JPS60210597A - Gas phase synthesizing method of diamond - Google Patents

Gas phase synthesizing method of diamond

Info

Publication number
JPS60210597A
JPS60210597A JP59066634A JP6663484A JPS60210597A JP S60210597 A JPS60210597 A JP S60210597A JP 59066634 A JP59066634 A JP 59066634A JP 6663484 A JP6663484 A JP 6663484A JP S60210597 A JPS60210597 A JP S60210597A
Authority
JP
Japan
Prior art keywords
diamond
transition metal
plasma
hydrocarbon
organic transition
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.)
Pending
Application number
JP59066634A
Other languages
Japanese (ja)
Inventor
Katsuyuki Nakamura
克之 中村
Susumu Kawachi
河内　進
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd, Asahi Kasei Kogyo KK filed Critical Asahi Chemical Industry Co Ltd
Priority to JP59066634A priority Critical patent/JPS60210597A/en
Publication of JPS60210597A publication Critical patent/JPS60210597A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond

Abstract

PURPOSE:To obtain diamond at especially high rate of formation by allowing an organic transition-metal comp. of prescribed quantity to coexist and converting hydrocarbon and gaseous hydrogen to plasma under reduced pressure. CONSTITUTION:Gaseous mixture of hydrocarbon (for example, CH4 and C2H6) and hydrogen in 10<-6>-1mol ratio is converted to plasma under reduced pressure to manufacture diamond by allowing organic transition-metal comps. of 10<-6>-5% range per hydrocarbon to coexist. Said hydrocarbon may be accompanied with carrier gasses or in the state of reduced pressure to supply it into the plasma and if possible, it is preferably supplied in the state of sublimation or gas. Also, as said reduced pressure, the pressure of said plasma reaction system is the range of <=1atm-10<-3>Torr. As the place wherein diamond is produced, a substrate such as Si and quartz is preferably provided. Further, as said organic transition-metal comps., for example, dis(cyclopentadienly)-iron (ferrocene) of the like is used.

Description

【発明の詳細な説明】 本発明は、低圧下でダイヤモンドを製造する気相合成法
に関する。特に、ダイヤモンドの生成速度を高めた方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas phase synthesis method for producing diamond under low pressure. In particular, it relates to a method that increases the rate of diamond production.

従来、低圧下でダイヤモンド全製造しようとする試みは
種々性なわれてきたが、その製造技術には多くの問題を
含んでいる。例えば、化学凶相析出法ではダイヤモンド
の形成とともに黒鉛や非ダイヤモンド炭素が形成された
。また、イオンビーム法では、雰囲気中の不活性ガスな
どの原子がダイヤモンド格子中に取りこまれやすい。一
方、低圧下のプラズマ法では、水素をかな多含有したア
モルファスカーボンが生成しやすく、ダイヤモンドが生
成しにくい上に、その生成速度が極めて遅かった。例え
ば、マイクロ波を照射して発生したプラズマの場合で、
ダイヤモンドの生成は、３時間当シ１〜２μｍ程度であ
る。このような方法では、工業的に活用することは極め
てむつかしい。In the past, various attempts have been made to manufacture diamonds entirely under low pressure, but these manufacturing techniques involve many problems. For example, in the chemical phase precipitation method, graphite and non-diamond carbon were formed along with the formation of diamond. Furthermore, in the ion beam method, atoms such as inert gases in the atmosphere are likely to be incorporated into the diamond lattice. On the other hand, in the plasma method under low pressure, amorphous carbon containing a large amount of hydrogen is easily produced, and diamond is difficult to produce, and the production rate is extremely slow. For example, in the case of plasma generated by microwave irradiation,
Diamond formation is approximately 1 to 2 μm per 3 hours. It is extremely difficult to use such a method industrially.

本発明者らは、種々の炭化水素についてプラズマ反応を
検討している過程から、ある種の有機金属化合物の存在
によって、特異な形態を有する生成物およびその生成速
度が変ることを見出し、さらに鋭意研究の結果、本発明
に到達した。In the process of examining plasma reactions for various hydrocarbons, the present inventors discovered that the presence of a certain type of organometallic compound changes the production rate of a product with a unique morphology. As a result of research, we have arrived at the present invention.

本発明は、炭化水素および水素ガスを低圧下でプラズマ
化しダイヤモンドを製造するに際し、該炭化水素に対し
１０−ｓ％から５−の範囲で有機遷移金属化合物全共存
させることを特徴とするダイヤモンドの気相合成法であ
る。The present invention is characterized in that when producing diamond by converting hydrocarbon and hydrogen gas into plasma under low pressure, an organic transition metal compound is allowed to coexist in the range of 10-s% to 5-s% with respect to the hydrocarbon. This is a gas phase synthesis method.

本発明において用いる炭化水素は、基本的に炭素と水素
からなる化合物であって、キャリヤーガスによシ、また
は減圧状態によシ、気体状、固体状、液体状で同伴され
、プラズマ中に供給されればよいが、きわめて微少状態
、できれば昇華または気体状態で供給されるものが好ま
しい。特に炭素数２８以下の炭化水素であシ、さらに取
り扱いやすさから１５以・下の炭化水素が好ましい。例
えば、メタン、エタン、プロパン、ブタン、イソブタン
、２．２−ジメチルプロパン等の飽和炭化水素、エチレ
ン、アセチレン、プロピレン、ブチレン、ブタジェン等
の不飽和炭化水素、シクロベンタン、ジシクロペンタン
、アダマンタン、ノルボルナン、デカリン、シクロヘキ
サン、およびシクロヘキサンの誘導体等の脂環式炭化水
素、ベンゼン、トルエン、キシレン、ナフタレン、アン
トラセン等の芳香族炭化水素等である。The hydrocarbon used in the present invention is basically a compound consisting of carbon and hydrogen, and is entrained in a carrier gas or under reduced pressure in a gaseous, solid, or liquid state and supplied into the plasma. However, it is preferable to supply it in a very small amount, preferably in a sublimated or gaseous state. In particular, hydrocarbons having 28 or less carbon atoms are preferable, and hydrocarbons having 15 or less carbon atoms are more preferable for ease of handling. For example, saturated hydrocarbons such as methane, ethane, propane, butane, isobutane, 2,2-dimethylpropane, unsaturated hydrocarbons such as ethylene, acetylene, propylene, butylene, butadiene, cyclobentane, dicyclopentane, adamantane, norbornane. , alicyclic hydrocarbons such as decalin, cyclohexane, and cyclohexane derivatives, and aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and anthracene.

本発明において、炭化水素と水素ガスの使用比率は、水
素に対する炭化水素のモル比で１０−６〜１であり、こ
れ以下ではダイヤモンドの生成速度が遅くな力、また、
１以上では黒色物が生成しゃすくなる。好ましい範囲は
１０−４〜０．５の範囲である。In the present invention, the ratio of hydrocarbon to hydrogen gas used is a molar ratio of hydrocarbon to hydrogen of 10-6 to 1; below this, the diamond formation rate is slow;
If it is 1 or more, black matter is less likely to be produced. The preferred range is 10-4 to 0.5.

本発明において、基本的な反応用材料は炭化水素と水素
ガスであるが、この他にアルゴンやヘリウムのような中
性ガスを併用することもできる。In the present invention, the basic reaction materials are hydrocarbon and hydrogen gas, but neutral gases such as argon and helium can also be used in combination.

これらの中性ガスは炭化水素の同伴用に用いたり、プラ
ズマ反応系の制御用に用いたりすることができる。These neutral gases can be used to entrain hydrocarbons or to control a plasma reaction system.

本発明において低圧下とは、プラズマ反応系中の圧力が
１気圧以下１０−’　ＴＯｒｒの範囲であシ、好ましく
は１００　Ｔｏｒｒから１０−’Ｔｏｒｒの範囲である
。この圧力は、使、用する炭化水素の種類、水素ガスと
の比率、アルゴンやヘリウムなど中性ガスの使用量、プ
ラズマ反応装置や真空発生装置の容量などによってバラ
ンスをとるべきものである。In the present invention, low pressure means that the pressure in the plasma reaction system is in the range of 1 atmosphere or less and 10-' Torr, preferably in the range of 100 Torr to 10-' Torr. This pressure must be balanced depending on the type of hydrocarbon used, its ratio to hydrogen gas, the amount of neutral gas such as argon or helium used, and the capacity of the plasma reactor or vacuum generator.

一般に、圧力が低すぎるとダイヤモンドの生成速度が遅
くなり、また、高すぎるとプラズマの安定性に欠けたシ
、生成物中に黒色のカーボンが生成しやすくなる。Generally, if the pressure is too low, the rate of diamond formation will be slow, and if the pressure is too high, the plasma will lack stability and black carbon will be more likely to be generated in the product.

本発明において、プラズマ化するためには、従来公知の
プラズマ化装置やプラズマ化の励起手段が用いられる。In the present invention, in order to generate plasma, a conventionally known plasma generator or plasma excitation means is used.

例えば、直流電場による電離、５０〜６０ヘルツ程度の
低周波数領域から１０４〜１０８ヘルツの高周波領域の
交流電場による電離、さらに、１０９〜ｔ　ｏｔｔヘル
ツの周波数を有するマイクロ波領域の電磁波による電離
などが用いられる。For example, ionization caused by a DC electric field, ionization caused by an AC electric field in a low frequency range of about 50 to 60 hertz to a high frequency range of 104 to 108 hertz, and ionization caused by electromagnetic waves in the microwave range with a frequency of 109 to ott Hertz. used.

この中で、高周波領域の交流電場による高周波プラズマ
およびマイクロ波によるマイクロ波プラズマが、本発明
のプラズマ化の手段としては好ましく、特にマイクロ波
プラズマが好ましい。このように、周波数の高い領域で
励起したプラズマの方が、水素含量の多いアモルファス
カーボンの副成が抑制され好ましい。Among these, high-frequency plasma using an alternating current electric field in a high-frequency region and microwave plasma using microwaves are preferable as the plasma generation means of the present invention, and microwave plasma is particularly preferable. In this way, plasma excited in a high frequency region is preferable because it suppresses the by-formation of amorphous carbon with a high hydrogen content.

本発明において、ダイヤモンド全生成させる場所として
基板を設置することは好ましい。そのような基板として
は、本発明のプラズマ雰囲気において基本的に分解され
たシ破損したシしない物質が用いることができる。例え
ば、シリコン、石英、炭化ケイ素、窒化ケイ素などのケ
イ素化合物、黒鉛、ダイヤモンドなどの炭素質物質、モ
リブデン、タングステン、ステンレス、鉄、ニッケル、
銅すどの金属、サファイヤ、アルミナ、シルコニアナど
の酸化物など広く用いられ、これらの基板は、板状、薄
片状、粒状、粉状、フィラメント状など種々の形状のも
のを用いることができる。In the present invention, it is preferable to install a substrate as a place where all diamonds are generated. Such a substrate can be any material that is essentially decomposed and undamaged in the plasma atmosphere of the present invention. For example, silicon compounds such as silicon, quartz, silicon carbide, and silicon nitride, carbonaceous materials such as graphite and diamond, molybdenum, tungsten, stainless steel, iron, nickel,
Metals such as copper threads, and oxides such as sapphire, alumina, and silconiana are widely used, and these substrates can be in various shapes such as plate, flake, granule, powder, and filament.

基板の温度は、ガス圧、プラズマ化の容量などによって
変化するが、１５０〜１２００Ｃの間、好ましくは２５
０〜１００ＯＵであり、５００〜１０００Ｃの間が最も
好ましく、ダイヤモンドの成長速度が速い。１５０Ｃ以
下では生成物は非晶質になりやすく、また、１２００Ｃ
以上では黒色炭素物質ができやすく好ましくない。The temperature of the substrate varies depending on gas pressure, plasma generation capacity, etc., but is between 150 and 1200C, preferably 25C.
0 to 100 OU, most preferably 500 to 1000 C, and the growth rate of diamond is fast. Below 150C, the product tends to become amorphous;
The above is not preferable since black carbon substances tend to be formed.

本発明において用いる有機遷移金属化合物は、基本的に
炭素、水素および遷移金属からなる化合物であり、例え
ば、シクロペンタジェニル系遷移金属化合物、ベンゼン
遷移金属比合物、アルキル、アリルあるいはアルキニル
遷移金属化合物など、基本的に炭化水素と遷移金属とか
らなる公知の有機遷移金属化合物が使用できる。また、
この有機遷移金属化合物は、部分的に、カルボニル、チ
オフェン、ピリジンあるいはアセチルアセトンなどが配
位して、安定な錯化合物を形成していてもよい。The organic transition metal compound used in the present invention is a compound basically consisting of carbon, hydrogen, and a transition metal, and includes, for example, a cyclopentadienyl transition metal compound, a benzene transition metal compound, an alkyl, allyl, or alkynyl transition metal compound. Known organic transition metal compounds basically consisting of a hydrocarbon and a transition metal can be used. Also,
This organic transition metal compound may be partially coordinated with carbonyl, thiophene, pyridine, acetylacetone, or the like to form a stable complex compound.

好ましい遷移金属としては、周基体表の■ｂ族に属する
Ｔｉ、　Ｚｒ、　Ｖｂ族に属するｖ、　ｖｉｂ族に属す
るＣｒ、　Ｍｏ、　Ｗ、■ｂ族に属する勘、■族に属す
るＦｅ、　Ｃｏ、　Ｎｉ、　Ｒｕ％Ｒｈ、　ＰｃＬ　Ｏ
ｓ、　Ｉｒ、　Ｐｔ、　■ｂ族に属するＣｕ、　Ａｇ、
　［ｂ族に属するＺｎ、　Ｃｄ　テあシ、特に、Ｔｉ％
Ｖ、　Ｃｒ、　Ｍｎ％Ｆｅ、　Ｃｏ、　Ｎｉ、　Ｒｕ、
　Ｒｈ、　Ｐｄであシ、最も好ましい遷移金属はＦｅ％
Ｃｏ、Ｎｉである。Preferred transition metals include Ti, Zr, which belongs to group ①b, Cr, Mo, W, which belongs to group ``vib'', Fe, Co, which belongs to group ②, Ni, Ru%Rh, PcL O
s, Ir, Pt, ■ Cu belonging to group b, Ag,
[Zn and Cd belonging to group b, especially Ti%
V, Cr, Mn%Fe, Co, Ni, Ru,
Rh, Pd, most preferred transition metal is Fe%
They are Co and Ni.

有機遷移金属化合物を例示するならば、ジシクロペンタ
ジェニル鉄（フェロセン）、ジシクロペンタジェニルニ
ッケルにシクロセン）、’）（１）チルシクロペンタジ
ェニル）ニッケル、ジシクロペンタジェニルコバルト（
コバルトセン）、ジシクロペンタジェニルチタン、ジシ
クロペンタジェニルバナジ／、ジシクロベ／タジエニル
クロム、ジシクロベ／タジエニルマンガン、ジシクロペ
ンタジェニルルビジウムなどのシクロペンタジェニル系
遷移金属化合物、ジベンゼンクロム、シクロペンタジェ
ニルベンゼンクロム、ジベンゼンハナジン、ジベンゼン
モリブデン、ジベンゼンタングステンなどのベンゼン−
遷移金属化合物、ジ（π−アリル）ニッケル、トリ（π
−アリル）鉄、トリ（π−アリル）コバルト、シクロベ
ンタジェニルテトラ力ルポニルバナジン、ビス（シクロ
ペンタジェニルジカルボニル鉄）、ビス（シクロペンタ
ジエニル力ルポニルニッケル）などの他、アセチレン化
合物との錯体などであり、好ましい有機遷移金属比合物
は、気化したシ昇華性を有し、プラズマ中へ導入が容易
なことが望ましい。特に好ましい有機遷移金属化合物は
、プラズマへの導入が容易なばかシでなく、ダイヤモン
ドの生成速度の促進効果が顕著なフェロセ／、ニラケロ
セン、コバルトセンである。Examples of organic transition metal compounds include dicyclopentadienyl iron (ferrocene), dicyclopentadienyl nickel (cyclocene), (1) (1) tylcyclopentadienyl) nickel, and dicyclopentadienyl cobalt (
cobaltocene), dicyclopentadienyl titanium, dicyclopentadienylvanady/, dicyclobe/tadienylchromium, dicyclobe/tadienylmanganese, dicyclopentadienylrubidium, and other cyclopentadienyl transition metal compounds, dibenzenechromium, Benzene such as cyclopentadienylbenzenechromium, dibenzenehanazine, dibenzenemolybdenum, dibenzenetungsten, etc.
Transition metal compounds, di(π-allyl)nickel, tri(π
- Allyl) iron, tri(π-allyl) cobalt, cyclobentadienyltetra-luponylvanadine, bis(cyclopentadienyl dicarbonyl iron), bis(cyclopentadienyl dicarbonyl nickel), as well as acetylene compounds. It is desirable that the organic transition metal compound has sublimation property when vaporized and can be easily introduced into the plasma. Particularly preferred organic transition metal compounds are ferrocetate, kerosene, and cobaltocene, which are not trivial and can be easily introduced into the plasma, and which have a remarkable effect of accelerating the diamond production rate.

これら有機遷移金属化合物の量は、原料の炭化水素に対
し１０−６％から５％の範囲で使用する。The amount of these organic transition metal compounds used is in the range of 10-6% to 5% based on the raw material hydrocarbon.

これ以下では、ダイヤモンドの生長速度を加速する効果
は認められず、また、５％以上では黒色炭素質の生成が
顕著になることや、生成物中に金属が包含されやすくな
り好ましくない。好ましくは１ｏ−４俤からｏ、ｓｌ、
特に１０−１％から０．１％の範囲である。If it is less than this, no effect of accelerating the growth rate of diamond will be observed, and if it is more than 5%, the formation of black carbonaceous material will become noticeable and metals will be easily included in the product, which is not preferable. Preferably from 1o-4 kou to o, sl,
In particular, it ranges from 10-1% to 0.1%.

有機遷移金属化合物をプラズマ中に導入する方法として
は、減圧下で有機遷移金属化合物を加熱し、気化または
昇華する方法、その際、キャリヤーガスや炭化水素に同
伴させる方法、あるいは炭化水素中に溶解しておき、こ
れを霧状にプラズマ域に導入する方法などが使用できる
。The organic transition metal compound can be introduced into the plasma by heating the organic transition metal compound under reduced pressure and vaporizing or sublimating it, by entraining it in a carrier gas or hydrocarbon, or by dissolving it in the hydrocarbon. It is possible to use a method in which the atomized material is left in place and then introduced into the plasma region in the form of a mist.

本発明を実施するには、種々の装置が使用できるが、そ
の例を第１図、第２図に示した。A variety of devices can be used to carry out the invention, examples of which are shown in FIGS. 1 and 2.

図中、１は水素ガス供給源、２は炭化水素および有機遷
移金属化合物供給装置、３，４は流量計、５は反応管、
６は真空排気装置、７，８，９．１０はパルプ、１１は
基板の支持体、１２は基板、１３はマイクロ波発振機、
１４はマイクロ波整合器、１５はマイクロ波導波管、１
６は高周波発振機、１７は高周波誘導用コイルである。In the figure, 1 is a hydrogen gas supply source, 2 is a hydrocarbon and organic transition metal compound supply device, 3 and 4 are flow meters, 5 is a reaction tube,
6 is a vacuum evacuation device, 7, 8, 9.10 is pulp, 11 is a substrate support, 12 is a substrate, 13 is a microwave oscillator,
14 is a microwave matching device, 15 is a microwave waveguide, 1
6 is a high frequency oscillator, and 17 is a high frequency induction coil.

一般的実験操作例を第１図、第２図を用いて示すならば
、まず、バルブ？全閉じ反応管５の中を１０”−’Ｔｏ
ｒｒ以下まで真空排気装置６によって排気した後、パル
プ８．９を開は水素ガス全所定量流す。次に、マイクロ
波発振機１３または高周波発振機１６の出力をあげなが
ら、第１図では導波管１５全通してマイクロ波を服射し
、その際、マイクロ波整合器によって調整しプラズマを
発生させる。また、第２図では高周波誘導用コイル１７
によってプラズマを発生させる。炭化水素および有機遷
移金属化合物は、パルプ８を開け、流量計４全通して調
節された水素ガスに同伴されて、炭化水素供給装置２か
ら所定量供給される。ダイヤモンドの生成は、基板の支
持体１１に乗せた基板１２の上に認められる。If we were to show examples of general experimental operations using Figures 1 and 2, first of all, what about valves? 10''-'To inside the fully closed reaction tube 5
After evacuating to below rr using the vacuum evacuation device 6, the pulp 8.9 is opened to allow a predetermined amount of hydrogen gas to flow through. Next, while increasing the output of the microwave oscillator 13 or the high-frequency oscillator 16, microwaves are emitted through the entire waveguide 15 in FIG. let In addition, in FIG. 2, the high frequency induction coil 17
generates plasma. Hydrocarbons and organic transition metal compounds are supplied in a predetermined amount from the hydrocarbon supply device 2 by opening the pulp 8 and entrained by hydrogen gas which is regulated through the flow meter 4 . Diamond formation is observed on the substrate 12 mounted on the substrate support 11.

このような操作において、炭化水素および有機遷移金属
化合物の供給量を制御するため、炭化水素供給装置２を
加熱したシ、冷却することができ、また、同伴用ガスと
して水素以外のアルゴン、ヘリウムなども使用できる。In such an operation, in order to control the supply amount of hydrocarbons and organic transition metal compounds, the hydrocarbon supply device 2 can be heated or cooled, and the entrained gas may be argon, helium, etc. other than hydrogen. can also be used.

基板は、発生するプラズマによっても暖められるが、温
度制御のために別途加熱源を用いて反応管の外部から、
あるいは反応管の内部に加熱源を設置して加熱すること
も可能である。The substrate is also heated by the generated plasma, but it is heated from outside the reaction tube using a separate heating source to control the temperature.
Alternatively, it is also possible to heat the reaction tube by installing a heating source inside the reaction tube.

本発明の方法によると、従来の公知の方法に比ベダイヤ
モンドの生成速度が格段に改善され、例えば、１時間当
υ４〜６μｍの厚さでダイヤモンド膜の形成も可能とな
るので、工業的な意義は大きい。According to the method of the present invention, the diamond production rate is significantly improved compared to conventional known methods, and it is possible to form a diamond film with a thickness of υ4 to 6 μm per hour, for example, making it possible to form a diamond film with a thickness of υ4 to 6 μm per hour. The significance is great.

このようにして得られたダイヤモンドは、膜状、粒状な
ど種々の形態を有するが、特に膜状物ではヒートシンク
、集積回路の熱伝導性絶縁膜、ドーピングして耐熱性半
導体、光学材料の透明高硬度保護膜などとして、なお、
粒状物は焼結用材料や研磨材料などとして極めて有用で
ある。Diamonds obtained in this way have various forms such as film-like and granular forms, but especially film-like materials are used for heat sinks, thermally conductive insulating films for integrated circuits, heat-resistant semiconductors by doping, and transparent high-performance optical materials. As a hardness protective film, etc.
The granules are extremely useful as sintering materials, polishing materials, and the like.

次に、実施例で本発明を説明する。Next, the present invention will be explained with examples.

実施例１ 第１図に示した装置を用い、炭化水素としてシクロヘキ
センを、また、有機遷移金属化合物としてフェロセンを
用い実施し友。第１図において、まずパルプ９を閉じ反
応管（石英製）５の中を１０’−’Ｔｏｒｒ付近捷で排
気した後、パルプ７を開は水素ガス流量−２１００ｍｌ
／ｍｉＲに調節し、マイクロ波発振機（周波数２．４５
　ＧＨｚ　）の出力を０．５ｋｗまで高め、プラズマを
発生させる。基板１２にはシリコンウェハを用い、基板
温度を熱伝対で測定し、はぼ８５０Ｃになるよう真空排
気装置６の排気速度で調節した。Example 1 An experiment was carried out using the apparatus shown in FIG. 1, using cyclohexene as the hydrocarbon and ferrocene as the organic transition metal compound. In FIG. 1, first, the pulp 9 is closed and the inside of the reaction tube (made of quartz) 5 is evacuated at around 10'-' Torr, and then the pulp 7 is opened at a hydrogen gas flow rate of -2100 ml.
/miR, and a microwave oscillator (frequency 2.45
GHz) to 0.5kw to generate plasma. A silicon wafer was used as the substrate 12, and the substrate temperature was measured with a thermocouple and adjusted by the evacuation speed of the evacuation device 6 so that the temperature reached approximately 850C.

次に、パルプ８を開は炭化水素および有機遷移金属化合
物供給装置２から０．００４％のフェロセンを含有する
シクロヘキサンを、平均的にほぼ５０　ｍｙ　／　ｂｒ
で供給した。２時間後、反応を停止し基板を取シ出した
ところ、シリコンウェハの上に透明で光沢のある膜が生
成していた。この膜の厚みは１２μｍ程度で、その成長
速度は約６μｍ／ｈｒであった。この膜のレーザーラマ
ン散乱スペクトルを測定したところ、１３５　ｓｃｍ−
”付近にピークを有するスペクトルが得られ、ダイヤモ
ンド膜であることが確認できた。第３図に本実施例で得
られたダイヤモンド膜のレーザーラマン散乱スペクトル
を示した。The pulp 8 is then injected with cyclohexane containing 0.004% ferrocene from the hydrocarbon and organo-transition metal compound feeder 2 at an average rate of approximately 50 my/br
It was supplied by After 2 hours, the reaction was stopped and the substrate was removed, and a transparent, glossy film was found to have formed on the silicon wafer. The thickness of this film was about 12 μm, and the growth rate was about 6 μm/hr. When the laser Raman scattering spectrum of this film was measured, it was found to be 135 scm-
A spectrum with a peak in the vicinity was obtained, confirming that it was a diamond film. Figure 3 shows the laser Raman scattering spectrum of the diamond film obtained in this example.

比較例１ 実施例１と同様の条件でフェロセンを使用せずに実施し
た。生成物は粒状で粒径が２．５μｍ程度であった。Comparative Example 1 Comparative example 1 was carried out under the same conditions as in Example 1 without using ferrocene. The product was granular and had a particle size of about 2.5 μm.

実施例２ 炭化水素としてシクロヘキサンの代シにジシクロペンタ
ンを用い、また、フェロセンの代りにコバルトセンｉ０
．００２％用いて、実施例１と同様の実験を行った。得
られたダイヤモンド膜の厚さは約９μｍであり、実施例
１とほぼ同様の成長速度が認められた。なお、生成した
膜のレーザーラマンスペクトルも実施例１の場合と一致
した。Example 2 As a hydrocarbon, dicyclopentane was used instead of cyclohexane, and cobaltocene i0 was used instead of ferrocene.
．． An experiment similar to Example 1 was conducted using 0.002%. The thickness of the obtained diamond film was about 9 μm, and the growth rate was observed to be almost the same as in Example 1. Note that the laser Raman spectrum of the produced film also matched that of Example 1.

実施例３ 第２図に示した装置を用い、炭化水素としてメチルシク
ロヘキサンを、また、有機遷移金属化合物トシてニツケ
ロセン０，００６％ｉ用いて実施した。第２図において
、まずパルプ９を閉じ反応管（石英製）５の中ｆ　１０
−’Ｔｏｒｒ付近まで排気した後、パルプ７を開け、水
素ガス流量全７０ゴ／關に調節し、高周波発振機（周波
数Ｉ　Ｓ、５６　ＭＨｚ　）より高周波を発生させ、誘
導用コイル１７に印加し、真空排気装置６で排気速度全
調節しプラズマを発生させた。基板（シリコンウェハ・
）温度は９００Ｃに設定し、これに、パルプ８を開は炭
化水素および有機遷移金属化合物供給装置２から、メチ
ルシクロヘキサンに０．００８　％ニラケロセンを含有
させた混合物を平均的にほぼ２５〜／ｈｒで供給した。Example 3 Using the apparatus shown in FIG. 2, an experiment was carried out using methylcyclohexane as a hydrocarbon and 0.006% i of nickelosene as an organic transition metal compound. In FIG. 2, first, the pulp 9 is closed and the inside of the reaction tube (made of quartz) 5 is
- After exhausting to around Torr, the pulp 7 is opened, the hydrogen gas flow rate is adjusted to 70 m/m, and a high frequency is generated from a high frequency oscillator (frequency IS, 56 MHz) and applied to the induction coil 17. The evacuation speed was fully adjusted using the evacuation device 6 to generate plasma. Substrate (silicon wafer/
) The temperature was set at 900C, and a mixture of 0.008% nirakerosene in methylcyclohexane was added to the pulp 8 from the hydrocarbon and organic transition metal compound feeder 2 for an average of approximately 25~/hr. It was supplied by

２時間後、反応を停止し基板を取シ出したところ、シリ
コンウェハの上に透明で光沢のある膜が生成してｔｎｆ
ｃｏこの膜の厚みは約８μｍ程度で、その成長速度は４
μｍ　／　ｈ　ｒであった。生成シた膜のレーザーラマ
ンスペクトルは、実施例１の場合よシ若干ブロードなが
らほぼ一致した。After 2 hours, the reaction was stopped and the substrate was taken out, and a transparent and shiny film was formed on the silicon wafer.
coThe thickness of this film is approximately 8 μm, and its growth rate is 4
It was μm/hr. The laser Raman spectrum of the produced film was almost the same as that of Example 1, although it was slightly broader.

比較例２ 実施例５と同様の実験全ニラケロセンを含有させないで
実施した。ただし、反応時間を４時間として実験を行っ
た結果、８μｍ強の厚さの膜が得られた。ダイヤモンド
の成長速度としては２μｍ／ｈｒ程度である。Comparative Example 2 An experiment similar to Example 5 was carried out without containing all nilakerosene. However, as a result of conducting an experiment with a reaction time of 4 hours, a film with a thickness of just over 8 μm was obtained. The growth rate of diamond is about 2 μm/hr.

実施例４ 実施例３と同様の方法において、炭化水素としてメタン
を用い、また、有機遷移金属化合物としてジベンゼンク
ロム０．ｏ　３　％　ｋ用い、水素ガス量２ｏｏ、ｚ／
＝、メタンノ平均供給量約１００　ｍ９／ｈｒとし、排
気速度を高めて実施した。基板（シリコンウェハ）温度
９７０Ｃで３時間反応を行った。Example 4 In the same method as in Example 3, methane was used as the hydrocarbon, and dibenzenechromium was used as the organic transition metal compound. o 3% k, hydrogen gas amount 2oo, z/
The experiment was carried out with an average methane supply rate of about 100 m9/hr and an increased pumping speed. The reaction was carried out at a substrate (silicon wafer) temperature of 970C for 3 hours.

得られたダイヤモンド膜は膜厚約８μｍであり、成長速
度として２．７μｍ　／　ｈ　ｒであった０なおル−ｆ
−ラマン散乱スペクトルは実施例５の場合、１）若干ブ
ロードになっていた。The obtained diamond film had a thickness of about 8 μm, and the growth rate was 2.7 μm/hr.
- In the case of Example 5, the Raman scattering spectrum was 1) slightly broad;

比較例３ 実施例４において、ジベンゼンクロムを用いないで４時
間の反応を実施した。得られた膜厚は約２．５μｍであ
り、ダイヤモンドの成長速度として約０．６μｍ／ｈｒ
であった。Comparative Example 3 In Example 4, the reaction was carried out for 4 hours without using dibenzenechromium. The obtained film thickness was approximately 2.5 μm, and the diamond growth rate was approximately 0.6 μm/hr.
Met.

実施例５　一 実施例１と同様の実験において、炭化水素としてアダマ
ンタンとシクロヘキサン１：２混合物を用い、有機遷移
金属化合物にフエロセ／を用い、基板温度を変えて実施
した。その結果、アダマンクンとシクロヘキサン混合物
の供給量が平均的に５０　ｍ９　／　ｈｒ　、水素ガス
量５０１ｎｅ／Ｍで基板温度８２０Ｃにおいて、フェロ
セン量’ｉｏ、００１％としたとき、生成したダイヤモ
ンド膜厚さは反応時間２時間で１０μｍであシ、ダイヤ
モンド成長速度として５μｍ　／　ｈｒであった。また
、フェロセン量０．０１％とし、基板温度が９００ｃの
とき、生成したダイヤモンド膜厚さは、反応時間２時間
で７μｍであり、成長速度は３．５μｍ　／　ｈｒであ
った。Example 5 An experiment similar to Example 1 was carried out using a 1:2 mixture of adamantane and cyclohexane as the hydrocarbon, FERROCE/ as the organic transition metal compound, and changing the substrate temperature. As a result, when the average supply rate of the adamancune and cyclohexane mixture was 50 m9/hr, the hydrogen gas amount was 501ne/M, the substrate temperature was 820C, and the amount of ferrocene was 'io, 001%, the thickness of the produced diamond film was as follows. The diamond growth rate was 10 μm in 2 hours, and the diamond growth rate was 5 μm/hr. Furthermore, when the amount of ferrocene was 0.01% and the substrate temperature was 900°C, the thickness of the diamond film produced was 7 μm in a reaction time of 2 hours, and the growth rate was 3.5 μm/hr.

フェロセン量をさらに増加させ０．０８％としたとき、
ダイヤモンドの生成と共に若干グラファイト的炭素が生
成してｂることが、レーザーラマン散乱スペクトルで認
められた。また、フェロセン量を減らし、１０−６％と
したときには、フェロセンを添加しない場合と成長速度
はほとんど変らず、２．５μｍ　／　ｈ　ｒ程度であっ
た。When the amount of ferrocene is further increased to 0.08%,
It was observed in the laser Raman scattering spectrum that some graphitic carbon was formed along with the formation of diamond. Furthermore, when the amount of ferrocene was reduced to 10-6%, the growth rate was almost the same as when no ferrocene was added, and was about 2.5 μm/hr.

【図面の簡単な説明】[Brief explanation of drawings]

第１図および第２図は、本発明において用いた装置例の
概略図、第３図は、実施例１で得られたダイヤモンド膜
のレーザーラマン散乱スペクトル図である。 １・・・・・・水素ガス供給源　２・・曲炭化水素およ
び有機遷移金属化合物供給装置　３，４・・曲流置針５
・・・・・・反応管　６・・間真空排気装置　７，８，
９，１０・・・・・・パルプ　１１・・開基板の支持体
　１２・・開基板１５・・・・・・マイクロ波発振機　
１４・・曲マイクロ波整合器１５・・・・・・マイクロ
波導波管　１６・・曲高周波発振機１７・・・・・・高
周波誘導用コイル 第１図 第３図1 and 2 are schematic diagrams of an example of the apparatus used in the present invention, and FIG. 3 is a laser Raman scattering spectrum diagram of the diamond film obtained in Example 1. 1... Hydrogen gas supply source 2... Curved hydrocarbon and organic transition metal compound supply device 3, 4... Curved flow positioning needle 5
...Reaction tube 6... Vacuum exhaust device 7, 8,
9,10...Pulp 11...Support for open substrate 12...Open substrate 15...Microwave oscillator
14...Curved microwave matching device 15...Microwave waveguide 16...Curved high frequency oscillator 17...High frequency induction coil Fig. 1 Fig. 3

Claims (6)

【特許請求の範囲】[Claims] （１）　炭化水素および水素ガスを低圧下でプラズマ化
しダイヤモンドを製造するに際し、該炭化水素に対し１
０−”％から５チの範囲で有機遷移金属化合物を共存さ
せることを特徴とするダイヤモンドの気相合成法。(1) When producing diamonds by turning hydrocarbons and hydrogen gas into plasma under low pressure,
A method for vapor phase synthesis of diamond characterized by coexisting an organic transition metal compound in a range of 0% to 5%. （２）有機遷移金属化合物の遷移金属がチタン、バナジ
ウム、クロム、マンガン、鉄、コバルト、ニッケル、ル
ビジウム、ロジウムまたはパラジウムである特許請求の
範囲第１項記載のダイヤモンドの気相合成法。(2) The method for vapor phase synthesis of diamond according to claim 1, wherein the transition metal of the organic transition metal compound is titanium, vanadium, chromium, manganese, iron, cobalt, nickel, rubidium, rhodium or palladium. （３）有機遷移金属化合物の遷移金属が鉄、コバルトま
たはニッケルである特許請求の範囲第１項記載のダイヤ
モンドの気相合成法。(3) The method for vapor phase synthesis of diamond according to claim 1, wherein the transition metal of the organic transition metal compound is iron, cobalt or nickel. （４）有機遷移金属化合物を該炭化水素に対し１０−４
％から１チ共存させる特許請求の範囲第１項記載のダイ
ヤモンドの気相合成法。(4) Adding an organic transition metal compound to the hydrocarbon at 10-4
The method for vapor phase synthesis of diamond according to claim 1, in which % to 1% of diamond coexists. （５）有機遷移金属化合物がシクロベンタジエらル遷移
金属化合物である特許請求の範囲第１項記載のダイヤモ
ンドの気相合成法。(5) The method for vapor phase synthesis of diamond according to claim 1, wherein the organic transition metal compound is a cyclobentadiene transition metal compound. （６）低圧下でプラズマ化するに際し、高周波プラズマ
またはマイクロ波プラズマによシプラズマ化する特許請
求の範囲第１項記載のダイヤモンドの気相合成法。(6) The method for vapor phase synthesis of diamond according to claim 1, in which plasma formation is performed under low pressure using high-frequency plasma or microwave plasma.
JP59066634A 1984-04-05 1984-04-05 Gas phase synthesizing method of diamond Pending JPS60210597A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59066634A JPS60210597A (en) 1984-04-05 1984-04-05 Gas phase synthesizing method of diamond

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59066634A JPS60210597A (en) 1984-04-05 1984-04-05 Gas phase synthesizing method of diamond

Publications (1)

Publication Number Publication Date
JPS60210597A true JPS60210597A (en) 1985-10-23

Family

ID=13321517

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59066634A Pending JPS60210597A (en) 1984-04-05 1984-04-05 Gas phase synthesizing method of diamond

Country Status (1)

Country Link
JP (1) JPS60210597A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63184304A (en) * 1986-09-26 1988-07-29 住友電気工業株式会社 Thermistor and manufacture of the same
JPH02217396A (en) * 1989-02-15 1990-08-30 Fujitsu Ltd Forming of diamond coating film
WO1995014553A1 (en) * 1993-11-23 1995-06-01 Plasmoteg Engineering Center An abrasive material for precision surface treatment and a method for the manufacturing thereof
US5478513A (en) * 1991-12-13 1995-12-26 General Electric Company CVD diamond growth on hydride-forming metal substrates
US5643343A (en) * 1993-11-23 1997-07-01 Selifanov; Oleg Vladimirovich Abrasive material for precision surface treatment and a method for the manufacturing thereof
US5711773A (en) * 1994-11-17 1998-01-27 Plasmoteg Engineering Center Abrasive material for precision surface treatment and a method for the manufacturing thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63184304A (en) * 1986-09-26 1988-07-29 住友電気工業株式会社 Thermistor and manufacture of the same
JPH02217396A (en) * 1989-02-15 1990-08-30 Fujitsu Ltd Forming of diamond coating film
US5478513A (en) * 1991-12-13 1995-12-26 General Electric Company CVD diamond growth on hydride-forming metal substrates
WO1995014553A1 (en) * 1993-11-23 1995-06-01 Plasmoteg Engineering Center An abrasive material for precision surface treatment and a method for the manufacturing thereof
US5643343A (en) * 1993-11-23 1997-07-01 Selifanov; Oleg Vladimirovich Abrasive material for precision surface treatment and a method for the manufacturing thereof
US5711773A (en) * 1994-11-17 1998-01-27 Plasmoteg Engineering Center Abrasive material for precision surface treatment and a method for the manufacturing thereof

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