JPH01290593A - Method for synthesizing diamond at high velocity - Google Patents
Method for synthesizing diamond at high velocityInfo
- Publication number
- JPH01290593A JPH01290593A JP11959988A JP11959988A JPH01290593A JP H01290593 A JPH01290593 A JP H01290593A JP 11959988 A JP11959988 A JP 11959988A JP 11959988 A JP11959988 A JP 11959988A JP H01290593 A JPH01290593 A JP H01290593A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- plasma
- substrate
- carbon source
- gas
- 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
- 239000010432 diamond Substances 0.000 title claims abstract description 25
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title description 19
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 21
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 6
- 229940050176 methyl chloride Drugs 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 carbon ions Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明はダイヤモンドの高速合成法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a method for high-speed synthesis of diamond.
従来技術
従来、放電を用い熱力学的に準安定領域でダイヤモンド
を合成する方法として、次のような方法が知られている
。Prior Art Conventionally, the following method has been known as a method for synthesizing diamond in a thermodynamically metastable region using electric discharge.
１）放電を用い炭素イオンあるいは炭化水素イオンを作
り、これを電位勾配によって加速し、基板表面に衝突さ
せてダイヤモンドを析出させるイオンビーム法、イオン
ブレーティンク法。1) Ion beam method or ion braking method in which carbon ions or hydrocarbon ions are created using electric discharge, accelerated by a potential gradient, and collided with the substrate surface to deposit diamond.
２） 炭化水素と水素の混合ガスを、グロー放電による
低温プラズマにより活性化させ、基板表面に当てダイヤ
モンドを析出させる活性化気相析出法。2) An activated vapor deposition method in which a mixed gas of hydrocarbon and hydrogen is activated by low-temperature plasma generated by glow discharge, and applied to the substrate surface to deposit diamond.
しかし、これらの方法はいずれも次のような欠点がある
。However, all of these methods have the following drawbacks.
即ち、１）の方法は常温で基板表面へダイヤモンド類を
析出させることができる利点があるが、加速されたイオ
ンを用いるために、析出したダイヤモンドに欠陥が多く
結晶性のよいものは得にく（、またイオンビーム密度を
高くできないので、析出速度がおそいなどの欠点がある
。That is, method 1) has the advantage of being able to deposit diamonds on the substrate surface at room temperature, but because accelerated ions are used, the deposited diamond has many defects and is difficult to obtain with good crystallinity. (Also, since the ion beam density cannot be increased, the deposition rate is slow.
２）の方法は基板上にダイヤモンドの微結晶を得ること
はできるが、グロー放電による低温プラズマであるため
、ガス圧が通常０．３気圧以下と低（しなければプラズ
マが発生せず、またイオン、ラジカル等の活性種濃度も
最大１０％程度と低いためダイヤモンドの成長速度がお
そい（最大数μｍ／ｈｒ）欠点がある。Method 2) can obtain diamond microcrystals on the substrate, but because it uses low-temperature plasma due to glow discharge, the gas pressure is usually low, 0.3 atmospheres or less (otherwise, plasma will not be generated, and Since the concentration of active species such as ions and radicals is as low as about 10% at most, the diamond growth rate is slow (up to several μm/hr), which is a drawback.
本出願人はこれらの従来法の欠点を改善する方法として
、さきに１７００＠に以上の熱プラズマを利用して高速
合成する方法を開発した。（特開昭６２−１５８１９５
号公報）この方法では炭素源として有機化合物を使用し
ていたが、炭素源について更に検討を加え本発明に到達
したものである。As a method to improve the drawbacks of these conventional methods, the present applicant has previously developed a method for high-speed synthesis using thermal plasma of 1700@ or more. (Unexamined Japanese Patent Publication No. 62-158195
In this method, an organic compound was used as a carbon source, but the present invention was achieved by further study of the carbon source.
発明の目的
本発明の目的は前記熱プラズマ利用の方法において、炭
素源として従来使用されていなかったハロゲンまたはリ
ンを含んだ有機化合物の使用によるダイヤモンドの高速
合成法を徒供しようとするものである。Purpose of the Invention The purpose of the present invention is to provide a high-speed diamond synthesis method using an organic compound containing halogen or phosphorus, which has not been conventionally used as a carbon source, in the method using thermal plasma. .
発明の構成
本発明者は、前記１７００°Ｋ以上の熱プラズマ使用に
よる高速ダイヤモンドの合成法において、炭素源として
使用する有機化合物について鋭意検討を加えた結果、ハ
ロゲンまたはリンを含んだ有機化合物も有効に利用し得
られることを確認し得、この知見に基づいて本発明を完
成するに至った。Structure of the Invention The present inventor has conducted intensive studies on organic compounds to be used as carbon sources in the high-speed diamond synthesis method using thermal plasma of 1700°K or more, and has found that organic compounds containing halogen or phosphorus are also effective. The present invention was completed based on this finding.
本発明の要旨は、水素、不活性ガスのいずれかあるいは
混合ガスに放電により発生させた１７０００に以上の熱
プラズマ中に、炭素源としてハロゲンまたはリンを含む
有機化合物の１種あるいは２種以上を導入して基板上で
ダイヤモンドを析出さの
せることを特徴とするダイヤモンｌ嵩速合成法にある。The gist of the present invention is to add one or more organic compounds containing halogen or phosphorus as a carbon source to a thermal plasma of 17,000 or more generated by discharging hydrogen, an inert gas, or a mixed gas. The present invention is a method for bulk synthesis of diamond, which is characterized by depositing diamond on a substrate.
本発明の方法において炭素源として使用するハロゲンま
たはリンを含む有機化合物としては、プラズマ中で分解
し、炭素を含むイオン種、ラジカル種を生成し得るもの
であれば、特にその性状をとわない０例えば塩化メチル
、クロロホルム等のハロゲンを含む化合物、ホスフィン
などのリンを含む化合物が挙げられる。The organic compound containing halogen or phosphorus to be used as a carbon source in the method of the present invention may have any particular properties as long as it can be decomposed in plasma and generate ionic species or radical species containing carbon. Examples include halogen-containing compounds such as methyl chloride and chloroform, and phosphorus-containing compounds such as phosphine.
放電に用いる電源は直流、高周波、低周波交流、マイク
ロ波のいずれでもよく、またそれらを組合せてもよい。The power source used for discharging may be direct current, high frequency, low frequency alternating current, or microwave, or a combination of these may be used.
プラズマ発生用ガスとしては、プラズマの安定性、ダイ
ヤモンド析出速度の制御の容易さ等で水素、不活性ガス
のいずれかあるいは混合ガスが使用される。これを放電
電源から電力を供給し１７００６に以上の熱プラズマを
発生させる。As the plasma generating gas, hydrogen, an inert gas, or a mixed gas is used in view of plasma stability, ease of controlling the diamond deposition rate, and the like. Power is supplied to this from a discharge power source to generate the above thermal plasma at 17006.
炭素源のハロゲンまたはリンを含む有機化合物はプラズ
マ発生用ガス供給口から供給してもよいし、あるいは別
に設けた供給口から供給してもよい、そのプラズマ発生
ガス圧は１０−’〜５Ｘ１０”気圧までの広い範囲で用
いることができる。しかし低い圧力ではダイヤモンドの
析出速度がおそく、高い圧力では圧力容器の取扱いに手
数がかかる。The organic compound containing halogen or phosphorus as a carbon source may be supplied from a plasma generation gas supply port, or may be supplied from a separately provided supply port, and the plasma generation gas pressure is 10-' to 5X10''. It can be used in a wide range up to atmospheric pressure.However, at low pressures the rate of diamond precipitation is slow, and at high pressures it is difficult to handle the pressure vessel.
プラズマ中あるいは尾炎部に基板を設けると基板上にダ
イヤモンド膜を形成し得られる。基板の温度は４００〜
１７００°Ｃであることが適当である。When a substrate is provided in the plasma or in the tail flame area, a diamond film can be formed on the substrate. The temperature of the board is 400~
A suitable temperature is 1700°C.
４００ ”Ｃより低いと析出したダイヤモンドに水素が
混入したり、あるいは欠陥が入ることがあり、また１７
００℃を趙えると黒鉛が混入し易くなる。If the temperature is lower than 400"C, hydrogen may be mixed into the precipitated diamond, or defects may occur;
If the temperature is increased to 00°C, graphite is likely to be mixed in.
この温度のコントロールは基板の位置を変えたり、ある
いは基板ホルダーや基板を不活性ガス。This temperature can be controlled by changing the position of the substrate, or by placing the substrate holder or substrate in an inert gas.
水素ガス、水等の冷媒により冷却することによって行う
ことができる。This can be done by cooling with a refrigerant such as hydrogen gas or water.
基板としては、モリブデン、タングステン、タンタルな
どの金属、アルミナなどのセラミックス、ダイヤモンド
単結晶が用いられる。As the substrate, metals such as molybdenum, tungsten, and tantalum, ceramics such as alumina, and single crystal diamond are used.
本発明の方法を実施する装置の例の概要図を示す。1 shows a schematic diagram of an example of a device implementing the method of the invention; FIG.
第１図はマイクロ波放電を用いた装置、第２図は高周波
放電を用いた装置を示す。FIG. 1 shows an apparatus using microwave discharge, and FIG. 2 shows an apparatus using high-frequency discharge.
図中、１はマイクロ波プラズマトーチ、２はマイクロ波
発振機、３は基板、４は基板ホルダー、５はプラズマ発
生室、６は排気装置、７はガス供給装置、８．８’、８
′は調整弁、９は高周波プラズマトーチ、１０は高周波
発振機、１１はワークコイル、１２は原料導入装置を示
す、その操業は実施例において示す。In the figure, 1 is a microwave plasma torch, 2 is a microwave oscillator, 3 is a substrate, 4 is a substrate holder, 5 is a plasma generation chamber, 6 is an exhaust device, 7 is a gas supply device, 8.8', 8
' is a regulating valve, 9 is a high-frequency plasma torch, 10 is a high-frequency oscillator, 11 is a work coil, and 12 is a raw material introduction device, the operation of which will be shown in the examples.
実施例１゜
第１図に示す装置を用い、ガス供給装置７がら調整弁８
．８’ 、８′を通してプラズマ発生室５にプラズマ発
生用ガス及び炭素源を供給する。即ち、８から塩化メチ
ルＩｆ／−ｉｎとアルゴン１１／讃ｉｎの混合ガスを、
８′からアルゴン３４！／ｗｉｎを、８′からアルゴン
１０１ ／ｗｉｎと水素１２ ｊ！ ／ｗｉｎの混合ガ
スを流し、プラズマ発生室５内の圧を１気圧と基板３と
して２０ｍφモリ
ブデン基板を用い、水冷により基板３の温度を１０００
°Ｃに調整した。放電を１０分間行った結果、基板３上
に約３０μｍのダイヤモンド膜が得られた。Example 1 Using the device shown in FIG. 1, a gas supply device 7 and a regulating valve 8
．． A plasma generating gas and a carbon source are supplied to the plasma generating chamber 5 through 8' and 8'. That is, from 8, a mixed gas of methyl chloride If/-in and argon 11/-in,
Argon 34 from 8'! /win, 8' to argon 101 /win and hydrogen 12 j! A mixed gas of /win was flowed, the pressure inside the plasma generation chamber 5 was set to 1 atm, a 20 mφ molybdenum substrate was used as the substrate 3, and the temperature of the substrate 3 was set to 1000 m by water cooling.
Adjusted to °C. As a result of performing the discharge for 10 minutes, a diamond film of about 30 μm was obtained on the substrate 3.
実施例λ
第２図に示す装置を用い、ガス供給装置７から調整弁８
．８’、８’を通してプラズマ発生室５にプラズマ発生
用ガス及び炭素源を供給する。即ち、８からメチルホス
フィン２４！／５ｈｉｎとアルゴン２４！／ｓｉｎの混
合ガスを、８′からアルゴン１０２／ｗｉｎを、８′か
らアルゴン２１ ｊ！ ／ｓｉｎと水素１５ｊ！／ｓｉ
ｎの混合ガスを流し、プラズマ発生室５内の圧を１気圧
とする６次に高周波発振機１０を作動して１と同様なも
のを使用し、水冷により表面温度を９００℃に調整した
。放電を１０分間行った結果、基板３上に厚さ４０μ■
のダイヤモンド膜が得られた。Example λ Using the device shown in FIG. 2, from the gas supply device 7 to the regulating valve 8
．． A plasma generation gas and a carbon source are supplied to the plasma generation chamber 5 through 8' and 8'. That is, from 8 to 24 methylphosphine! /5hin and argon 24! /sin mixed gas, argon 102/win from 8', argon 21 j! /sin and hydrogen 15j! /si
The 6-order high-frequency oscillator 10 was operated to set the pressure inside the plasma generation chamber 5 at 1 atmosphere, and the same one as 1 was used, and the surface temperature was adjusted to 900° C. by water cooling. As a result of discharging for 10 minutes, a thickness of 40μ■ was formed on the substrate 3.
A diamond film was obtained.
発明の効果
本発明の方法によると従来炭素源として使用することが
知られていなかったハロゲンまたはリンを含む存機化合
物を用い、従来のＣＶＤ法に比べ数百倍の高速度でダイ
ヤモンドを析出可能とした効果を存する。Effects of the Invention According to the method of the present invention, diamond can be precipitated at a rate several hundred times higher than that of the conventional CVD method, using organic compounds containing halogen or phosphorus, which have not been previously known to be used as carbon sources. It has the effect of
図面は本発明の方法を実施する装置の実施例の概要図で
、第１図はマイクロ波放電を用いた装置、第２図は高周
波放電を用いた装置を示す。
１：マイクロ波プラズマトーチ、
２：マイクロ波発振機、３８基板、
４：基板ホルダー、 ５：プラズマ発生室、６：排気
装置、 ７：ガス供給装置、８．８’ 、８′：
調整弁、
９：高周波プラズマトーチ、The drawings are schematic diagrams of embodiments of apparatus for carrying out the method of the present invention, with FIG. 1 showing an apparatus using microwave discharge and FIG. 2 showing an apparatus using high-frequency discharge. 1: Microwave plasma torch, 2: Microwave oscillator, 38 substrates, 4: Substrate holder, 5: Plasma generation chamber, 6: Exhaust device, 7: Gas supply device, 8.8', 8':
Regulating valve, 9: High frequency plasma torch,
Claims (1)
より発生させた１７００°Ｋ以上の熱プラズマ中に、炭
素源としてハロゲンまたはリンを含む有機化合物の１種
あるいは２種以上を導入して基板上でダイヤモンドを析
出させることを特徴とするダイヤモンドの高速合成法。One or more organic compounds containing halogen or phosphorus are introduced as a carbon source into a thermal plasma of 1700°K or more generated by electric discharge in hydrogen, an inert gas, or a mixed gas, and then the substrate is heated. A high-speed diamond synthesis method characterized by precipitating diamond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11959988A JPH01290593A (en) | 1988-05-17 | 1988-05-17 | Method for synthesizing diamond at high velocity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11959988A JPH01290593A (en) | 1988-05-17 | 1988-05-17 | Method for synthesizing diamond at high velocity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01290593A true JPH01290593A (en) | 1989-11-22 |
Family
ID=14765378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11959988A Pending JPH01290593A (en) | 1988-05-17 | 1988-05-17 | Method for synthesizing diamond at high velocity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01290593A (en) |
-
1988
- 1988-05-17 JP JP11959988A patent/JPH01290593A/en active Pending
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