JP2584480B2 - Diamond film manufacturing method - Google Patents

Diamond film manufacturing method

Info

Publication number
JP2584480B2
JP2584480B2 JP63073874A JP7387488A JP2584480B2 JP 2584480 B2 JP2584480 B2 JP 2584480B2 JP 63073874 A JP63073874 A JP 63073874A JP 7387488 A JP7387488 A JP 7387488A JP 2584480 B2 JP2584480 B2 JP 2584480B2
Authority
JP
Japan
Prior art keywords
diamond
diamond film
substrate
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.)
Expired - Fee Related
Application number
JP63073874A
Other languages
Japanese (ja)
Other versions
JPH01246196A (en
Inventor
正明 飛岡
明彦 池ケ谷
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.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries Ltd
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 Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to JP63073874A priority Critical patent/JP2584480B2/en
Publication of JPH01246196A publication Critical patent/JPH01246196A/en
Application granted granted Critical
Publication of JP2584480B2 publication Critical patent/JP2584480B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)

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。
Description: TECHNICAL FIELD The present invention relates to a method for forming a diamond film having a color tone close to natural diamond on a substrate.

〔従来の技術〕[Conventional technology]

ダイヤモンドは硬度が高く、高絶縁性であつて化学的
に安定しているので、工具などの他、最近ではIC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。
Since diamond has high hardness, is highly insulating, and is chemically stable, it has recently been developed for use as an electronic material such as an IC substrate in addition to tools.

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℃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 applications are manufactured industrially from carbon using ultra-high pressure equipment, and recently, a thin film of diamond is synthesized from hydrocarbons and hydrogen on a substrate heated to 700 to 1200 ° C. Many vapor-phase synthesis methods for coating have been proposed.

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
属フイラメントで予熱する方法(熱CVD法:特願昭56−1
89423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57−12966号公報参照)など
がある。
As a method for producing a diamond film from this gas phase,
Preheating a mixed raw material gas of hydrocarbons such as methane and hydrogen with heated metal filament (thermal CVD method: Japanese Patent Application No. 56-1)
No. 89423), a method of exciting the above mixed material gas by microwave non-polar discharge (see Japanese Patent Application No. 56-204321), and a method of mixing hydrogen excited by high frequency application with hydrocarbons (Japanese Patent Application No. Reference is made to JP-A-57-12966).

例えば、代表的な熱CVD法では、炭化水素と水素の混
合原料ガスを2000℃程度に加熱した金属フイラメント
(一般的にはタングステンフイラメント)で予熱し、70
0〜800℃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、X線回折法、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 CVD method, a mixed raw material gas of hydrocarbon and hydrogen is preheated with a metal filament (generally, a tungsten filament) heated to about 2000 ° C.
Diamond is deposited as a thin film on a substrate heated to 0 to 800 ° C. It is known that a diamond film obtained by this method has a crystal structure very similar to natural diamond by electron diffraction, X-ray diffraction, Raman spectroscopy, or the like.

〔発明が解決しようとする課題〕[Problems to be solved by the invention]

上記の如く、熱CVD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つたが、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つた。
As described above, it has become possible to form a diamond film on a substrate by a vapor phase synthesis method such as a thermal CVD method, but any diamond film obtained by such a conventional technique has a gray or black color. The color tone was far from the colorless and transparent of natural diamond.

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
形成することを目的とする。
The present invention has been made in view of such conventional circumstances, and has as its object to form a diamond film having a color tone as close as possible to natural diamond on a substrate.

〔課題を解決するための手段〕[Means for solving the problem]

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ものである。
As a means for achieving the above object, the method for producing a diamond film of the present invention comprises the steps of: synthesizing a diamond film on a substrate from a raw material gas of hydrocarbon and hydrogen; And treating 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
テン等の金属フイラメントで約2000℃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 generating atomic hydrogen, a method in which reduced-pressure hydrogen is heated to about 2000 ° C. or higher with a metal filament such as tungsten, or a method in which plasma is generated by glow discharge is preferable.

〔作用〕[Action]

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 the reason why the diamond film formed on the substrate by a vapor phase synthesis method such as a thermal CVD method has 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 presumed that the reason for this was that a small amount of carbon other than diamond was precipitated, and tried to remove the carbon other than diamond to complete 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. Although carbon of diamond is hardly etched by atomic hydrogen, carbon other than diamond is etched and removed by atomic hydrogen in a heated state, and the gray or black diamond film is decolorized 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℃〜1900℃とすべきであり、この温度が500℃未
満ではダイヤモンド膜の脱色効果が認められず、又1900
℃を超えるとダイヤモンドからグラフアイトへの変態が
無視できなくなるからである。
The temperature of the diamond-coated substrate during treatment with atomic hydrogen should be 500 ° C. to 1900 ° C. If the temperature is less than 500 ° C., no decolorizing effect of the diamond film is observed, and 1900 ° C.
If the temperature exceeds ℃, the transformation from diamond to graphite cannot 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、一般的には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。
The processing 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, and the like. However, in the case of a usual film thickness of 1 to 20 μm, generally, a treatment time of 5 minutes to 5 hours is preferable, and a treatment time of less than 5 minutes is insufficient for the decolorizing effect by etching of carbon other than diamond, Conversely, if the time exceeds 5 hours, the etching of the diamond cannot be ignored.

〔実施例〕〔Example〕

ダイヤモンド砥粒にて傷入れ処理したSi基板をCVD装
置内に配置し、850℃に加熱した。この装置内にSi基板
から10mm離して設置したタングステンフイラメントを21
00℃に加熱し、1cc/minのメタンと99cc/minの水素を80t
orr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。
The Si substrate scratched with diamond abrasive was placed in a CVD apparatus and heated to 850 ° C. In this device, tungsten filament placed 10 mm away from the Si substrate
Heated to 00 ° C, 80t of 1cc / min methane and 99cc / min hydrogen
It was supplied by orr, 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であつて、
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つた。
The obtained diamond film has a thickness of about 5 μm,
Raman spectroscopy confirmed that it had a diamond crystal structure, but the color 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Si
基板を上記CVD装置内に再び配置して、1050℃に加熱し
た。この装置内に100cc/minの水素を80torrにて導入
し、2100℃に加熱したタングステンフイラメントに接触
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、ほぼ白色を呈
していた。
Si coated with this gray or black diamond film
The substrate was placed again in the CVD apparatus and heated to 1050 ° C. Hydrogen of 100 cc / min was introduced into the apparatus at 80 torr, and was brought into contact with a tungsten filament heated to 2100 ° C. to generate atomic hydrogen, and a diamond film was treated in the atomic hydrogen for 30 minutes. The diamond film on the substrate removed from the apparatus after the treatment was decolorized and exhibited almost white.

〔発明の効果〕〔The invention's effect〕

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 natural diamond than before can be formed on a substrate from a gas phase.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】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。
The present invention is characterized in that after a diamond film is synthetically coated on a substrate from a raw material gas of hydrocarbon and hydrogen, the diamond-coated substrate is treated with atomic hydrogen while maintaining the temperature at 500 to 1900 ° C. Method for producing a diamond film.
JP63073874A 1988-03-28 1988-03-28 Diamond film manufacturing method Expired - Fee Related JP2584480B2 (en)

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 JPH01246196A (en) 1989-10-02
JP2584480B2 true 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)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4711677B2 (en) * 2002-09-06 2011-06-29 エレメント シックス リミテッド Colored diamond
GB0220772D0 (en) * 2002-09-06 2002-10-16 Diamanx Products Ltd Coloured diamond

Also Published As

Publication number Publication date
JPH01246196A (en) 1989-10-02

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