JPS63310795A - Vapor phase synthesis method for diamond by microwave plasma jet - Google Patents
Vapor phase synthesis method for diamond by microwave plasma jetInfo
- Publication number
- JPS63310795A JPS63310795A JP14400687A JP14400687A JPS63310795A JP S63310795 A JPS63310795 A JP S63310795A JP 14400687 A JP14400687 A JP 14400687A JP 14400687 A JP14400687 A JP 14400687A JP S63310795 A JPS63310795 A JP S63310795A
- Authority
- JP
- Japan
- Prior art keywords
- plasma
- diamond
- microwave
- jet
- vapor phase
- 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
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 18
- 239000010432 diamond Substances 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title claims description 4
- 239000012808 vapor phase Substances 0.000 title abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 150000001722 carbon compounds Chemical class 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000009834 vaporization Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- 239000010453 quartz Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 4
- 230000005684 electric field Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔概 要〕
水素とガス状の炭素化合物とを含む原料ガスにマイクロ
波を集中させて、生成した化学的活性度の高い熱プラズ
マを基板に向けて噴出し、急冷させて基板上にダイヤモ
ンド薄膜を形成する。[Detailed Description of the Invention] [Summary] Microwaves are concentrated on a raw material gas containing hydrogen and a gaseous carbon compound, and the generated thermal plasma with high chemical activity is ejected toward the substrate to rapidly cool it. A diamond thin film is formed on the substrate.
本発明はダイヤモンドの気相合成方法に関し、特に、製
膜速度が高く、連続的にダイヤモンドを合成できる方法
に関する。The present invention relates to a method for vapor phase synthesis of diamond, and in particular to a method that has a high film forming rate and can synthesize diamond continuously.
良質の結晶質ダイヤモンドの気相合成法としては、熱フ
イラメント法（Ｓ、Ｍａｔｓｕｍｏｔｏ ｅｔ ａｌ、
：Ｊｐｎ。As a vapor phase synthesis method for high-quality crystalline diamond, the hot filament method (S, Matsumoto et al.
:Jpn.
Ｊ、＾ｐｐ１．Ｐｈｙｓ、２１（１９８１）Ｌ１８３）
、マイクロ波プラズマＣＶＤ法（Ｍ、Ｋａｍｏ ｅｔ
ａｌ、：Ｊ、Ｃｒｙｓｔ、Ｇｒｏｗｔｈ ６２（１９
８３） ６４２）、電子線照射ＣＶＤ法（Ａ、５ａｉｖ
ａｂｅ ｅｔａｌ、：Ａｐｐｌ、Ｐｈｙｓ、Ｌｅｔｔ、
４６（１９８５）１４６）等のＣＶＤ法が知られている
。J, ^pp1. Phys, 21 (1981) L183)
, microwave plasma CVD method (M, Kamo et al.
al, :J,Cryst, Growth 62(19
83) 642), electron beam irradiation CVD method (A, 5aiv
abe etal, :Appl, Phys, Lett,
46 (1985) 146) are known.
気相合成によって形成したダイヤモンド膜は、熱伝導率
、硬度、絶縁性、透光性、耐食性が優れているので、半
導体素子の高密度実装用の基板、各種工具の高硬度コー
テイング膜、光学部品等として使用することが、期待さ
れているが、上記いずれの製法によっても、製膜速度が
ｌｌＲｎ／ｈ以下と遅いので、コスト、生産性の上で問
題であった。Diamond films formed by vapor phase synthesis have excellent thermal conductivity, hardness, insulation, translucency, and corrosion resistance, so they can be used as substrates for high-density mounting of semiconductor devices, as hard coating films for various tools, and as optical components. However, since the film formation rate is slow at less than 11Rn/h by any of the above-mentioned manufacturing methods, there are problems in terms of cost and productivity.
本発明は、上記の問題点を解決し、製膜速度の高いダイ
ヤモンドの気相合成法を提供することを目的とする。An object of the present invention is to solve the above-mentioned problems and provide a method for vapor phase synthesis of diamond with a high film forming rate.
上記問題点は、マイクロ波を導波管（３）内の単電極（
８）に集中させるとともに、この単電極（８）に向けて
水素とガス状の炭素化合物とを含む原料ガスを導入し、
これによってマイクロ波のエネルギーを原料ガスに移行
させて、化学的活性度の高い熱プラズマを生成し、この
熱プラズマを真空中の基板に向けて噴出し、急冷させて
基板上にダイヤモンド薄膜を形成することを特徴とする
、マイクロ波プラズマジェットによるダイヤモンド気相
合成方法によって解決することができる。The problem mentioned above is that the microwave is transmitted to a single electrode in the waveguide (3) (
8), and introduce a raw material gas containing hydrogen and a gaseous carbon compound toward this single electrode (8),
This transfers microwave energy to the source gas to generate a highly chemically active thermal plasma, which is ejected towards the substrate in vacuum and rapidly cooled to form a diamond thin film on the substrate. This problem can be solved by a diamond vapor phase synthesis method using a microwave plasma jet, which is characterized by the following.
第１図に示すように、マグネトロン１から発生したマイ
クロ波は、矩型導波管２、同軸導波管３を通り、単電極
７を受信アンテナとし、電極先端部で極めて高い電界を
発生する。大気圧もしくは、それ以上の圧力で同軸円筒
石英管５の中を通った原料ガスは電極先端で活性度の高
い高温熱プラズマとなり、この際の急激な熱膨張により
、プラズマジェットＡとなり、ノズル８から噴出する。As shown in Figure 1, microwaves generated from a magnetron 1 pass through a rectangular waveguide 2 and a coaxial waveguide 3, and a single electrode 7 serves as a receiving antenna, generating an extremely high electric field at the tip of the electrode. . The raw material gas that passes through the coaxial cylindrical quartz tube 5 at atmospheric pressure or higher pressure becomes a highly active high-temperature thermal plasma at the tip of the electrode, and due to rapid thermal expansion at this time, it becomes a plasma jet A, and the nozzle 8 erupts from.
こうして、従来のＣＶＤ法で得られるよりも、活性度の
高いプラズマをプラズマジエッＩ−Ａとして得られる。In this way, a plasma with higher activity than that obtained by the conventional CVD method can be obtained as Plasma Jet I-A.
このプラズマジェットＡを、水冷された基板９に噴き当
てることにより、従来のＣＶＤに比べ格段に高い速度で
ダイヤモンドを気相合成させることができる。By spraying this plasma jet A onto the water-cooled substrate 9, diamond can be synthesized in a vapor phase at a much higher rate than conventional CVD.
原料ガスは、従来よりＣＶＤ法によるダイヤモンド合成
に用いられたもの、たとえば、Ｈ２−１％ＣＨ４を使用
できる。プラズマの安定度を高めるために、ＨｅやＡｒ
等の希ガスを加えても良い。As the raw material gas, those conventionally used in diamond synthesis by CVD method, such as H2-1% CH4, can be used. In order to increase the stability of the plasma, He and Ar
A rare gas such as may be added.
ただし、製膜速度は、希ガス混合によりいくぶん、低下
する。また、単電極７としては電子を放出しやすく、消
耗が少ないＴｈ０ｚ 、 ＬａｚＯｔ＋ＹｚＯｔ等を添
加したＷが好ましい。However, the film forming speed is somewhat reduced by the rare gas mixture. Further, as the single electrode 7, it is preferable to use W added with Th0z, LazOt+YzOt, etc., which easily emits electrons and consumes less.
２．４５ＧＨｚ 、２に−のマグネトロン１は、第１図
に示すように、断面９６ Ｘ ３７ ｍｍの導波管２お
よび同軸導波管３を介して真空チャンバ１１に接続され
ている。同軸導波管３と石英管４との内にある同軸石英
管５に、ガス導入管６から原料ガスを圧力２ｋｇ／ ａ
ｍ” 、流ＩＨｚ １０１！／ｍｉｎ ＸＣ８４０，５
ｆｆ／ｍｉｎで導入した。同軸石英管５の先端はノズル
８となって開口し、同軸石英管５内にはノズル８に近い
位置に単電極７があり、単電極７の先端で活性度の高い
高温度の熱プラズマシェアドＡを発生させた。真空チャ
ンバ１１内の圧力を２００Ｔｏｒｒとし、ノズル８から
４Ｏｎ離して、水冷基板ホルダＩＯ上に３０Ｘ３０鰭、
厚み０．５ ｕのＳｉウェハ９を置き、Ｓｉウェハ９の
温度が９００℃になるように、冷却水管１３からの水流
をコントロールし、１時間、ダイヤモンドの合成を行な
った。A 2.45 GHz, 2-min magnetron 1 is connected to a vacuum chamber 11 via a waveguide 2 and a coaxial waveguide 3 with a cross section of 96 x 37 mm, as shown in FIG. Source gas is supplied from the gas introduction tube 6 to the coaxial quartz tube 5 between the coaxial waveguide 3 and the quartz tube 4 at a pressure of 2 kg/a.
m”, current IHz 101!/min XC840,5
It was introduced at a rate of ff/min. The tip of the coaxial quartz tube 5 is opened as a nozzle 8, and inside the coaxial quartz tube 5 there is a single electrode 7 at a position close to the nozzle 8. A was generated. The pressure inside the vacuum chamber 11 was set to 200 Torr, and a 30×30 fin was placed on the water-cooled substrate holder IO, 4 On apart from the nozzle 8.
A Si wafer 9 having a thickness of 0.5 μm was placed, and the water flow from the cooling water pipe 13 was controlled so that the temperature of the Si wafer 9 was 900° C., and diamond synthesis was performed for 1 hour.
生成した膜は厚み３０Ｉｒｍの無色透明の膜で、Ｘ線回
折では、ダイヤモンドのピークのみが検出され、ラマン
分光では、ダイヤモンドのピークの他に、ブロードな非
晶質炭素によるピークもいくらか、検出された。The produced film was a colorless and transparent film with a thickness of 30 Irm, and in X-ray diffraction, only the diamond peak was detected, and in Raman spectroscopy, in addition to the diamond peak, some broad peaks due to amorphous carbon were also detected. Ta.
本発明のマイクロ波プラズマジェットを利用することに
より、気相合成ダイヤモンドの成膜速度を迅速化するこ
とができ、コストおよび生産性の向上を達成できる。By utilizing the microwave plasma jet of the present invention, it is possible to speed up the deposition rate of vapor-phase synthetic diamond, and it is possible to achieve improvements in cost and productivity.
第１図はマイクロ波プラズマジェット気相合成装置の説
明図である。
Ａ・・・プラズマジェット、
■・・・マグネトロン、 ２・・・導波管、３・・・
同軸導波管、 ４・・・石英管、５・・・同軸石英
管、 ６・・・ガス導入管、７・・・単電極、
８・・・ノズル、９・・・基板、
１０・・・基板ホルダ、１１・・・真空チャンバ、
１２・・・排気管、１３・・・冷却水管。FIG. 1 is an explanatory diagram of a microwave plasma jet vapor phase synthesis apparatus. A...Plasma jet, ■...Magnetron, 2...Waveguide, 3...
Coaxial waveguide, 4... Quartz tube, 5... Coaxial quartz tube, 6... Gas introduction tube, 7... Single electrode,
8... Nozzle, 9... Board,
10... Substrate holder, 11... Vacuum chamber,
12...Exhaust pipe, 13...Cooling water pipe.
Claims (1)
させるとともに、この単電極（８）に向けて、水素とガ
ス状の炭素化合物とを含む原料ガスを導入し、これによ
ってマイクロ波のエネルギーを原料ガスに移行させて、
化学的活性度の高い熱プラズマを生成し、この熱プラズ
マを真空中の基板に向けて噴出し、急冷させて基板上に
ダイヤモンド薄膜を形成することを特徴とする、マイク
ロ波プラズマジェットによるダイヤモンド気相合成方法
。 ２、炭素化合物がメタンである、特許請求の範囲第１項
記載の方法。 ３、原料ガスがさらに希ガスを含む、特許請求の範囲第
１または２項に記載の方法。[Claims] 1. The microwave is concentrated on a single electrode (8) in the waveguide (3), and a raw material containing hydrogen and a gaseous carbon compound is directed toward the single electrode (8). Introducing a gas, which transfers the microwave energy to the raw material gas,
Diamond vaporization using a microwave plasma jet is characterized by generating thermal plasma with high chemical activity, ejecting this thermal plasma toward a substrate in vacuum, and rapidly cooling it to form a diamond thin film on the substrate. Phase synthesis method. 2. The method according to claim 1, wherein the carbon compound is methane. 3. The method according to claim 1 or 2, wherein the raw material gas further contains a rare gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14400687A JPS63310795A (en) | 1987-06-11 | 1987-06-11 | Vapor phase synthesis method for diamond by microwave plasma jet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14400687A JPS63310795A (en) | 1987-06-11 | 1987-06-11 | Vapor phase synthesis method for diamond by microwave plasma jet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63310795A true JPS63310795A (en) | 1988-12-19 |
| JPH0449518B2 JPH0449518B2 (en) | 1992-08-11 |
Family
ID=15352119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14400687A Granted JPS63310795A (en) | 1987-06-11 | 1987-06-11 | Vapor phase synthesis method for diamond by microwave plasma jet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63310795A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126164A (en) * | 1988-06-06 | 1992-06-30 | Research Development Corporation Of Japan | Method of forming a thin polymeric film by plasma reaction under atmospheric pressure |
| US6593507B2 (en) | 1998-10-23 | 2003-07-15 | Mitsubishi Heavy Industries, Ltd. | Method of decomposing organic halide |
| JP2009533872A (en) * | 2006-04-14 | 2009-09-17 | シリカ テック リミテッド ライアビリティ カンパニー | Plasma deposition apparatus and method for manufacturing solar cells |
| GB2513439A (en) * | 2013-03-15 | 2014-10-29 | Agilent Technologies Inc | Integrated microwave source and plasma torch and related methods |
-
1987
- 1987-06-11 JP JP14400687A patent/JPS63310795A/en active Granted
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126164A (en) * | 1988-06-06 | 1992-06-30 | Research Development Corporation Of Japan | Method of forming a thin polymeric film by plasma reaction under atmospheric pressure |
| US6593507B2 (en) | 1998-10-23 | 2003-07-15 | Mitsubishi Heavy Industries, Ltd. | Method of decomposing organic halide |
| US6600084B2 (en) | 1998-10-23 | 2003-07-29 | Mitsubishi Heay Industries, Ltd. | Method of decomposing organic halide |
| US6635997B2 (en) | 1998-10-23 | 2003-10-21 | Mitsubishi Heavy Industries, Ltd. | Microwave plasma generator, method of decomposing organic halide, and system for decomposing organic halide |
| US6650059B2 (en) | 1998-10-23 | 2003-11-18 | Mitsubishi Heavy Industries, Ltd. | Method of decomposing organic halide |
| DE19982291C2 (en) * | 1998-10-23 | 2003-11-27 | Mitsubishi Heavy Ind Co | Microwave plasma generator and method of decomposing organic halides |
| JP2009533872A (en) * | 2006-04-14 | 2009-09-17 | シリカ テック リミテッド ライアビリティ カンパニー | Plasma deposition apparatus and method for manufacturing solar cells |
| GB2513439A (en) * | 2013-03-15 | 2014-10-29 | Agilent Technologies Inc | Integrated microwave source and plasma torch and related methods |
| US9427821B2 (en) | 2013-03-15 | 2016-08-30 | Agilent Technologies, Inc. | Integrated magnetron plasma torch, and related methods |
| GB2513439B (en) * | 2013-03-15 | 2019-02-06 | Agilent Technologies Inc | Integrated microwave source and plasma torch, and related methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0449518B2 (en) | 1992-08-11 |
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