs, etc. are used. [Example] Example 1 Sheet-like base material made of SUS304 (thickness 0.2 mm),
was placed in the synthesis chamber and the base material was heated to 950℃, then benzene vapor was introduced into the synthesis chamber and the pressure was increased to 1.0.
Maintained at mmHg. After that, a high frequency electric field (13.56MHz output 4.0W) was applied to perform a plasma reaction. Film thickness 20− with metallic luster on the base material
A 22 μm carbon film was formed. 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 heated to 3200
A graphite film was obtained by heat treatment at ℃. As a result of measuring the electrical conductivity of the obtained graphite film, it was found that the electrical conductivity was 1.2×10 4 S/cm, which was significantly increased compared to the 2.2×10 3 S/cm of the carbon film before heat treatment. In addition, from the results of X-ray diffraction, short (002), (004), and (006) diffraction lines were observed.
It was found that graphite formation had progressed. Furthermore, the graphite film had a lattice spacing of d = 3.355 Å, which was extremely close to the lattice spacing of natural black smoke, 2 = 3.354 Å. This shows that the obtained graphite film has high crystallinity, and data other than electrical conductivity also show the effectiveness of this method. Example 2 The graphite film obtained in Example 1
Doped with AsF5 . Doping conditions were room temperature,
It is 7.98×10 4 Pa. The electrical conductivity of the obtained graphite film was 1.1×10 5 S/cm. Example 3 The graphite film obtained in Example 1 was left standing on fuming nitric acid for 21.5 hours to perform doping. The doping conditions were room temperature and 1 atm. The electrical conductivity of the obtained graphite film is 7.8×10 4 S/cm
It was hot. Example 4 The graphite membrane obtained in Example 1 was doped by placing it on fuming sulfuric acid for 5 minutes. The doping conditions were room temperature and 1 atm. The electrical conductivity of the obtained graphite film was 2.1×10 4 S/cm. Example 5 A carbon film was formed under the same conditions as in Example 1, and then heat treated at a temperature of 2000°C to obtain a graphite film. The electrical conductivity of the obtained graphite film is 5.0
×10 3 S/cm. [Effects of the Invention] Since the present invention is a method for manufacturing a conductive graphite film as described above, it has the following effects. () It has superior conductivity compared to graphite films obtained using conventional pyrolysis methods, and by doping with a dopant,
Conductivity can be further improved. () Since the carbon film synthesis method is a plasma polymerization method, it is possible to obtain a graphite film with a richer thickness, shape, size, etc., compared to a thermal decomposition method. () 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 (1)
熱された基材上に高周波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
行うことを特徴とする導電性グラフアイト膜の形
成方法。 ２ 基材が、遷移金属を含むことを特徴とする特
許請求の範囲第１項記載の導電性グラフアイト膜
の形成方法。 ３ 炭化水素ガスを原料として、700℃以上に加
熱された基材上に高周波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アイト膜の形成方法。 ４ 基材が、遷移金属を含むことを特徴とする特
許請求の範囲第３項記載の導電性グラフアイト膜
の形成方法。[Claims] 1. A carbon film is formed by high-frequency 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. A method for forming a conductive graphite film. 2. The method for forming a conductive graphite film according to claim 1, wherein the base material contains a transition metal. 3 Using hydrocarbon gas as a raw material, a carbon film is formed by high-frequency plasma discharge on a substrate heated to 700°C or higher, then heat treated at a temperature of 2000°C or higher, and then doped with a dopant. A method for forming a conductive graphite film. 4. The 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 JPS61170570A (en) | 1986-08-01 |
| JPH0362791B2 true 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) |
Families Citing this family (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 |
| 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 |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61170570A (en) | 1986-08-01 |
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