JPH01246196A - Production of diamond film - Google Patents
Production of diamond filmInfo
- Publication number
- JPH01246196A JPH01246196A JP7387488A JP7387488A JPH01246196A JP H01246196 A JPH01246196 A JP H01246196A JP 7387488 A JP7387488 A JP 7387488A JP 7387488 A JP7387488 A JP 7387488A JP H01246196 A JPH01246196 A JP H01246196A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- substrate
- diamond film
- hydrogen
- film
- 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
- 239000010432 diamond Substances 0.000 title claims abstract description 53
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000758 substrate Substances 0.000 claims abstract description 25
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000005530 etching Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 11
- 239000012808 vapor phase Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、基板上に天然ダイヤモンドに近い色調のダイ
ヤモンド膜を形成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming a diamond film having a color similar to that of natural diamond on a substrate.
ダイヤモンドは硬度が高く、高絶縁性であって化学的に
安定しているので、工具などの他、最近ではＩＯ基板な
どエレクトロニクス材料としての用途も開発されつつあ
る。Diamond has high hardness, high insulating properties, and is chemically stable, so in addition to tools, diamond has recently been developed for use as an electronics material such as IO substrates.
これらの用途に用いる人工ダイヤモンドは超高圧装置を
用いて炭素から粒状のものが工業的に製造されるほか、
最近では炭化水素と水素から７００〜１２００ ｔ：”
に加熱した基板上にダイヤモンドの薄膜を合成被覆させ
る気相合成法が数多く提案されている。Artificial diamonds used for these purposes are manufactured industrially in granular form from carbon using ultra-high pressure equipment, and
Recently, 700 to 1200 tons from hydrocarbons and hydrogen:
Many vapor phase synthesis methods have been proposed in which a thin diamond film is synthetically coated on a heated substrate.
この気相からのダイヤモンド膜の製造方法としては、メ
タン等の炭化水素と水素の混合原料ガスを加熱した金属
フィラメントで予熱する方法（熱０’ＶＤ法：特願昭５
６−１８９４２３号公報参照）、上記の混合原料ガスを
マイクロ波無極放電により励起する方法（特願昭５６−
２０４３２１号公報参照）、及び高周波印加等により励
起した水素を炭化水素と混合する方法（特願昭５７−１
２９６６号公報参照）などがある。A method for producing a diamond film from the gas phase is a method in which a mixed raw material gas of hydrocarbons such as methane and hydrogen is preheated with a heated metal filament (thermal 0'VD method:
6-189423), a method of exciting the above mixed raw material gas by microwave non-polar discharge (Japanese Patent Application No. 1983-
204321), and a method of mixing hydrogen excited by high frequency application etc. with hydrocarbons (Japanese Patent Application No. 1987-1).
(See Publication No. 2966).
例えば、代表的な熱ＯＶＤ法では、炭化水素と水素の混
合原料゛ガスを２０００ Ｃ程度に加熱した金属フィラ
メント（−船釣にはタングステンフィラメント）で予熱
し、７００〜ｓｏｏ Ｃに加熱した基板上にダイヤモン
ドを薄膜状に析出させる。この方法で得られたダイヤモ
ンド膜は、電子線回折法、ｘＩｓ回折法、ラマン分光法
などにより、天然ダイヤモンドに極めて類似した結晶構
造であることが知られている。For example, in a typical thermal OVD method, a mixed raw material gas of hydrocarbon and hydrogen is preheated with a metal filament (tungsten filament for boat fishing) heated to about 2000 C, and then deposited on a substrate heated to 700 to soo C. diamond is deposited in a thin film. The diamond film obtained by this method is known to have a crystal structure extremely similar to natural diamond, as determined by electron beam diffraction, xIs diffraction, Raman spectroscopy, and the like.
上記の如く、熱ｃｖｐ法などの気相合成法により基板上
にダイヤモンド膜を形成することは可能となったが、か
かる従来の技術により得られたダイヤモンド膜はいずれ
も灰色ないし黒色を呈しており、天然ダイヤモンドの無
色透明とは程遠い色調であった。As mentioned above, it has become possible to form diamond films on substrates by vapor phase synthesis methods such as thermal CVP, but all diamond films obtained by such conventional techniques have a gray or black color. The color tone was far from the colorless transparency of natural diamonds.
本発明はこのような従来の事情に鑑み、基板上に天然ダ
イヤモンドにできるだけ近い色調のダイヤモンド膜を形
成することな目的とする。In view of these conventional circumstances, an object of the present invention is to form a diamond film on a substrate with a color tone as close to that of natural diamond as possible.
上記目的を達成するための手段として、本発明のダイヤ
モンド膜の製造方法は、炭化水素と水素の原料ガスより
基板上にダイヤモンド膜を合成被覆させた後、該ダイヤ
モンド被覆基板を５００Ｃ〜１９００ Ｃの温度に保持
しつつ原子状水素で処理することを特徴とするものであ
る。As a means for achieving the above object, the method for producing a diamond film of the present invention includes synthetically coating a diamond film on a substrate using raw material gases of hydrocarbon and hydrogen, and then heating the diamond coated substrate at 500C to 1900C. This method is characterized by treatment with atomic hydrogen while maintaining the temperature.
原子状水素の生成方法としては、減圧水素をタングステ
ン等の金属フィラメントで約２０００Ｃ以上に加熱する
方法、或いはグロー放電によりプラズマ化する方法など
が好ましい。As a method for producing atomic hydrogen, it is preferable to heat reduced-pressure hydrogen to about 2000 C or higher using a metal filament such as tungsten, or to turn it into plasma by glow discharge.
熱ＣＶＤ法などの気相合成法により基板上に形成したダ
イヤモンド膜が灰色ないし黒色を呈する理由については
、従来から種々の説があり、詳細は不明である。There have been various theories as to why a diamond film formed on a substrate by a vapor phase synthesis method such as a thermal CVD method exhibits a gray or black color, and the details are unknown.
しかし、本発明者等はこの理由についてダイヤモンド以
外の炭素が微量ながら析出しているためではないかと推
察し、このダイヤモンド以外の炭素を除去することを試
み、本発明を完成したものである。However, the present inventors surmised that the reason for this was that a small amount of carbon other than diamond was precipitated, and they attempted to remove this carbon other than diamond, and completed the present invention.
即ち、本発明方法では、熱ＣＶＤ法などの気相合成法に
より基板上に形成したダイヤモンド膜中に析出している
ダイヤモンド以外の炭素を、原子状水素でエツチングす
る。ダイヤモンドの炭素は原子状水素でエツチングされ
難いが、ダイヤモンド以外の炭素は加熱状態で原子状水
素によりエツチング除去され、灰色ないし黒色のダイヤ
モンド膜は白色に近い色に脱色される。That is, in the method of the present invention, carbon other than diamond deposited in a diamond film formed on a substrate by a vapor phase synthesis method such as a thermal CVD method is etched with atomic hydrogen. Carbon in diamond is difficult to be etched by atomic hydrogen, but carbon other than diamond is etched away by atomic hydrogen under heating, and the gray or black diamond film is bleached to a color close to white.
原子状水素で処理する際のダイヤモンド被覆基板の温度
は５００ Ｃ〜１９００ ｔｌ？とすべさであり、この
温度が５００Ｃ未満ではダイヤモンド膜の脱色効果が認
められず、又１９００ Ｃを超えるとダイヤモンドから
グラファイトへの変態が無視でき６くなるからである。The temperature of the diamond-coated substrate during treatment with atomic hydrogen is 500 C to 1900 tl? This is because if the temperature is less than 500C, no decolorizing effect of the diamond film is observed, and if it exceeds 1900C, the transformation from diamond to graphite can be ignored.
又、原子状水素での処理時間はダイヤモンド被覆基板の
温度、原子状水素の濃度、ダイヤモンド膜の膜厚などに
より適宜選択できる。しかし、通常の１〜２０μｍの膜
厚の場合、−船釣には５分〜５時間の処理時間が好まし
く、５分未満の処理時間ではダイヤモンド以外の炭素の
エツチングによる脱色効果が不充分であり、逆に５時間
を超えると、ダイヤモンドのエツチングが無視できなく
なるからである。Further, the treatment time with atomic hydrogen can be appropriately selected depending on the temperature of the diamond-coated substrate, the concentration of atomic hydrogen, the thickness of the diamond film, etc. However, in the case of a typical film thickness of 1 to 20 μm, a treatment time of 5 minutes to 5 hours is preferable for boat fishing, and a treatment time of less than 5 minutes will result in insufficient decolorization effect due to etching of carbon other than diamond. On the other hand, if the time exceeds 5 hours, the etching of the diamond cannot be ignored.
ダイヤモンド砥粒にて傷入れ処理した８１基板をＣＶＤ
装置内に配置し、８５０Ｃに加熱した。この装置内に８
１基板から１０１１１１離して設置したタングステンフ
ィラメントを２１０Ｏｒに加熱し、ＩＯＣ／ｍｉｎのメ
タンと９９ ｃｃ／ｍｉｎの水素を８０ ｔｏｒｒにて
供給し、Ｓｉ基板上にダイヤモンドを３時間析出させた
。CVD of 81 substrate scratched with diamond abrasive grains
It was placed in an apparatus and heated to 850C. 8 in this device
A tungsten filament placed 101111 apart from the substrate was heated to 210 Orr, methane at IOC/min and hydrogen at 99 cc/min were supplied at 80 torr, and diamond was deposited on the Si substrate for 3 hours.
得られたダイヤモンド膜は膜厚が約５μｍであって、ラ
マン分光法によりダイヤモンドの結晶構造を有すること
が認められたが、色調は灰色ないし黒色であった。The obtained diamond film had a thickness of about 5 μm, and was found to have a diamond crystal structure by Raman spectroscopy, but the color tone was gray to black.
この灰色ないし黒色のダイヤモンド膜で被覆された８１
基板を上記ＣＶＤ装置内に再び配置して、１０５０ Ｃ
に加熱した。この装置内に１００ ｏｃ／ｍｉｎの水素
を８０ ｔｏｒｒにて導入し、２１００Ｃに加熱したタ
ングステンフィラメントに接触させて原子状水素を発生
させ、この原子状水素の中でダイヤモンド膜を３０分間
処理した。処理後に装置から取出した基板上のダイヤモ
ンド膜は脱色され、はぼ白色を呈していた。81 coated with this gray or black diamond film
The substrate was placed back into the CVD apparatus and heated at 1050C.
heated to. Hydrogen was introduced into this apparatus at 100 oc/min at 80 torr and brought into contact with a tungsten filament heated to 2100C to generate atomic hydrogen, and the diamond film was treated in this atomic hydrogen for 30 minutes. The diamond film on the substrate taken out from the apparatus after treatment was decolored and had a pale white color.
本発明によれば、従来よりも遥かに天然ダイヤモンドに
近い色調のダイヤモンド膜を気相から基板上に形成する
ことができる。According to the present invention, a diamond film having a color tone much closer to that of natural diamond than ever before can be formed on a substrate from the vapor phase.
Claims (1)
ンド膜を合成被覆させた後、該ダイヤモンド被覆基板を
５００〜１９００℃の温度に保持しつつ原子状水素で処
理することを特徴とするダイヤモンド膜の製造方法。(1) A diamond film characterized by synthetically coating a diamond film on a substrate using raw material gases of hydrocarbon and hydrogen, and then treating the diamond-coated substrate with atomic hydrogen while maintaining the diamond-coated substrate at a temperature of 500 to 1900°C. Membrane manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073874A JP2584480B2 (en) | 1988-03-28 | 1988-03-28 | Diamond film manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073874A JP2584480B2 (en) | 1988-03-28 | 1988-03-28 | Diamond film manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01246196A true JPH01246196A (en) | 1989-10-02 |
| JP2584480B2 JP2584480B2 (en) | 1997-02-26 |
Family
ID=13530780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63073874A Expired - Fee Related JP2584480B2 (en) | 1988-03-28 | 1988-03-28 | Diamond film manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2584480B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022821A1 (en) * | 2002-09-06 | 2004-03-18 | Element Six Limited | Coloured diamond |
| CN100366802C (en) * | 2002-09-06 | 2008-02-06 | 六号元素有限公司 | Coloured diamond |
-
1988
- 1988-03-28 JP JP63073874A patent/JP2584480B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022821A1 (en) * | 2002-09-06 | 2004-03-18 | Element Six Limited | Coloured diamond |
| GB2409675A (en) * | 2002-09-06 | 2005-07-06 | Element Six Ltd | Coloured diamond |
| JP2005538018A (en) * | 2002-09-06 | 2005-12-15 | エレメント シックス リミテッド | Colored diamond |
| GB2409675B (en) * | 2002-09-06 | 2007-04-25 | Element Six Ltd | Modification of the colour of a single crystal CVD diamond |
| CN100366802C (en) * | 2002-09-06 | 2008-02-06 | 六号元素有限公司 | Coloured diamond |
| JP4711677B2 (en) * | 2002-09-06 | 2011-06-29 | エレメント シックス リミテッド | Colored diamond |
| EP2253746A3 (en) * | 2002-09-06 | 2013-10-02 | Element Six Limited | Coloured diamond |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2584480B2 (en) | 1997-02-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |