JPS62202809A - Production of thermally decomposed graphite - Google Patents
Production of thermally decomposed graphiteInfo
- Publication number
- JPS62202809A JPS62202809A JP61045755A JP4575586A JPS62202809A JP S62202809 A JPS62202809 A JP S62202809A JP 61045755 A JP61045755 A JP 61045755A JP 4575586 A JP4575586 A JP 4575586A JP S62202809 A JPS62202809 A JP S62202809A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- argon gas
- benzene
- substrate
- anisotropy
- 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 abstract description 51
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 43
- 239000010439 graphite Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 230000008021 deposition Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052786 argon Inorganic materials 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000010790 dilution Methods 0.000 abstract description 3
- 239000012895 dilution Substances 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005297 pyrex Substances 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 abstract description 2
- 238000005292 vacuum distillation Methods 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈発明の技術分野〉
本発明は、１０００℃前ｉ後またはそれ以下の比較的低
温で、熱分解ＣＶＤ（化学気相堆積）法により、異方性
の優れた高配向熱分解黒鉛を製造する方法及び該熱分解
黒鉛の異方性の制御技術に関するものであり、新規な機
能素子を創作するだめの極めて有用な基本材料技術を確
立した点で技術的意義を有する。Detailed Description of the Invention <Technical Field of the Invention> The present invention is directed to the production of highly anisotropic materials using a pyrolytic CVD (chemical vapor deposition) method at a relatively low temperature of around 1000°C or lower. This invention relates to a method for producing oriented pyrolytic graphite and a technology for controlling the anisotropy of the pyrolytic graphite, and has technical significance in that it establishes an extremely useful basic material technology for creating new functional devices. .
〈従来の技術とその問題点〉
化学的に安定で、３０００℃以上の高温まで相変態せず
、熱と電気の伝導性に関して著しい異方性を有する黒鉛
の人工合成には、通常長期間に亘る高温高圧の製造プロ
セスが必要とされてきた。例えば、メタンを出発物質と
する場合には高温（約２０００℃以上）で熱分解しさら
に高配向化する目的で高温高圧下での熱処理が用いられ
ている。また、高分子繊維を高温処理することによシ、
繊維状炭素を得る方法も古くから知られている。しかし
ながら、これらの方法は高温で処理するために、画一化
された構造材料としては利用できるが、異方性を制御し
た機能電子材料への応用は困難である。他方、比較的低
温で熱分解黒鉛を得る方法として、出発物質に特殊な有
機化合物を用い、脱水素反応、脱ハロゲン化水素反応、
脱炭酸反応または脱水反応等を利用した形成法も度々用
いられているが１、炭素堆積物の高配向化が達成された
例は皆無であり、従って結晶性（異方性）の制御を達成
した例も存在しない。黒鉛の異方性を利用した機能材料
または機能素子を実現するためには、低温における熱分
解黒鉛の高配向化及び異方性の制御等の新技術の確立が
必要である。<Conventional technology and its problems> Artificial synthesis of graphite, which is chemically stable, does not undergo phase transformation even at high temperatures of 3000°C or higher, and has significant anisotropy in terms of thermal and electrical conductivity, usually requires a long period of time. A wide range of high-temperature, high-pressure manufacturing processes have been required. For example, when methane is used as a starting material, heat treatment at high temperature and high pressure is used to thermally decompose it at a high temperature (approximately 2000° C. or higher) and further improve orientation. In addition, by high-temperature treatment of polymer fibers,
Methods for obtaining fibrous carbon have also been known for a long time. However, since these methods are processed at high temperatures, although they can be used as standardized structural materials, it is difficult to apply them to functional electronic materials with controlled anisotropy. On the other hand, as a method for obtaining pyrolytic graphite at relatively low temperatures, special organic compounds are used as starting materials, and dehydrogenation, dehydrohalogenation,
Formation methods that utilize decarboxylation or dehydration reactions are often used, but there are no examples of achieving highly oriented carbon deposits, and therefore controlling crystallinity (anisotropy). There are no examples of this. In order to realize functional materials or functional devices that utilize the anisotropy of graphite, it is necessary to establish new technologies such as increasing the orientation of pyrolytic graphite at low temperatures and controlling the anisotropy.
〈発明の目的〉
本発明は、上記従来の現状に鑑みてなされたもので、１
０００℃前後またはそれ以下の比較的低温で優れた異方
性を有する熱分解黒鉛を基板上に形成するとともに得ら
れた熱分解黒鉛の異方性の制御も可能とする技術を確立
したものであり、その異方性を利用した機能材料または
機能素子の実現を可能とする熱分解墨鉛の製造技術及び
該熱分解黒鉛の異方性の制御技術を提供することを目的
とする。<Object of the invention> The present invention has been made in view of the above-mentioned conventional situation, and has the following features:
We have established a technology that allows us to form pyrolytic graphite with excellent anisotropy on a substrate at a relatively low temperature of around 000°C or lower, and also to control the anisotropy of the obtained pyrolytic graphite. The purpose of the present invention is to provide a technology for producing pyrolytic black lead and a technology for controlling the anisotropy of the pyrolytic graphite, which makes it possible to realize functional materials or functional devices utilizing its anisotropy.
〈発明の概要〉
本発明の熱分解黒鉛形成法は、芳香族炭化水素または不
飽和炭化水素を原料とし、基板上へ熱分解黒鉛を形成す
るに際して、熱分解雰囲気中に、反応管壁に付着させた
炭素薄膜の効果を導入することにより、ｔｏｏｏ℃前後
またはそれ以下の低温で、異方性の優れた熱分解黒鉛を
堆積させるとともに基板上への該熱分解黒鉛の堆積速度
を制御することで、熱分解黒鉛の結晶性及び異方性を制
御することを特徴とする。<Summary of the Invention> The method for forming pyrolytic graphite of the present invention uses aromatic hydrocarbons or unsaturated hydrocarbons as raw materials, and when forming pyrolytic graphite on a substrate, it adheres to the wall of a reaction tube in a pyrolysis atmosphere. By introducing the effect of a thin carbon film, it is possible to deposit pyrolytic graphite with excellent anisotropy at a low temperature of around 100°C or lower, and to control the deposition rate of the pyrolytic graphite on the substrate. This method is characterized by controlling the crystallinity and anisotropy of pyrolytic graphite.
〈実施例〉
図面は本発明の！実施例に用いられる熱分解黒鉛生成装
置のブロック構成図である。<Example> The drawings are of the present invention! FIG. 1 is a block diagram of a pyrolytic graphite production device used in Examples.
出発物質として使用される炭化水素としては、芳香族炭
化水素または不飽和炭化水素が望ましく、これらは１０
００℃前後またはそれ以下の温度で熱分解される。熱分
解黒鉛が形成される基板としては、シリコン、サファイ
ア、炭化珪素（α形及びβ形）、窒化硼素、キッシュ黒
鉛、高配向黒鉛等の単結晶または石英ガラスを用いる。The hydrocarbon used as a starting material is preferably an aromatic hydrocarbon or an unsaturated hydrocarbon;
It is thermally decomposed at temperatures around 00°C or lower. As a substrate on which pyrolytic graphite is formed, single crystals such as silicon, sapphire, silicon carbide (α-type and β-type), boron nitride, Quiche graphite, highly oriented graphite, or quartz glass are used.
これらは約１０００℃の反応温度でも変質しない条件を
満足するものでなければならない。These must satisfy the condition that they do not deteriorate even at a reaction temperature of about 1000°C.
反応管への原料供給方法は常圧バブラー法または減圧法
を用いる。いずれの方法でも、後述する様に、原料の供
給量及び黒鉛の堆積速度を制御することにより高配向熱
分解黒鉛が得られ、異方性の制御も可能である。常圧バ
ブラー法ではキアリアガスとしてアルゴンガスを使用す
る。図面は常圧バブラー法を利用した装置構成を示して
いるが、この装置で減圧ＣＶＤ法を利用することもでき
る。A normal pressure bubbler method or a reduced pressure method is used to supply raw materials to the reaction tube. In either method, highly oriented pyrolytic graphite can be obtained by controlling the supply amount of raw materials and the deposition rate of graphite, as will be described later, and it is also possible to control anisotropy. In the normal pressure bubbler method, argon gas is used as Chiaria gas. Although the drawing shows an apparatus configuration using the normal pressure bubbler method, it is also possible to use the low pressure CVD method with this apparatus.
この場合には黒鉛の膜厚を常圧バブラー法に比べてより
均一に実現することが可能である。In this case, it is possible to achieve a more uniform graphite film thickness than in the normal pressure bubbler method.
以下製造工程に従って説明する。The manufacturing process will be explained below.
真空蒸留による精製操作を行ったベンゼンが収納された
バブル容器ｌ内にアルゴンガス制御系２よりアルゴンガ
スを供給してベンゼンをバブルさせ、パイレックスガラ
ス管８を介して石英反応管４ヘベンゼン分子を給送する
。この際パズル容器１内の液体ベンゼンの温度を一定に
保持してアルゴンガス流量をバルブ５で調節し、ベンゼ
ン分子の反応管４内への供給量を毎時数ミリモルに一定
制御する。一方、希釈ライン６よりアルゴンを流し、反
応管４へ給送されるベンゼン分子数密度及び流速を最適
化する。反応管４には、前述したシリコン等の成長用基
板の載置された試料台７が設置されており、その周囲の
反応管内壁には炭素薄膜を付着させている。反応管４の
外周囲には加熱炉８が友けられてお９、この加熱炉８に
よって反応管４内の成長用基板は１０００℃前後または
それ以下の温度に保持されている。Argon gas is supplied from the argon gas control system 2 into a bubble container l containing benzene purified by vacuum distillation to bubble the benzene, and benzene molecules are supplied to the quartz reaction tube 4 through the Pyrex glass tube 8. send At this time, the temperature of the liquid benzene in the puzzle container 1 is kept constant, the argon gas flow rate is adjusted by the valve 5, and the amount of benzene molecules supplied into the reaction tube 4 is controlled to be constant at several mmol per hour. On the other hand, argon is flowed through the dilution line 6 to optimize the benzene molecule number density and flow rate fed to the reaction tube 4. The reaction tube 4 is equipped with a sample stage 7 on which the aforementioned growth substrate of silicon or the like is placed, and a thin carbon film is attached to the inner wall of the reaction tube around the sample stage 7. A heating furnace 8 is provided around the outer periphery of the reaction tube 4, and the growth substrate inside the reaction tube 4 is maintained at a temperature of about 1000° C. or lower by this heating furnace 8.
反応管４内に導入されたベンゼン分子は１０００℃前後
またはそれ以下の温度に加熱されて熱分解し、順次成長
用基板上に成長形成される０この際、成長形成される熱
分解黒鉛は、反応雰囲気中で反応管４に付着された炭素
薄膜の効果が導入されて異方性の優れた黒鉛となり、従
来に比べて低い温度で高配向化が達成される。また、反
応管４内に導入されるベンゼン分子の流速及び濃度を変
化させると、堆積速度が変化し、それに応じて結晶性も
変化するので異方性の制御も容易に可能となる。The benzene molecules introduced into the reaction tube 4 are heated to a temperature of around 1000°C or lower and thermally decomposed, and are sequentially grown and formed on the growth substrate.At this time, the pyrolytic graphite that is grown and formed is In the reaction atmosphere, the effect of the carbon thin film attached to the reaction tube 4 is introduced, resulting in graphite with excellent anisotropy, and highly oriented graphite can be achieved at a lower temperature than in the past. Furthermore, by changing the flow rate and concentration of benzene molecules introduced into the reaction tube 4, the deposition rate changes and the crystallinity changes accordingly, making it possible to easily control the anisotropy.
熱分解黒鉛の結晶性または異方性は、得られた熱分解黒
鉛のＣ軸方向及びＣ軸に垂直な面内の比抵抗測定により
評価した。表１によれば、従来の低温熱分解黒鉛の面内
比抵抗の値（１〜２×ｌ０−３Ω・、）に比べて、上記
実施例で得られた熱分解黒鉛の比抵抗値が１桁程度低く
なっており、明らかに結晶性が向上したことを示してい
る。また、熱分解黒鉛の結晶性は堆積速度に顕著に依存
し、遅い堆積速度で高配向熱分解黒鉛が得られる。The crystallinity or anisotropy of the pyrolytic graphite was evaluated by measuring the specific resistance of the obtained pyrolytic graphite in the C-axis direction and in a plane perpendicular to the C-axis. According to Table 1, compared to the in-plane resistivity value of conventional low-temperature pyrolytic graphite (1 to 2×l0-3Ω・,), the resistivity value of pyrolytic graphite obtained in the above example is 1 It is several orders of magnitude lower, clearly indicating that the crystallinity has improved. Furthermore, the crystallinity of pyrolytic graphite is significantly dependent on the deposition rate, and highly oriented pyrolytic graphite can be obtained at slow deposition rates.
尚表１は本発明の１実施例の結果であり、本発明は何ら
これのみに限定されるものでない。Table 1 shows the results of one example of the present invention, and the present invention is not limited to this in any way.
表１
〈発明の効果〉
本発明の熱分解黒鉛形成法によれば、熱分解雰囲気の効
果を取り込んで、異方性の優れた高配向熱分解黒鉛が、
従来より低い１０００℃前後またはそれ以下の低温で得
られる。また、堆積速度を制御することにより、異方性
の制御も可能となるため、これを利用した機能電子材料
への応用を促准させることができると期待される。Table 1 <Effects of the Invention> According to the method for forming pyrolytic graphite of the present invention, highly oriented pyrolytic graphite with excellent anisotropy can be produced by incorporating the effect of the pyrolysis atmosphere.
It can be obtained at a low temperature of around 1000°C or lower than conventionally. Furthermore, by controlling the deposition rate, it is also possible to control anisotropy, so it is expected that this will be used to promote application to functional electronic materials.
添付図面は本発明の！実施例の説明に供する熱分解黒鉛
製造装置のブロック構成図である。
ｌ・・・バブル容器 ２・・・アルゴンガス制御系３
・・・ガラス管 ４・・・反応管６・・・希釈ライ
ン ７・・・試料台８・・・加熱炉The attached drawings are of the invention! FIG. 1 is a block configuration diagram of a pyrolytic graphite manufacturing apparatus for explaining an example. l... Bubble container 2... Argon gas control system 3
... Glass tube 4 ... Reaction tube 6 ... Dilution line 7 ... Sample stage 8 ... Heating furnace
Claims (1)
し、該炭化水素を毎時一定量反応系へ供給して、１００
０℃前後またはそれ以下の低温熱分解により、基板上へ
異方性を有する高配向化黒鉛を形成することを特徴とす
る熱分解黒鉛の製造方法。 ２、反応系として透光性中空内壁に炭素薄膜を付着させ
た反応管を用いた特許請求の範囲第１項記載の熱分解黒
鉛の製造方法。 ３、炭化水素の供給量及び基板上への黒鉛の堆積速度を
制御することで、熱分解黒鉛の結晶性（異方性）を制御
する特許請求の範囲第１項又は第２項記載の熱分解黒鉛
の製造方法。[Claims] 1. An aromatic hydrocarbon or an unsaturated hydrocarbon is used as a starting material, and a certain amount of the hydrocarbon is supplied to the reaction system every hour,
A method for producing pyrolytic graphite, which comprises forming highly oriented graphite having anisotropy on a substrate by low-temperature pyrolysis at around 0°C or lower. 2. The method for producing pyrolytic graphite according to claim 1, which uses a reaction tube having a transparent hollow inner wall with a thin carbon film attached as the reaction system. 3. The heat treatment according to claim 1 or 2, which controls the crystallinity (anisotropy) of pyrolytic graphite by controlling the amount of hydrocarbon supplied and the rate of graphite deposition on the substrate. A method for producing decomposed graphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61045755A JPS62202809A (en) | 1986-02-28 | 1986-02-28 | Production of thermally decomposed graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61045755A JPS62202809A (en) | 1986-02-28 | 1986-02-28 | Production of thermally decomposed graphite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62202809A true JPS62202809A (en) | 1987-09-07 |
| JPH048367B2 JPH048367B2 (en) | 1992-02-14 |
Family
ID=12728112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61045755A Granted JPS62202809A (en) | 1986-02-28 | 1986-02-28 | Production of thermally decomposed graphite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62202809A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008540316A (en) * | 2005-05-13 | 2008-11-20 | クリー インコーポレイテッド | Method and apparatus for producing silicon carbide crystal |
| JP2011187675A (en) * | 2010-03-09 | 2011-09-22 | Mitsubishi Electric Corp | Method for manufacturing silicon carbide semiconductor device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59232904A (en) * | 1983-06-14 | 1984-12-27 | Agency Of Ind Science & Technol | Manufacture of electrically conductive thin film |
| JPS6037045A (en) * | 1983-08-09 | 1985-02-26 | Ricoh Co Ltd | Information memory |
-
1986
- 1986-02-28 JP JP61045755A patent/JPS62202809A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59232904A (en) * | 1983-06-14 | 1984-12-27 | Agency Of Ind Science & Technol | Manufacture of electrically conductive thin film |
| JPS6037045A (en) * | 1983-08-09 | 1985-02-26 | Ricoh Co Ltd | Information memory |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008540316A (en) * | 2005-05-13 | 2008-11-20 | クリー インコーポレイテッド | Method and apparatus for producing silicon carbide crystal |
| JP2011187675A (en) * | 2010-03-09 | 2011-09-22 | Mitsubishi Electric Corp | Method for manufacturing silicon carbide semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH048367B2 (en) | 1992-02-14 |
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