JPH03166378A - Diamond synthesizing method - Google Patents
Diamond synthesizing methodInfo
- Publication number
- JPH03166378A JPH03166378A JP1305055A JP30505589A JPH03166378A JP H03166378 A JPH03166378 A JP H03166378A JP 1305055 A JP1305055 A JP 1305055A JP 30505589 A JP30505589 A JP 30505589A JP H03166378 A JPH03166378 A JP H03166378A
- Authority
- JP
- Japan
- Prior art keywords
- cathode
- mesh
- diamond
- pitch
- shape
- 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
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 19
- 239000010432 diamond Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 title 1
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 11
- 238000001308 synthesis method Methods 0.000 claims description 5
- 239000012808 vapor phase Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000007704 transition Effects 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】
〈産業上の利用分野〉
この発明は、ダイヤモンドの気相合成方法に関するもの
であり、詳しくは陰極としてメッシュを用いることによ
り、長時間安定に放電を維持でき、低温かつ大面積にダ
イヤモンドを形成できる合成方法に関するものである。[Detailed Description of the Invention] <Industrial Application Field> This invention relates to a method for vapor phase synthesis of diamond. Specifically, by using a mesh as a cathode, a stable discharge can be maintained for a long time, and it can be used at low temperatures and This invention relates to a synthesis method that allows diamond to be formed over a large area.
〈従来の技術〉
ダイヤモンドは、高硬度、耐摩耗性を有し、圧縮率・熱
膨張率が小さく、かつ絶縁体でありながら熱伝導度が非
常に高い。また、屈折率が高く、光学的（紫外・可視・
赤外）に透明、耐薬品性などという優れた特性をも同時
に備えた物質である。また、音波の伝播速度に優れ、さ
らに、特定の不純物をドーブすることにより半導体特性
を与えることができる。このため各種分野での応用が考
えられており、産業界に於て必要不可欠な物質となって
いる。<Prior Art> Diamond has high hardness and wear resistance, low compressibility and low coefficient of thermal expansion, and although it is an insulator, it has extremely high thermal conductivity. In addition, it has a high refractive index and optical (ultraviolet, visible,
It is a material that also has excellent properties such as transparency to infrared (infrared) and chemical resistance. It also has excellent sound wave propagation speed, and can be given semiconductor properties by doping with specific impurities. For this reason, it has been considered for application in various fields, and has become an indispensable substance in industry.
周知の通り、マイクロ波ＣＶＤ法あるいは熱フィラメン
トＣＶＤ法をはじめとする各種のＣＶＤ法により、気相
からのダイヤモンド合成が実現されており、ダイヤモン
ドの持つ優れた特性を膜状にして、あるいは他の材料表
面に被覆して利用できるようになり、その応用範囲が更
に拡大されつつある。これら多くの気相合成法の中で直
流放電を利用したダイヤモンド合成も既に開発されてお
り、グイ・ヤモンドの高速合成が可能な一手法であるこ
とが知られている。As is well known, diamond synthesis from the gas phase has been achieved using various CVD methods, including microwave CVD and hot filament CVD. It can now be used by coating the surface of materials, and its range of applications is expanding further. Among these many vapor phase synthesis methods, diamond synthesis using direct current discharge has already been developed, and is known to be a method capable of high-speed synthesis of Gouy Yamond.
〈発明が解決しようとする課題〉
しかしながら、従来の直流放電を利用したダイヤモンド
合成は、比較的圧力の高い条件（１００ Ｔｏｒｒ以上
）での放電を利用したものであり、ガス温度が比較的高
く、大幅な低温化は難しいと考えられる。また、異常グ
ローないしはグロー・アーク移行領域での放電であるこ
とから、プラズマを安定に長時間維持すること、さらに
は、放電領域の拡大も非常に困難である。加えて、３次
元形状を有する基体への被覆も難しい。<Problems to be Solved by the Invention> However, conventional diamond synthesis using direct current discharge utilizes discharge under relatively high pressure conditions (100 Torr or more), and the gas temperature is relatively high. It is considered difficult to significantly lower the temperature. Furthermore, since the discharge occurs in the abnormal glow or glow-arc transition region, it is extremely difficult to maintain the plasma stably for a long time and furthermore to expand the discharge region. In addition, it is difficult to coat a substrate having a three-dimensional shape.
この発明は、直流放電を長時間安定に維持でき、しかも
、ダイヤモンド合成に於ける低温化、大面積化が容易で
、さらには３次元形状を有する基体上への被覆が可能な
合成方法を提供することを目的とするものである。The present invention provides a synthesis method that can maintain stable DC discharge for a long time, can easily reduce the temperature and increase the area of diamond synthesis, and can coat a substrate having a three-dimensional shape. The purpose is to
〈課題を解決するための手段〉
この発明は上記のような課題を解消すべく鋭意検討した
結果、陰極にメッシュを用いることにより解消しうるこ
とを見出し、この発明に至ったものである。<Means for Solving the Problems> As a result of intensive studies to solve the above-mentioned problems, it was discovered that the problems could be solved by using a mesh for the cathode, and this invention was achieved.
即ち、この発明はダイヤモンド気相合成用原料ガスを直
流放電によりプラズマ化し、基体上にダイヤモンドを析
出させる方法に於て、陰極としてＭｏ、Ｗ，Ｔａから選
ばれた少なくとも１種あるいは複数の材質で構成された
線径０． ５ｍｍ以下、ピッチ３ｍｍ以下のメッシュを
用いることを特徴とするダイヤモンド合成方法を提供す
るものである。That is, the present invention provides a method for converting raw material gas for diamond vapor phase synthesis into plasma by direct current discharge and depositing diamond on a substrate, in which the cathode is made of at least one or more materials selected from Mo, W, and Ta. Constructed wire diameter 0. The present invention provides a diamond synthesis method characterized by using a mesh having a mesh size of 5 mm or less and a pitch of 3 mm or less.
く作用〉
以下、この発明を図面を参照しつつ詳細に説明すると、
直流放電を行なう際に、陰極にメッシュを用いることに
より電子の放射率が向上し、高密度なプラズマを極めて
安定に長時間維持することができる。加えて、初期の放
電の点火も容易に行なえる。また、グロー放電を利用し
ているため基体の温度は水冷することなく低温に保持で
きる。Function> This invention will be described in detail below with reference to the drawings.
When performing DC discharge, by using a mesh for the cathode, the emissivity of electrons is improved, and high-density plasma can be maintained extremely stably for a long time. In addition, the initial discharge can be easily ignited. Furthermore, since glow discharge is used, the temperature of the substrate can be maintained at a low temperature without water cooling.
この際用いられるメッシュは線径０． ５ｍｍ以下、ピ
ッチ３ｍｍ以下が望ましく、これ以上のものを使用した
場合には放電が不安定となる。これは、電子の放射率の
向上に対する効果が該メッシュ寸法内に存在するためで
ある。The mesh used at this time has a wire diameter of 0. Desirably, the pitch is 5 mm or less and the pitch is 3 mm or less; if larger than this, the discharge becomes unstable. This is because the effect on improving the electron emissivity exists within the mesh size.
陰極としてのメッシュは、その形状を工夫することによ
り、例えば第１図に示すように多数のフィンを備え付け
た形状の陰極とすることによりその表面積が増加し、更
に効率よく電子の放射がなされ、基体上でより高密度な
プラズマを発生させることができる。By devising the shape of the mesh as a cathode, for example, by creating a cathode with a large number of fins as shown in Figure 1, its surface area can be increased and electrons can be emitted more efficiently. Higher density plasma can be generated on the substrate.
また、この発明の方法では電子の放射効率のよいメッシ
ュを陰極電極として用いているため陰極の形状を複雑に
した場合に於いても安定な放電を発生させることが可能
である。このため被覆物の形状に対応した形状の陰極を
用いることができ、それにより３次元形状を有する基体
への被覆をも行なうことができる。簡単な一例として、
第２図に示すように電極と基体との形状を対応させるこ
とにより両者のギャップが一定となり均一にダイヤモン
ドの被覆が行なえる。これはより形状が複雑な場合にも
対応でき非球面上への被覆も可能である。Further, in the method of the present invention, since a mesh with high electron emission efficiency is used as the cathode electrode, stable discharge can be generated even when the cathode has a complicated shape. Therefore, it is possible to use a cathode having a shape corresponding to the shape of the coating, thereby making it possible to coat even a substrate having a three-dimensional shape. As a simple example,
As shown in FIG. 2, by matching the shapes of the electrode and the substrate, the gap between them becomes constant and uniform diamond coating can be achieved. This can be used even when the shape is more complex, and it is also possible to coat aspherical surfaces.
さらに、放電領域は電極面積を増加させることにより容
易に拡大することができる。このため大面積への被覆も
可能である。Furthermore, the discharge area can be easily expanded by increasing the electrode area. Therefore, it is possible to cover a large area.
〈実施例〉 次にこの発明を実施例により詳細に説明する。<Example> Next, the present invention will be explained in detail with reference to examples.
実施例１
陰極として用いるメッシュの線径およびピッチを第１表
に示すように種々変化させて直流放電を行なった。その
結果を第１表に示した。電極の形状は第３図に示したよ
うに陰極にはＬ字型に作或したＭｏメッシュ１を用い、
陽極２はＷの円柱形状のものを使用した。両電極間の距
離は１０ｍｍと固定し、放電条件としては真空容器内に
メタン２ｓｅｃｍ 、水素２００ｓｅｃｍを導入し、系
内の圧力を４０Ｔｏｒｒとした。陰極に使用したメッシ
ュの線径が０． ５ｍｍ以下ではグロー放電が安定に発
生するが、線径を０． ６ｍｍとした場合には両電極間
でスパーク放電が起こりグロー放電へ移行しなかった。Example 1 Direct current discharge was performed while varying the wire diameter and pitch of the mesh used as the cathode as shown in Table 1. The results are shown in Table 1. The shape of the electrode is as shown in Figure 3, using Mo mesh 1 made in an L shape as the cathode.
The anode 2 was made of W and had a cylindrical shape. The distance between both electrodes was fixed at 10 mm, and as discharge conditions, methane at 2 sec and hydrogen at 200 sec were introduced into the vacuum vessel, and the pressure in the system was set at 40 Torr. The wire diameter of the mesh used for the cathode is 0. Glow discharge occurs stably when the wire diameter is 5 mm or less, but when the wire diameter is reduced to 0. When the diameter was 6 mm, spark discharge occurred between both electrodes and did not shift to glow discharge.
また、ピッチを変化させた場合には３ｍｍ以下では放電
が発生するが、ピッチを４ｍｍと増加させると、グロー
放電の発生が起こらなかった。これは、メッシュの材質
をＷ，Ｔａとした場合にも同様であった。Further, when the pitch was changed, discharge occurred when the pitch was 3 mm or less, but when the pitch was increased to 4 mm, no glow discharge occurred. This was also the case when the mesh material was W or Ta.
第
ｌ
表
実施例２
第４図に示すように、電極はＬ字型のＭｏメッシュｌを
陰極とし、直流電源５を接続し陽極２はＷの円柱形状の
ものを使用した。寸法はそれぞれ陰極のＬ字底部が３０
Ｘ ３０ｍｍ，線径０．２＋ｎｍ ，ビッチ１ｍｒＱの
メッシュを、陽極は直径３ ０ ｍ ｍ ％高さ１０ｍ
ｍの円柱を用いた。電極間距離は１０ｍｍとした。基体
３は２０Ｘ２０ｍｍの単結晶ＳＬを使用し、陽極を介し
ヒーター４により加熱され６００℃に保持された。真空
容器内にメタン２ｓＣＣｆｆｉ、水素２００ｓｃｃｍを
導入し系内の圧力を４０Ｔｏｒｒとした。そして上記電
極間で直流放電を発生させ２０時間の反応を行なった。Table 1 Example 2 As shown in FIG. 4, an L-shaped Mo mesh 1 was used as a cathode, a DC power source 5 was connected, and a W cylindrical anode 2 was used. The dimensions of each cathode L-shaped bottom are 30mm.
x 30mm, wire diameter 0.2+nm, pitch 1mrQ mesh, anode diameter 30mm % height 10m
A cylinder of m was used. The distance between the electrodes was 10 mm. The substrate 3 was a 20×20 mm single crystal SL, heated by a heater 4 through an anode, and maintained at 600°C. Methane (2s CCffi) and hydrogen (200 sccm) were introduced into the vacuum vessel, and the pressure inside the system was set to 40 Torr. Then, a direct current discharge was generated between the electrodes, and a reaction was carried out for 20 hours.
このときの電圧、電流はそれぞれ３５０ Ｖ， ０．８
Ａであった。その結果、約８ ｕｍの膜が得られ、ラ
マン分光分析により良質なダイヤモンドであることが確
認された。また、ＳＥＭ観察により膜表面は０．１μｍ
程度の微粒子で覆われた非常に緻密で平坦な膜面である
ことがわった。The voltage and current at this time were 350 V and 0.8, respectively.
It was A. As a result, a film with a thickness of about 8 um was obtained, and Raman spectroscopic analysis confirmed that it was a good quality diamond. Furthermore, SEM observation revealed that the membrane surface was 0.1 μm thick.
The surface of the film was found to be extremely dense and flat, covered with very fine particles.
〈発明の効果〉
以上説明したように、この発明は陰極としてメッシュを
用いることにより電子の放射率が向上し、高密度なプラ
ズマを極めて安定に長時間維持することができるのであ
る。また、基体温度の低温化および大面積化に適し、加
えて形状が複雑な陰極を用いる場合に於いても安定な放
電を発生させることが可能であり、３次元形状を有する
基体への被覆が可能である。<Effects of the Invention> As explained above, in the present invention, by using a mesh as a cathode, the electron emissivity is improved, and high-density plasma can be maintained extremely stably for a long time. In addition, it is suitable for lowering the substrate temperature and increasing the area, and in addition, it is possible to generate stable discharge even when using a cathode with a complicated shape, and it is possible to coat a substrate with a three-dimensional shape. It is possible.
第１図および第２図はこの発明の方法において、陰極と
して用いるメッシュの形状の一例を示す説明図、第３図
はこの発明の他の実施例を示す電極形状の説明図であり
、第４図はこの発明の実施例にて使用する装置の概略図
である。1 and 2 are explanatory diagrams showing an example of the shape of a mesh used as a cathode in the method of this invention, FIG. 3 is an explanatory diagram of an electrode shape showing another embodiment of this invention, and FIG. The figure is a schematic diagram of an apparatus used in an embodiment of the invention.
Claims (1)
ズマ化し、基体上にダイヤモンドを析出させる方法に於
て、陰極としてＭｏ、Ｗ、Ｔａから選ばれた少なくとも
１種あるいは複数の材質で構成された線径０．５ｍｍ以
下、ピッチ３ｍｍ以下のメッシュを用いることを特徴と
するダイヤモンド合成方法。In the method of converting raw material gas for diamond vapor phase synthesis into plasma by direct current discharge and depositing diamond on a substrate, a wire diameter made of at least one or more materials selected from Mo, W, and Ta is used as a cathode. A diamond synthesis method characterized by using a mesh having a mesh size of 0.5 mm or less and a pitch of 3 mm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1305055A JPH03166378A (en) | 1989-11-24 | 1989-11-24 | Diamond synthesizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1305055A JPH03166378A (en) | 1989-11-24 | 1989-11-24 | Diamond synthesizing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03166378A true JPH03166378A (en) | 1991-07-18 |
Family
ID=17940575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1305055A Pending JPH03166378A (en) | 1989-11-24 | 1989-11-24 | Diamond synthesizing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03166378A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008230896A (en) * | 2007-03-20 | 2008-10-02 | Ulvac Japan Ltd | Remote plasma cvd device and manufacturing method of carbon nano-tube using the same |
-
1989
- 1989-11-24 JP JP1305055A patent/JPH03166378A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008230896A (en) * | 2007-03-20 | 2008-10-02 | Ulvac Japan Ltd | Remote plasma cvd device and manufacturing method of carbon nano-tube using the same |
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