JPS60118693A - Method for synthesizing diamond under low pressure - Google Patents
Method for synthesizing diamond under low pressureInfo
- Publication number
- JPS60118693A JPS60118693A JP58221808A JP22180883A JPS60118693A JP S60118693 A JPS60118693 A JP S60118693A JP 58221808 A JP58221808 A JP 58221808A JP 22180883 A JP22180883 A JP 22180883A JP S60118693 A JPS60118693 A JP S60118693A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- mixed gas
- arc discharge
- pressure
- diamond
- 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
Links
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
Description
【発明の詳細な説明】
本発明はダイヤモンドの低圧合成方法の改良に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in a low pressure synthesis method for diamond.
ダイヤモンドを超高圧を用いずに合成する方法の開発が
盛んに行われ、その１つの方法として低圧ＣＶｒｌ法が
発明された。この方法は３００℃〜１，１００℃に加熱
した基体上に圧力０．１〜１００’１．”ｏｒｒのｌｌ
２−Ｃχｌ−１ｙ混合ガスを活性化状態で導入すること
によって基体上にダイヤモンド構造を有する薄膜を成長
させるものである。また、同一方法で１０μ以下のダイ
ヤモンド粒子を合成することも可能となっている。Many efforts have been made to develop methods for synthesizing diamond without using ultra-high pressure, and the low-pressure CVrl method was invented as one of these methods. This method uses a substrate heated to 300°C to 1,100°C and a pressure of 0.1 to 100'1. ”orr no ll
A thin film having a diamond structure is grown on a substrate by introducing a 2-Cxl-1y mixed gas in an activated state. Furthermore, it is also possible to synthesize diamond particles of 10 μm or less using the same method.
上記の方法を工業化するには、しかＩ２多くθつ問題を
解決しなければならない。そθ−）１つの問題は混合ガ
スを活性化状態にする方法σ）開発ＶＣある。従来、３
通りの方法が知られて（・る力１、それぞれ利点と問題
点がある。すなわち、第１の方法は熱電子放射法と呼ば
れるもので、混合ガスを、赤熱した熱電子放射性のフィ
ラメントの近傍を通過させることＫＪ、って活性化状態
にするものである。この方法は基体σ）種類を選（了す
適用でき、装置的に単純であって大型化することも困難
ではなし・と言えるが、現在知らＪｔているタングステ
ンフィラメントを熱電子放射材として用いる限りにお、
いて、タングステンカニ混合ガスと反応して炭化物を形
成するために、その寿命が非常に短かく、この解決が必
要であ２）。To industrialize the above method, only I2 and θ problems must be solved. θ-) One problem is how to bring the mixed gas into an activated state σ) Development VC. Conventionally, 3
There are two known methods, each with its own advantages and problems.The first method is called the thermionic emission method, in which a mixed gas is placed in the vicinity of a red-hot thermionic filament. By passing KJ, the activated state is obtained.This method can be applied to any type of substrate σ, and it can be said that it is simple in terms of equipment and can be scaled up without difficulty. However, as long as the currently known Jt tungsten filament is used as a thermionic emitting material,
However, since the tungsten crab reacts with the mixed gas to form carbide, its lifespan is very short, and a solution to this problem is needed 2).
第２の方法は高周波プラズマ法と呼ｋｉ２するものて、
外部より高周波電圧をガスの導入部に加え、水素主体の
プラズマを発生させて混合ガスを活性化状態に導び（も
のである。この方法は１１ｆ現性如すぐれ、消耗部品が
ない利点はあるが、プラズマ空間と基体の位置の関係に
おいて汎用性にとぼしく、また条件的には高真空側のみ
に限定される問題を有している。The second method is called the high frequency plasma method.
A high-frequency voltage is applied from the outside to the gas introduction part to generate hydrogen-based plasma and lead the mixed gas to an activated state. However, there are problems in that the versatility is limited due to the relationship between the plasma space and the position of the substrate, and the conditions are limited only to the high vacuum side.
第３の方法はマイクロ波法と呼ばれるもので、外部で発
信したマイクロ波を導入管を通して、反応管のガス導入
部へ導入し、そこでマイクロ波によるプラズマを形成し
、混合ガスを活性化状態にするものである。この方法は
活性化状態の再現性がよく、消耗部品がない利点はある
が金属性基体への適用がむつかしく、また大型化にあた
っては、プラズマ空間と基体との位置の関係において汎
用性に劣るという問題を有している。The third method is called the microwave method, in which externally transmitted microwaves are introduced into the gas introduction part of the reaction tube through the introduction tube, where the microwaves form a plasma and activate the mixed gas. It is something to do. Although this method has the advantage of good reproducibility of the activation state and no consumable parts, it is difficult to apply to metallic substrates, and when increasing in size, it is less versatile due to the relationship between the plasma space and the substrate. I have a problem.
」二記３通りの方法はそれぞれ問題を有しながら装置の
改良努力がなされているが、本発明はこれらとまったく
異なった混合ガスの活性化方法を提供し、ダイヤモンド
の低圧合成を工業化へ導び（ものである。Efforts have been made to improve the equipment for the three methods, each of which has its own problems, but the present invention provides a method for activating a mixed gas that is completely different from these methods, and will lead to the industrialization of low-pressure diamond synthesis. It is a thing.
すなわち、本発明は基体を３００℃〜１１００℃に加熱
し、圧力０．１−１００ＴｏｒｒのＩＴ２− ｃχｔｒ
ｙ主体の混合ガスを活性化状態として、ダイヤモンドヲ
基体上に低圧合成する方法であって、混合ガスを連続的
または間けり的に（たとえば毎秒１〜１００サイクル）
アーク放電する空間を通すことによって活性化状態とす
るものである。That is, in the present invention, the substrate is heated to 300°C to 1100°C, and IT2-cχtr is heated at a pressure of 0.1 to 100 Torr.
A method of low-pressure synthesis on a diamond substrate by activating a mixed gas mainly consisting of
It is activated by passing it through a space where arc discharge occurs.
本発明方法の長所の一つは、アーク放電を制御すイ）こ
とによって活性化に必要なエネルギーを制御できること
である。また、電極は若干消耗はするが、熱電子放射フ
ィラメントと比較して、はるかに長寿命で安定した条件
を再現できること、基体との位置関係を自由にかえられ
る汎用性を有すること、基体から制限を受けないことな
ども本方法による長所である。One of the advantages of the method of the invention is that by controlling the arc discharge, the energy required for activation can be controlled. In addition, although the electrode wears out slightly, compared to a thermionic emission filament, it has a much longer life and can reproduce stable conditions, has the versatility of being able to freely change the positional relationship with the substrate, and is limited by the substrate. Another advantage of this method is that it is not subject to
アーク放電に必要な電圧は電極間距離、電極材質、電極
形状およびガス組成に依存するが、ＩＫＶ〜ｌ０ＫＶの
程度がよい。The voltage required for arc discharge depends on the distance between the electrodes, electrode material, electrode shape, and gas composition, but is preferably in the range of IKV to 10KV.
、アーク放電は直流電源、交流電源のいずれでも可能で
ある。アーク放電はまた連続的であっても間けり的であ
ってもよく、また電極は１対以上、多数対を用いること
ができる。装置の概略を図−１に示す。ここで■は反応
容器、■は混合ガス導入管、■はアーク放電の電極、■
は基体、■は基体の支持台、■はアーク用電源、■は基
体加熱用ヒーター、■は圧力調整バルブ、（ｊ）は真空
ポンプである。, arc discharge is possible with either a DC power source or an AC power source. The arc discharge may be continuous or intermittent, and one or more pairs of electrodes or multiple pairs of electrodes may be used. A schematic diagram of the device is shown in Figure 1. Here, ■ is the reaction vessel, ■ is the mixed gas introduction tube, ■ is the arc discharge electrode, and ■
2 is a base, 2 is a support for the base, 2 is an arc power source, 2 is a heater for heating the base, 2 is a pressure adjustment valve, and (j) is a vacuum pump.
基体温度は３００℃〜１，１００℃がＪ：＜、これより
高い温度でも、低い温度でもダイヤモンドは合成されな
い。圧力はＯ，ＩＴｏ ｒ ｒ 〜Ｉ ００ Ｔ’ｏ
ｒ ｒが」：＜、この上限あるいは下限をはずれるとダ
イヤモンドの合成は困難である。The substrate temperature is J:< 300°C to 1,100°C, and diamond is not synthesized at temperatures higher or lower than this. The pressure is O, ITo r r ~ I 00 T'o
When r r is outside this upper or lower limit, it is difficult to synthesize diamond.
ガス成分は水素を主体とし、炭化水素ＣχｒＴｙは揮発
性であれば種々用いることができるが、メタンを用いる
と効率がよい。また、水素と炭化水素の他に不活性ガス
を混合してもよく、あるいはダイヤモンド核の形成を促
進する第３の反応ガスを用いてもよい。ＡｌＣｌ３ある
いはＴｉＣｌ４ガスを少量混合するとダイヤモンド核の
生成がより容易になる。The gas component is mainly hydrogen, and various hydrocarbons CχrTy can be used as long as they are volatile, but methane is more efficient. Furthermore, in addition to hydrogen and hydrocarbons, an inert gas may be mixed, or a third reactive gas that promotes the formation of diamond nuclei may be used. When a small amount of AlCl3 or TiCl4 gas is mixed, diamond nuclei can be generated more easily.
実施例−１
図−１の構造をした装置において、基体加熱温度７００
℃、圧力５ Ｔｏ ｒ ｒとし、ＩＩ２ ；９５ ％、
ＣＬＩ、；５％の混合ガスを流しながら、アーク電極間
に２．５ＫＶの直流を毎秒１０ザイクルの割合で流し、
アーク放電を行わせた。基体のタングステン上には２０
分間の反応でダイヤモンドの膜が形成され、４時間の反
応で３μｍのダイヤモンド膜が成長した。Example 1 In the apparatus having the structure shown in Figure 1, the substrate heating temperature was 700.
℃, pressure 5 Torr, II2; 95%,
CLI; While flowing a 5% mixed gas, a 2.5 KV direct current was passed between the arc electrodes at a rate of 10 cycles per second.
Arc discharge was caused. 20 on the tungsten base
A diamond film was formed after a minute's reaction, and a 3 μm diamond film was grown after a 4-hour reaction.
実施例−２
図−１の構造をした装置において、基本加熱温度７５０
℃、圧力４Ｔｏｒｒとし、ＩＮ２；９６％、Ｃ１ｌ、
ｉ ３．９％、Ｔ、 ｒ ＣＩ４ ； （１１％の混合
ガスを流しながら、電極間に２ＫＶＯ高電圧を半波整流
（５０サイクル）でかけ、電極間にアーク放電を行わせ
た。基体の超硬合金ｌ５ＯＫ−ＩＱの表面に１０分間で
ダイヤモンド構造物質の合成ができることが電子線回折
で確認され、さらに反応時間を２時間とすると厚み２μ
７ｎのダイヤモンド膜が合成できた。Example-2 In the device having the structure shown in Figure-1, the basic heating temperature is 750.
℃, pressure 4 Torr, IN2; 96%, C1l,
i 3.9%, T, r CI4; (While flowing a 11% mixed gas, a 2KVO high voltage was applied between the electrodes with half-wave rectification (50 cycles) to cause arc discharge between the electrodes. It was confirmed by electron diffraction that a diamond structure material could be synthesized on the surface of hard alloy l5OK-IQ in 10 minutes, and if the reaction time was increased to 2 hours, a diamond structure material with a thickness of 2 μm could be synthesized on the surface of the hard alloy l5OK-IQ.
A 7n diamond film was synthesized.
第１図は本発明の方法を実施するための装置の一例の模
式図である。図中、■は反応容器、■は混合ガス導入管
、■はアーク放電電極、■は基体、■は基体の支持台、
（９はアーク用電渕ミ、■は基体加熱用ヒーター、■は
圧力調整バルブ、■は真空ポンプである。FIG. 1 is a schematic diagram of an example of an apparatus for carrying out the method of the present invention. In the figure, ■ is a reaction vessel, ■ is a mixed gas introduction tube, ■ is an arc discharge electrode, ■ is a substrate, ■ is a support for the substrate,
(9 is an arc electric wire, 2 is a heater for heating the substrate, 2 is a pressure adjustment valve, and 2 is a vacuum pump.
Claims (1)
〜１００ ’Ｔ’、ｏｒｒのＩ Ｉ２−Ｃｙ、Ｈｙ主体
の混合ガスを活性化状態として、ダイヤモンドを基体上
に低圧合成する方法であって、混合ガスを連続的または
間けり的にアーク放電する空間を通すことによって活性
化状態とすることを特徴とするダイヤモンドの低圧合成
方法。1) Heat the substrate at 300°C to 1. Heat to too °C and pressure 01
A method of low-pressure synthesis of diamond on a substrate by activating a mixed gas of ~100'T', orr mainly consisting of II2-Cy and Hy, in which the mixed gas is continuously or intermittently arc-discharged. A low-pressure method for synthesizing diamond, which is characterized by bringing it into an activated state by passing it through a space.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58221808A JPS60118693A (en) | 1983-11-25 | 1983-11-25 | Method for synthesizing diamond under low pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58221808A JPS60118693A (en) | 1983-11-25 | 1983-11-25 | Method for synthesizing diamond under low pressure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60118693A true JPS60118693A (en) | 1985-06-26 |
Family
ID=16772518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58221808A Pending JPS60118693A (en) | 1983-11-25 | 1983-11-25 | Method for synthesizing diamond under low pressure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60118693A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003307A1 (en) * | 1985-11-25 | 1987-06-04 | Showa Denko Kabushiki Kaisha | Process for synthesizing diamond |
| JPS6385094A (en) * | 1986-09-26 | 1988-04-15 | Imai Yoshio | Production of diamond film |
| JPS63176399A (en) * | 1987-01-13 | 1988-07-20 | Nippon Soken Inc | Production of diamond film |
| JPS6433096A (en) * | 1987-04-03 | 1989-02-02 | Fujitsu Ltd | Gaseous phase synthesis for diamond |
| US4915977A (en) * | 1987-02-26 | 1990-04-10 | Nissin Electric Co., Ltd. | Method of forming a diamond film |
| US5368897A (en) * | 1987-04-03 | 1994-11-29 | Fujitsu Limited | Method for arc discharge plasma vapor deposition of diamond |
| US5616373A (en) * | 1990-09-14 | 1997-04-01 | Balzers Aktiengesellschaft | Plasma CVD method for producing a diamond coating |
| CN113818004A (en) * | 2021-09-22 | 2021-12-21 | 吉林大学 | Diamond growth device and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59174507A (en) * | 1983-03-18 | 1984-10-03 | Yoshitoshi Nanba | Manufacture of superhard carbon membrane and its apparatus |
-
1983
- 1983-11-25 JP JP58221808A patent/JPS60118693A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59174507A (en) * | 1983-03-18 | 1984-10-03 | Yoshitoshi Nanba | Manufacture of superhard carbon membrane and its apparatus |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003307A1 (en) * | 1985-11-25 | 1987-06-04 | Showa Denko Kabushiki Kaisha | Process for synthesizing diamond |
| JPS6385094A (en) * | 1986-09-26 | 1988-04-15 | Imai Yoshio | Production of diamond film |
| JPS63176399A (en) * | 1987-01-13 | 1988-07-20 | Nippon Soken Inc | Production of diamond film |
| JPH0569800B2 (en) * | 1987-01-13 | 1993-10-01 | Nippon Soken | |
| US4915977A (en) * | 1987-02-26 | 1990-04-10 | Nissin Electric Co., Ltd. | Method of forming a diamond film |
| JPS6433096A (en) * | 1987-04-03 | 1989-02-02 | Fujitsu Ltd | Gaseous phase synthesis for diamond |
| JPH0477710B2 (en) * | 1987-04-03 | 1992-12-09 | Fujitsu Ltd | |
| US5368897A (en) * | 1987-04-03 | 1994-11-29 | Fujitsu Limited | Method for arc discharge plasma vapor deposition of diamond |
| US5403399A (en) * | 1987-04-03 | 1995-04-04 | Fujitsu Limited | Method and apparatus for vapor deposition of diamond |
| US5616373A (en) * | 1990-09-14 | 1997-04-01 | Balzers Aktiengesellschaft | Plasma CVD method for producing a diamond coating |
| CN113818004A (en) * | 2021-09-22 | 2021-12-21 | 吉林大学 | Diamond growth device and method |
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