JPH0483874A - Method for forming conductive graphite film - Google Patents
Method for forming conductive graphite filmInfo
- Publication number
- JPH0483874A JPH0483874A JP2200682A JP20068290A JPH0483874A JP H0483874 A JPH0483874 A JP H0483874A JP 2200682 A JP2200682 A JP 2200682A JP 20068290 A JP20068290 A JP 20068290A JP H0483874 A JPH0483874 A JP H0483874A
- Authority
- JP
- Japan
- Prior art keywords
- graphite film
- people
- graphite
- temperature
- raw material
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 50
- 229910002804 graphite Inorganic materials 0.000 title claims description 43
- 239000010439 graphite Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000428 dust Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- -1 Hensen Chemical class 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 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
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 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
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001294 propane Substances 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
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- 229910015844 BCl3 Inorganic materials 0.000 description 1
- 229910015890 BF2 Inorganic materials 0.000 description 1
- 101100522123 Caenorhabditis elegans ptc-1 gene Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910015400 FeC13 Inorganic materials 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019788 NbF3 Inorganic materials 0.000 description 1
- PWHVEHULNLETOV-UHFFFAOYSA-N Nic-1 Natural products C12OC2C2(O)CC=CC(=O)C2(C)C(CCC2=C3)C1C2=CC=C3C(C)C1OC(O)C2(C)OC2(C)C1 PWHVEHULNLETOV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 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
- 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
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 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
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical compound F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Manufacturing Of Electric Cables (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
- Conductive Materials (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は優れた導電性を有するグラファイト膜を比較的
低温において形成する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for forming graphite films with excellent electrical conductivity at relatively low temperatures.
従来の技術
高い導電性を与える炭素材料として、コークス等の選択
的配向性の良い、いわゆる“易グラファイト化性炭素″
が知られており、その−船釣な炭素の格子定数（Ｃｏ）
及び常温における電導度は、処理温度が１０００℃の場
合、約６．９１人、約１００Ｓ／ａｍ、２０００℃の場
合、約６．８１人、約３００Ｓ／ａｍ、３０００℃の場
合、約６．７１人約２００ ＯＳ／ｃｍであることが［
炭素化工学の基礎Ｊ（大釜ら著、オーム社発行、１９８
０年）に示されている。Conventional technology As a carbon material that provides high conductivity, so-called "graphitizable carbon", which has good selective orientation such as coke, is used.
is known, and the lattice constant of carbon (Co)
And the conductivity at room temperature is about 6.91 people, about 100 S/am when the processing temperature is 1000°C, about 6.81 people, about 300 S/am, about 6.8 people when the processing temperature is 2000°C, and about 6. Approximately 200 OS/cm for 71 people [
Fundamentals of Carbonization Engineering J (written by Ohkama et al., published by Ohmsha, 198
Year 0).
易グラファイト化性炭素の中でも、特に配向性に優れて
いるのが、メタン、プロパン等の炭化水素ガスの気相熱
分解により得られる“熱分解炭素”であり、２０００〜
２２００℃で沈積されたものは２５００〜５０００ Ｓ
／ｃｍを発現することが「炭素材料入門Ｊ（長油ら、炭
素材料学会、１９７９年）に示されている。又、これを
３００〜５００ ｋｇ／Ｃ１ｎ”の−軸性の圧力を加え
ながら３０００℃以上で熱処理することによりＣｏ＜６
．７２人（グラファイト単結晶：Ｃｏ＝６．７０８人）
を有する高配向熱分解グラファイト（ＨＯＰＧ）の得ら
れることが、「炭素材料工学」（稲垣ら２日刊工業新聞
社、１９８５年）に示されており、これはグラファイト
単結晶に匹敵するような電導度ｌ〜２Ｘ１０’Ｓ／ａｍ
を持つことが知られている。Among easily graphitizable carbons, "pyrolytic carbon" obtained by gas-phase thermal decomposition of hydrocarbon gases such as methane and propane has particularly excellent orientation.
2500-5000 S for those deposited at 2200℃
/cm is shown in ``Introduction to Carbon Materials J (Nagayu et al., Carbon Materials Society of Japan, 1979). Co<6 by heat treatment at 3000℃ or higher
．． 72 people (graphite single crystal: Co=6.708 people)
It has been shown in "Carbon Materials Engineering" (Inagaki et al. 2, Nikkan Kogyo Shimbunsha, 1985) that highly oriented pyrolytic graphite (HOPG) can be obtained, which has electrical conductivity comparable to that of single crystal graphite. degree l~2X10'S/am
is known to have.
本発明人の出願による「導電性グラファイト膜の形成方
法Ｊ（特願昭６０−２６１３８３号）では、ベンゼンを
原料としてｌ０００℃のステンレス鋼基村上にプラズマ
放電により炭素膜形成後、３３００℃て熱処理すること
により２．２Ｘ１０’Ｓ／ａｍの高導電性グラファイト
膜を得ている。In the "Method for Forming Conductive Graphite Film J (Japanese Patent Application No. 60-261383) filed by the present inventor, a carbon film is formed by plasma discharge on a stainless steel substrate at 1000°C using benzene as a raw material, and then heat-treated at 3300°C. By doing so, a highly conductive graphite film of 2.2×10'S/am was obtained.
発明が解決しようとする課題
］−クス等の一般的な易グラファイト化性炭素の場合、
高結晶性、高導電性のグラファイトを得るには３０００
℃以上の高温処理が必要であるが、それで漸く、約２０
００ Ｓ／ｃｍの電導度が得られる程度である。Problems to be Solved by the Invention] - In the case of general graphitizable carbon such as carbon,
3000 to obtain highly crystalline and highly conductive graphite
Although high-temperature treatment above ℃ is necessary, the temperature of about 20
This is the level at which an electrical conductivity of 0.00 S/cm can be obtained.
又、特に配向性が良く、グラファイト化性に優れた熱分
解炭素では、Ｃｏ＜６．７２人、電導度ｌ〜２ｘｌＯ’
Ｓ／ｃｍが得られているが、その作製には、かなりの高
温（＞３０００℃）、高圧（３００〜５００ｋｇ／ｃｍ
りを要するという問題があった。In addition, for pyrolytic carbon which has particularly good orientation and excellent graphitization properties, Co<6.72 and conductivity 1~2xlO'
S/cm has been obtained, but its production requires considerable high temperature (>3000°C) and high pressure (300 to 500 kg/cm
The problem was that it required a lot of work.
従来のプラズマ放電法でも、Ｇｏ＜６．７２人を得るに
は、２７５０℃以上の高温熱処理が必要であっいずれに
せよ、従来の炭素材料において、高電導性（高結晶性）
を得るには、形成後、更に２７５０〜３０００°Ｃを越
える高温処理の実施が不可欠であり、このことは、これ
ら材料の応用範囲を著しく狭めるという欠点となってい
た。Even with the conventional plasma discharge method, high-temperature heat treatment of 2750°C or higher is required to obtain Go < 6.72. In any case, conventional carbon materials have high conductivity (high crystallinity).
In order to obtain this, it is necessary to further perform a high-temperature treatment at temperatures exceeding 2750 to 3000° C. after formation, which has been a disadvantage of significantly narrowing the range of applications of these materials.
それ故、セラミックス等の各種素材と複合化して応用範
囲を広げるため、高結晶性・高導電性グラファイトを２
０００℃以下の比較的低温で得ｆこいという要求がある
。Therefore, in order to expand the range of applications by compounding with various materials such as ceramics, highly crystalline and highly conductive graphite is
There is a demand for high performance at a relatively low temperature of 000°C or less.
２０００℃以下の比較的低温でグラファイトを得る方法
として、キッシュグラファイトの生成機構と同様、炭素
を金属に溶解させ、その溶融金属から、グラファイトを
析出させる方法が良く知られている。グラファイトを鉄
、鋼に１８００〜１９００℃で溶解し、溶融鉄、あるい
は鋼を１５００℃以下に徐々に冷却する事により溶融鉄
表面にグラファイト膜が生成する事が野田らによって開
示されている（Ｃａｒｂｏｎ ６ ８１３（１９６８
））。A well-known method for obtaining graphite at a relatively low temperature of 2000° C. or lower is a method in which carbon is dissolved in metal and graphite is precipitated from the molten metal, similar to the production mechanism of Quiche graphite. Noda et al. have disclosed that a graphite film is formed on the surface of molten iron by melting graphite into iron or steel at 1800 to 1900°C and gradually cooling the molten iron or steel to 1500°C or less (Carbon et al. 6 813 (1968
)).
しかし、この方法では、−度、炭素を十分に溶解させ、
１８００℃以上に加熱された溶融鉄か必要となり、生成
するクラファイト膜は溶融鉄表面形状により形状か限定
される。さらに１８００°Ｃから鉄の融点である１５０
０℃まで冷却する必要があり、冷却速度も５℃／分以下
とおそく、精密な温度コントロールが要求される。However, in this method, the carbon is sufficiently dissolved,
Molten iron heated to 1800° C. or higher is required, and the shape of the graphite film formed is limited by the surface shape of the molten iron. Furthermore, from 1800°C to 150, which is the melting point of iron.
It is necessary to cool down to 0°C, and the cooling rate is slow at 5°C/min or less, requiring precise temperature control.
課題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、高導電性、
高結晶性のグラファイト膜を従来よりも低い温度で、し
かも後の熱処理過程を経ずに、１段で形成させる方法を
提供するものである。Means for Solving the Problems In view of the problems of the above-mentioned prior art, the present invention provides high conductivity,
The present invention provides a method for forming a highly crystalline graphite film in one step at a lower temperature than conventional methods and without a subsequent heat treatment process.
その要旨とするところは、分離されたプラズマ放電室と
形成室とを有するプラズマＣＶＤ装置において、炭化水
素を原料とし、１２００℃以上に加熱した遷移金属を含
む基材上にプラズマ放電によって格子定数Ｃｏ＜６．７
２人、電導度２０００Ｓ／ｃｍ以上の導電性グラファイ
ト膜を形成させる方法にある。The gist of this is that in a plasma CVD apparatus having a separate plasma discharge chamber and formation chamber, a hydrocarbon is used as a raw material, and a lattice constant Co <6.7
Two people are involved in a method for forming a conductive graphite film with an electrical conductivity of 2000 S/cm or more.
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ＣｎＨ２ｎ＋ｚ；アルケン、アルキノ等の不
飽和誘導体、即ち１つまたはそれ以上の二重結合或いは
三重結合を有するもの；ヘンセン、ナフタレン、アント
ラセン、ピレン等の芳香族化合物か用いられる。In this invention, the raw material hydrocarbons include substances that can become gases, such as aliphatic compounds CnH2n+z such as methane, ethane, and propane; unsaturated derivatives such as alkenes and alkinos, that is, one or more double bonds or triple bonds; Those having a bond; aromatic compounds such as Hensen, naphthalene, anthracene, and pyrene are used.
プラズマ放電により基材上にグラファイト膜を形成させ
る方法は、真空チャンバー及び反応管内を真空引きし、
基材を加熱して定温に保った後、原料である炭化水素蒸
気を所定の圧力で流しながら高周波電界を印加し、その
蒸気を基材上に供給することによって、基材上にグラフ
ァイト膜を形成するもので、例えば第１図に示すような
装置が用いられる。The method of forming a graphite film on a substrate by plasma discharge involves evacuating the inside of a vacuum chamber and reaction tube,
After heating the base material and keeping it at a constant temperature, a high-frequency electric field is applied while flowing hydrocarbon vapor as a raw material at a predetermined pressure, and the vapor is supplied onto the base material to form a graphite film on the base material. For example, an apparatus as shown in FIG. 1 is used.
第１図において、真空チャンバー１内にヒーター２が設
けられており、ヒーター２の中間に基材３が設置されて
、ヒーター２により加熱される。In FIG. 1, a heater 2 is provided in a vacuum chamber 1, and a base material 3 is placed between the heaters 2 and heated by the heater 2.
真空チャンバー１はバルブ５を介して、油回転ポンプ４
により真空引される。又、真空チャンバー１には反応管
６が接続され、反応管６の回りにはスパイラル状の電極
８が設置されている。電極８には整合器９と高周波発振
器ｌＯが接続され、電気エネルギーが加えられて、反応
管６内にプラズマが発生する。The vacuum chamber 1 is connected to an oil rotary pump 4 via a valve 5.
is evacuated by. Further, a reaction tube 6 is connected to the vacuum chamber 1, and a spiral electrode 8 is installed around the reaction tube 6. A matching device 9 and a high frequency oscillator IO are connected to the electrode 8, and electric energy is applied to generate plasma in the reaction tube 6.
原料容器１２内の原料１３は、恒１１ｔ１４により一定
温度に保持されて気化し、バルブ１１を介して反応管６
に導入され、プラズマ放電により活性化された後、ノズ
ル７より真空チャン）＜−１内の基材３上に導びかれグ
ラファイト膜の形成に供される。The raw material 13 in the raw material container 12 is kept at a constant temperature by the constant temperature controller 11t14 and vaporized, and is passed through the valve 11 to the reaction tube 6.
After being activated by plasma discharge, it is guided from a nozzle 7 onto a substrate 3 in a vacuum chamber (<-1) to form a graphite film.
この発明において、基材としては、遷移金属、例えば鉄
、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
用することりかでき、ファイバ状のもの及びその織布、
或いは、パウダー、及びその成形品も使用することがで
きる。In this invention, the substrate may be a plate, sheet, film, or other molded product made of a transition metal such as iron, cobalt, or nickel, or an alloy such as stainless steel. things and their woven fabrics,
Alternatively, powders and molded products thereof can also be used.
得られたグラファイト膜に適当なドーパントをドープす
ることによって、更に導電性を増すことができる。The electrical conductivity can be further increased by doping the obtained graphite film with a suitable dopant.
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、Ｃ１，、Ｂｒｔ、Ｉ ｔｓＩＣＬ
ＩＣＩ３、ｒＢｒ）、ルイス酸、プロトン酸（例えば、
ＰＦ５、Ａ ｓ Ｆ ｓ、ＳｂＦ５、ＡｇＣｌ０．、Ａ
ｇＢＦ、、ＢＦ２、ＢＣｌ３、ＢＢｒ３、ＦＳｏ、００
Ｓ０２Ｆ、（ＮＯ，）（Ｓ ｂＦ ｅ）、（Ｎｏ）Ｓｂ
Ｃ１，、（Ｎ Ｏ２ＸＢ Ｆ 、）、ＳＯ３、ＴｉＦ４
、ＮｂＦ３、ＴａＦ５、ＮｂＣ１１、ＴａＣｌ５、Ｍｎ
Ｃ１，、ＭｏＣ１，、Ｍ。Suitable dopants include, as examples of electron-accepting reagents, halogens (e.g. C1, Brt, ItsICL).
ICI3, rBr), Lewis acids, protic acids (e.g.
PF5, AsFs, SbF5, AgCl0. ,A
gBF, BF2, BCl3, BBr3, FSo, 00
S02F, (NO,) (S bF e), (No) Sb
C1, (N O2XB F ,), SO3, TiF4
, NbF3, TaF5, NbC11, TaCl5, Mn
C1,,MoC1,,M.
Ｃ１ｓ、Ｍｏ０Ｃ１，、ＮｉＣ１，、ＺｎＣｌ、、Ｃｒ
０ｚＣＬ、Ｆ ｅＣ１３、ＣｄＣｌ２、ＡｕＣｌ３、Ｃ
ｒＣｌ３、ＡｌＣｌ３、ＡｌＢｒ３、Ｇ ａＢ ｒ３、
ＰｔＣ１，、Ｓ ｂＣ１５、ＵＣｌ３．５ＯＣ１２、Ｘ
ｅＦｅ、Ｈ，ＳＯ，、ＨＣｌＯ４、ＨＮ Ｏ３、ＦＳＯ
３Ｈ，ＣＦ３５○３Ｈ）及び電子供与性試薬Ｌｉ５Ｎａ
、に、Ｒｂ、Ｃｓ等が使用される。C1s, Mo0C1,, NiC1,, ZnCl,, Cr
0zCL, FeC13, CdCl2, AuCl3, C
rCl3, AlCl3, AlBr3, GaB r3,
PtC1,,S bC15, UCl3.5OC12,X
eFe, H, SO,, HClO4, HN O3, FSO
3H, CF35○3H) and electron donating reagent Li5Na
, Rb, Cs, etc. are used.
作用
第１図に示した装置を用いた場合に導電性グラファイト
膜の形成は以下のように行われる。Operation When the apparatus shown in FIG. 1 is used, a conductive graphite film is formed as follows.
遷移金属を含む基材３を真空チャンバー１内のヒーター
２間に設置する。又、原料容器１２内に炭化水素原料１
３を充填し、原料１３が液相の場合は、凍結脱気を行っ
た後、所定の蒸気圧を得るため、恒温槽１４により一定
温度に保持する。その後、真空チャンバー１、反応管６
を含む系全体を油回転ポンプ４によりＩ Ｏ−２ｍｍＨ
ｇ程度に真空引きし、ヒーター２により基材３を１２０
０°Ｃ以上に加熱する。バルブ１１を開いて、原料１３
の蒸気を反応管６→ノズル７−真空チャンバー１−バル
ブ５−油回転ポンプ４のルートを経由して、系内を所定
の圧力に保ちながら流す。A base material 3 containing a transition metal is placed between heaters 2 in a vacuum chamber 1. In addition, the hydrocarbon raw material 1 is contained in the raw material container 12.
3 and when the raw material 13 is in a liquid phase, the temperature is maintained at a constant temperature in a constant temperature bath 14 in order to obtain a predetermined vapor pressure after freezing and deaeration. After that, vacuum chamber 1, reaction tube 6
The entire system including
Vacuum the base material 3 to about 120g using the heater 2.
Heat above 0°C. Open the valve 11 and release the raw material 13.
The vapor flows through the reaction tube 6 -> nozzle 7 - vacuum chamber 1 - valve 5 - oil rotary pump 4 route while maintaining the system at a predetermined pressure.
そこで、電極８に高周波電場（例えば１３．５６ＭＨｚ
）を印加することにより原料蒸気はプラズマ放電し、ノ
ズル７より引き出されて基材３上に達し、グラファイト
膜が形成される。Therefore, a high frequency electric field (for example, 13.56 MHz) is applied to the electrode 8.
), the raw material vapor is plasma-discharged, is drawn out from the nozzle 7, reaches the base material 3, and forms a graphite film.
同方法では、熱エネルギーの代替えとしてプラズマ放電
を利用したことにより、従来の熱分解法に比ベグラファ
イト化温度の低温化を図ることが出来る。また、従来の
プラズマ法によるグラファイト形成では放電室にヒータ
ー及び基材があったため、加熱は１０００℃前後が限界
であった。（第１図のように外部電極を用いる場合、反
応管はパイレックスか石英ガラス製である。）本発明に
おいては、第１図に示す如く、形成室（基材設置、加熱
域）を放電室から分離した装置を用いたことにより、基
材を１２００°Ｃ以上に加熱することか可能となり、又
、基材や生成膜かプラズマ損傷を受けないという効果ら
期待てきる。In this method, by using plasma discharge as an alternative to thermal energy, it is possible to lower the graphitization temperature compared to the conventional thermal decomposition method. Furthermore, in the conventional plasma method for graphite formation, since a heater and a base material were provided in the discharge chamber, heating was limited to around 1000°C. (When external electrodes are used as shown in Figure 1, the reaction tube is made of Pyrex or quartz glass.) In the present invention, as shown in Figure 1, the formation chamber (substrate installation, heating area) is connected to the discharge chamber. By using a separate device, it is possible to heat the substrate to 1200° C. or higher, and it is also expected that the substrate and the produced film will not be damaged by the plasma.
このため、従来法（１０００°Ｃでの合成）では、Ｃｏ
＝６．８１−６．９人、Ｌｃ＝３０〜７０人程戻しか得
られず、Ｃｏ＜６．７２人、Ｌｃ＞１０００．Ａを得る
には更に２７５０°Ｃ以上の高温熱処理が必要であった
が、本発明では１２００℃以上の温度での１段法で得る
ことができる。Therefore, in the conventional method (synthesis at 1000°C), Co
= 6.81-6.9 people, Lc = only about 30-70 people returned, Co < 6.72 people, Lc > 1000. In order to obtain A, a further high-temperature heat treatment at 2750°C or higher was required, but in the present invention it can be obtained by a one-step process at a temperature of 1200°C or higher.
実施例
実施例１
グラファイト製ボートに鉄パウダー（１００メツシユ）
を充填して平らに成形したものを基材とし、第１図３の
位置に静置した。真空チャンバー内を１０−”ｍｍＨｇ
まで減圧し、基材を１３２０℃に加熱した後、原料のベ
ンゼン蒸気を反応管から真空チャンバーに、系内圧力を
１ａｍＨｇに保ちながら流した。然る後、高周波電界（
１３，５６ＭＨｚ、出力５００Ｗ）を印加してプラズマ
放電を起こし、ベンゼン蒸気を加熱された碁打上に送り
、碁打上に膜厚的３０μｍのグラファイト膜を形成させ
た。Examples Example 1 Iron powder (100 mesh) on graphite boat
A base material that was filled with and molded flat was placed at the position shown in FIG. 1, 3. 10-”mmHg inside the vacuum chamber
After reducing the pressure to 1,320° C. and heating the base material to 1,320° C., benzene vapor as a raw material was flowed from the reaction tube into the vacuum chamber while maintaining the system internal pressure at 1 amHg. After that, a high frequency electric field (
13.56 MHz, output 500 W) was applied to generate plasma discharge, and benzene vapor was sent onto the heated Go board to form a graphite film with a thickness of 30 μm on the Go board.
得られたグラファイト膜の電導塵は９０００〜ｌ川Ｘ
Ｉ Ｏ’Ｓ ７ｃｍであった。又、Ｘ線回折の結果第２
図に示す如く、ンヤープなＣ（００２）、Ｃ（００４）
等の各回折線が測定され、極めて結晶性の高いことがわ
かった。格子定数Ｃｏ＝６．７０８人、Ｃ軸方向の人品
Ｃ軸方向さＬｃ＞ Ｉ ０００人であった。The conductive dust of the obtained graphite film is 9000 to 1 river
I O'S was 7 cm. In addition, the second result of X-ray diffraction
As shown in the figure, Nyaap C (002), C (004)
The following diffraction lines were measured, and it was found that the crystallinity was extremely high. The lattice constant Co = 6.708 people, and the length of the human body in the C-axis direction was Lc > I 000 people.
このグラフフィト膜に室温でＡ ｓ Ｐ ｓドーピング
を行った（ＡｓＦｓ圧８Ｘ１０’Ｐａ）結果、電導塵は
１．４Ｘ１０５Ｓ／Ｃｍとなった。This graphite film was doped with AsPs at room temperature (AsFs pressure 8×10'Pa), and as a result, the conductive dust was 1.4×105S/Cm.
実施例２
基材を１２４０℃に加熱する他は実施例１と同様の条件
で膜厚的２０μｍのグラファイト膜を形成した。Example 2 A graphite film having a thickness of 20 μm was formed under the same conditions as in Example 1 except that the substrate was heated to 1240° C.
得られたグラファイト膜の電導塵は２８００〜４１００
Ｓ／ａｍであった。又、Ｇｏ＝６．７１８人。The conductive dust of the obtained graphite film is 2800 to 4100
It was S/am. Also, Go = 6.718 people.
Ｌｃ＞１０００人であった。Lc>1000 people.
実施例３
基材を１４３０℃に加熱する他は実施例１と同様の条件
で膜厚的１５μｍのグラファイト膜を形成した。Example 3 A graphite film having a thickness of 15 μm was formed under the same conditions as in Example 1 except that the substrate was heated to 1430° C.
得られｆこグラファイト膜の電導塵は５９００〜６３０
０ Ｓ／ａｍであった。又、Ｃｏ＝６．７１５人Ｌｃ＞
ｌ ＯＯ０人であった。The conductive dust of the obtained graphite film is 5900 to 630
It was 0 S/am. Also, Co=6.715 people Lc>
l OO There were 0 people.
実施例４
基材を１６９０℃に加熱する他は実施例１と同様の条件
で膜厚的３５μｍのグラファイト膜を形成した。Example 4 A graphite film having a thickness of 35 μm was formed under the same conditions as in Example 1 except that the substrate was heated to 1690° C.
得られたグラファイト膜の電導塵は７５００〜ｌ Ｘ
１０’ ９７ｃｍであった。又、Ｃｏ＝６．７１人。The conductive dust of the obtained graphite film is 7500~l
It was 10' 97cm. Also, Co=6.71 people.
Ｌｃ＞１０００人であった。Lc>1000 people.
比較例１
基材を１３４０℃に加熱し、プラズマを印加しない他は
実施例１と同様の条件で、膜厚的４０μｍのグラファイ
ト膜を形成した。得られたグラファイト膜の電導塵は４
４００〜５８００ Ｓ／ａｍでありプラズマ印加した場
合の１／２の値であった。又、Ｃｏ＝６．７２５人、Ｌ
ｃ＞ ｌ ＯＯ０人であつ比較例２
基材を１１００℃に加熱する他は実施例１と同様の条件
で膜厚的４５μｍの炭素膜を形成した。Comparative Example 1 A graphite film having a thickness of 40 μm was formed under the same conditions as in Example 1 except that the substrate was heated to 1340° C. and no plasma was applied. The conductive dust of the obtained graphite film was 4
It was 400 to 5800 S/am, which was 1/2 the value when plasma was applied. Also, Co=6.725 people, L
c> l OO 0 persons Comparative Example 2 A carbon film having a thickness of 45 μm was formed under the same conditions as in Example 1 except that the substrate was heated to 1100° C.
得られた炭素膜の電導塵は６５０〜８００Ｓ／ｃｍであ
った。又、Ｃｏ＝６．８８５人、Ｌｃ＝４０人であった
。The conductive dust of the obtained carbon film was 650 to 800 S/cm. Moreover, Co=6.885 people and Lc=40 people.
比較例３
基材を１６９０℃に加熱し、プラズマを印加しない他は
実施例１と同様の条件で、膜厚的２５μｍのグラファイ
ト膜を形成した。Comparative Example 3 A graphite film having a thickness of 25 μm was formed under the same conditions as in Example 1 except that the substrate was heated to 1690° C. and no plasma was applied.
得られたグラファイト膜の電導塵は２６００〜４１００
Ｓ／ａｍであり、プラズマを印加した場合の２１５〜
１／３の値であった。又、Ｃｏ＝６．７４２人、Ｌｃ＞
１０００人であった。The conductive dust of the obtained graphite film is 2600 to 4100
S/am, 215~ when plasma is applied
The value was 1/3. Also, Co=6.742 people, Lc>
There were 1000 people.
発明の効果
本発明は、プラズマＣＶＤ法を採用することにより、熱
分解法に比べ、高結晶性、高導電性のグラファイト膜を
形成することが出来る。さらに、基材遷移金属の触媒作
用によりグラファイト形成温度の低温化を図ることが出
来、金属の溶融に至らない低温下でグラファイト膜の形
成が可能となりｆこ。Effects of the Invention By employing the plasma CVD method, the present invention can form a graphite film with higher crystallinity and higher conductivity than the thermal decomposition method. Furthermore, the graphite formation temperature can be lowered due to the catalytic action of the base transition metal, making it possible to form a graphite film at a low temperature that does not lead to melting of the metal.
第１図は本発明において使用されるプラズマＣＶＤ法の
装置の概略図、第２図は１３２０℃で形成したグラファ
イト膜のＸ線回折図である。
１は真空チャンバー、２はヒーター、３は基材、４は油
回転ポンプ、５はバルブ、６は反応管、７はノズル、８
は電極、９は整合器、ＩＯは高周波発振器、１１はバル
ブ、１２は原料容器、Ｉ３は原料、１４は恒温槽を示す
。
特許出願人住友電気工業株式会社
代理人弁理士 青 山 葆 ほか１名
第
図FIG. 1 is a schematic diagram of an apparatus for the plasma CVD method used in the present invention, and FIG. 2 is an X-ray diffraction diagram of a graphite film formed at 1320°C. 1 is a vacuum chamber, 2 is a heater, 3 is a base material, 4 is an oil rotary pump, 5 is a valve, 6 is a reaction tube, 7 is a nozzle, 8
9 is an electrode, 9 is a matching box, IO is a high frequency oscillator, 11 is a valve, 12 is a raw material container, I3 is a raw material, and 14 is a constant temperature bath. Patent applicant Sumitomo Electric Industries, Ltd. Patent attorney Aoyama Ao and one other person Figure
Claims (1)
ラズマＣＶＤ装置において、炭化水素を原料とし、１２
００℃以上に加熱した遷移金属を含む基材上にプラズマ
放電により格子定数Ｃｏが６．７２Å以下、電導度が２
０００Ｓ／ｃｍ以上の特性を有する導電性グラファイト
膜を形成する方法。(1) In a plasma CVD apparatus having a separate plasma discharge chamber and a forming chamber, a hydrocarbon is used as a raw material, and 12
The lattice constant Co is 6.72 Å or less and the electrical conductivity is 2 by plasma discharge on a substrate containing a transition metal heated to 00°C or higher.
A method of forming a conductive graphite film having characteristics of 000 S/cm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2200682A JP2794913B2 (en) | 1990-07-25 | 1990-07-25 | Method of forming conductive graphite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2200682A JP2794913B2 (en) | 1990-07-25 | 1990-07-25 | Method of forming conductive graphite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0483874A true JPH0483874A (en) | 1992-03-17 |
| JP2794913B2 JP2794913B2 (en) | 1998-09-10 |
Family
ID=16428498
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2200682A Expired - Fee Related JP2794913B2 (en) | 1990-07-25 | 1990-07-25 | Method of forming conductive graphite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2794913B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101858879A (en) * | 2010-05-24 | 2010-10-13 | 清华大学 | A method and device for measuring electrical conductivity of graphite |
| GB2527209A (en) * | 2014-06-13 | 2015-12-16 | Fgv Cambridge Nanosystems Ltd | Apparatus and method for plasma synthesis of graphitic products including graphene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9235468B2 (en) | 2013-04-12 | 2016-01-12 | Qualcomm Incorporated | Systems and methods to improve the reliability and lifespan of flash memory |
| JP6248754B2 (en) | 2014-03-28 | 2017-12-20 | 三浦工業株式会社 | Boiler system |
-
1990
- 1990-07-25 JP JP2200682A patent/JP2794913B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101858879A (en) * | 2010-05-24 | 2010-10-13 | 清华大学 | A method and device for measuring electrical conductivity of graphite |
| GB2527209A (en) * | 2014-06-13 | 2015-12-16 | Fgv Cambridge Nanosystems Ltd | Apparatus and method for plasma synthesis of graphitic products including graphene |
| GB2527209B (en) * | 2014-06-13 | 2019-08-28 | Fgv Cambridge Nanosystems Ltd | Apparatus and method for plasma synthesis of graphitic products including graphene |
| US11802052B2 (en) | 2014-06-13 | 2023-10-31 | Levidian Nanosystems Limited | Apparatus and method for plasma synthesis of graphitic products including graphene |
| US12252402B2 (en) | 2014-06-13 | 2025-03-18 | Levidian Nanosystems Limited | Apparatus and method for plasma synthesis of graphitic products including graphene |
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| Publication number | Publication date |
|---|---|
| JP2794913B2 (en) | 1998-09-10 |
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