JPS63139095A - Method for synthesizing diamond by vapor phase process - Google Patents
Method for synthesizing diamond by vapor phase processInfo
- Publication number
- JPS63139095A JPS63139095A JP18238086A JP18238086A JPS63139095A JP S63139095 A JPS63139095 A JP S63139095A JP 18238086 A JP18238086 A JP 18238086A JP 18238086 A JP18238086 A JP 18238086A JP S63139095 A JPS63139095 A JP S63139095A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- gas
- arc discharge
- hydrogen
- compd
- 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 49
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000012808 vapor phase Substances 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010891 electric arc Methods 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 26
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- 238000001308 synthesis method Methods 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052776 Thorium Inorganic materials 0.000 abstract description 2
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910052712 strontium Inorganic materials 0.000 abstract description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910001080 W alloy Inorganic materials 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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
- 238000009834 vaporization Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は有機炭素化合物から気相法でダイヤモンドを合
成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for synthesizing diamond from organic carbon compounds by a vapor phase method.
ダイヤモンド合成には黒鉛を超高圧下でダイヤモンドに
変換する方法と炭化水素等のガスを加熱でプラズマ等の
エネルギーで励起し、そのガスからダイヤモンドを析出
させるいわゆる気相法ダ・イヤモンド合成法がある。前
者は主として粒状のダイヤモンドが得られ、後者は微粒
子状あるいは膜状のダイヤモンドが得られる。Diamond synthesis methods include a method in which graphite is converted into diamond under ultra-high pressure, and a so-called vapor phase diamond synthesis method in which a gas such as a hydrocarbon is heated and excited with energy such as plasma, and diamond is precipitated from the gas. . The former method mainly yields granular diamonds, and the latter method yields fine grain or film diamonds.
従来の技術
気相法ダイヤモンド合成で従来発表されているものはガ
スは殆んどメタン、エタン等の炭化水素と水素ガスの混
合ガスを用いている。このガスの励起には各種の方法が
あり、大別すると加熱フィラメントを用いる方法（特開
昭５９−８１１００） 、マイクロ波による方法（４Ｉ
Ｆ開閉５９−３０９８ ） 、高周波による方法（特開
昭５８−１３５１１７ ）があり、その他特殊なものと
してはグロー放電、アーク放電、スパッタリング法、イ
オンビーム法、紫外線照射法などがある。Conventional techniques Most of the gas-phase diamond synthesis methods that have been published so far use a mixed gas of hydrocarbon gas such as methane or ethane and hydrogen gas. There are various methods for excitation of this gas, which can be roughly divided into a method using a heated filament (Japanese Patent Application Laid-Open No. 59-81100), a method using microwaves (4I
There are methods using high frequency (JP-A No. 58-135117), and other special methods such as glow discharge, arc discharge, sputtering, ion beam method, and ultraviolet irradiation method.
発明が解決しようとする問題点
気相法によるダイヤモンド合成においては有機化合物が
分解し、中間に生成するメチル基等を介してその炭２が
析出するときダイヤモンド構造になると考えられている
。またこのとき同時に非ダイヤモンド炭素（以下非ダイ
ヤ炭素という）が析出する。従って析出状態ではダイヤ
モンドと非ダイヤ炭素が混在した形になっている。析出
物をダイヤモンドのみにするには析出物から絶えず非ダ
イヤ炭素を除去しなければならない。通常この除去作用
は原子状等に励起された水素原子が行なっている。気相
法ダイヤモンド合成において、有機化合物に多量の水素
ガスを混合し、水素ガスを励起してダイヤモンド析出面
に接触させているのは、この析出した非ダイヤ炭素を除
去するためである。原子状水素による非ダイヤ炭素の除
去は炭素が炭化水素系の化合物、例えばメタン等となっ
て気化することによると云われている。ところがダイヤ
モンドは原子状水素とは殆んど反応しないのでそのまま
残る。Problems to be Solved by the Invention In diamond synthesis using the vapor phase method, it is believed that a diamond structure is formed when an organic compound is decomposed and the charcoal 2 is precipitated via intermediately formed methyl groups. At the same time, non-diamond carbon (hereinafter referred to as non-diamond carbon) is precipitated. Therefore, the precipitated state is a mixture of diamond and non-diamond carbon. In order to reduce the precipitate to diamond only, non-diamond carbon must be constantly removed from the precipitate. Usually, this removal action is carried out by atomically excited hydrogen atoms. In vapor phase diamond synthesis, a large amount of hydrogen gas is mixed with an organic compound, and the hydrogen gas is excited and brought into contact with the diamond precipitation surface in order to remove the precipitated non-diamond carbon. It is said that the removal of non-diamond carbon by atomic hydrogen is due to the carbon becoming a hydrocarbon compound such as methane and vaporizing. However, diamond hardly reacts with atomic hydrogen, so it remains as is.
この様なことからダイヤモンドの生成量を増し、またそ
の純度を高めるには析出した非ダイヤ炭素を如何に能率
よく除去するか力（重要となる。For this reason, in order to increase the amount of diamond produced and to improve its purity, it is important to efficiently remove the precipitated non-diamond carbon.
それには高い濃度の原子状、或いはイオン化した活性の
高い水素（以下本発明ではこれらを励起した水素という
）を得ることが必要である。For this purpose, it is necessary to obtain highly concentrated atomic or ionized hydrogen (hereinafter referred to as excited hydrogen in the present invention).
従来の励起水素を得る方法は高周波電圧、マイクロ波、
熱フィラメントなどが用いられているが、殆んどがかな
りの減圧下で行なわれている。Conventional methods for obtaining excited hydrogen include high frequency voltage, microwave,
Hot filaments and the like are used, but most of the work is done under considerably reduced pressure.
工業的な実施を考えると常圧付近で実施できるのが望ま
しい。Considering industrial implementation, it is desirable to be able to perform the process near normal pressure.
本発明の目的は励起された水素を多量につくることがで
き、それによってダイヤモンドの生成量を増すことがで
きること、またこの操作を常圧付近でもできるようにす
ることにある。The object of the present invention is to be able to produce a large amount of excited hydrogen, thereby increasing the amount of diamond produced, and to be able to perform this operation even at near normal pressure.
問題点を解決するための手段
本発明は上記の目的を達成するため水素を含むガスを特
定の電極を用いたアーク放電帯を通すことにより、少な
くとも水素ガスを励起し、この励起ガスをダイヤモンド
析出部に導いて、非ダイヤ炭素を除去するようにしたも
のである。ここで特定の電極とはタングステン系の電極
である。Means for Solving the Problems In order to achieve the above object, the present invention excites at least hydrogen gas by passing hydrogen-containing gas through an arc discharge zone using a specific electrode, and uses this excited gas to deposit diamond. The non-diamond carbon is removed. Here, the specific electrode is a tungsten-based electrode.
アーク放電であれば常圧付近でも可能であり、また大き
なエネルギーも容易に供給できるので、多量の励起水素
を得ることが期待できる。これまでもアーク放電を利用
しようとする試みはいくつか見られる０例えば特開昭Ｇ
ｏ−１７１２９４、同６゜−１１８６９３である。この
場合の電極は前者が炭素電極、後者は記載がないので不
明である。Arc discharge is possible even at near normal pressure, and large amounts of energy can be easily supplied, so it is expected that a large amount of excited hydrogen can be obtained. Until now, there have been several attempts to utilize arc discharge.For example, JP-A-Sho G
o-171294 and 6°-118693. The electrode in this case is unknown because the former is a carbon electrode and the latter is not described.
本発明者は気相法ダイヤモンド合成におけるガスの励起
をアーク放電により行なうことについて種々研究した結
果、電極の材質によって結果が大きく変ってくることが
わかった。上記の炭素電極を用いると、水素ガスの雰囲
気に起因するためか、アーク放電中の炭素電極の昇華、
揮散、崩壊が大きく、−・ＩＳＳ上上続使用は不可能で
あった。The present inventor has conducted various studies on excitation of gas by arc discharge in vapor phase diamond synthesis, and has found that the results vary greatly depending on the material of the electrode. When using the above carbon electrode, sublimation of the carbon electrode during arc discharge, probably due to the hydrogen gas atmosphere,
Vaporization and disintegration were significant, making subsequent use on the ISS impossible.
上記二つの特許の方法は１００Ｔｏｒｒ以下、あるいは
３００Ｔｏｒｒ以下といずれもかなりの減圧下で行なわ
れているつ
本発明は水素雰囲気下でアーク放電させる電極としてタ
ングステン系の電極が最適であることを発見したもので
ある。ここでタングステン系とはタングステン系独の金
属の外、これとトリウム、バリウム、ストロンチウム等
の金属を５０％以下で添加した合金を意味する。The methods in the above two patents are both carried out under considerably reduced pressures of 100 Torr or less, or 300 Torr or less.The present invention has discovered that a tungsten-based electrode is optimal as an electrode for arc discharge in a hydrogen atmosphere. It is something. Here, tungsten-based metals mean not only tungsten-based metals but also alloys in which 50% or less of metals such as thorium, barium, and strontium are added to these metals.
本発明で使用される有機化合物としては従来公知のメタ
ン、エタン、プロパン、メタン、ｘｆレン、プロピレン
等の炭化水素の外、先に特許出願したアルコール、アセ
トン、有機酸、エステル等の含酸素有機化合物、さらに
窒素、硫黄、ハロゲン等を含む有機化合物が使用できる
。The organic compounds used in the present invention include conventionally known hydrocarbons such as methane, ethane, propane, methane, Compounds, as well as organic compounds containing nitrogen, sulfur, halogens, etc. can be used.
これらの有機化合物の外に一般的には水素ガスが併用さ
れるが、有機化合物の分解により水素ガスの発生量の多
い場合は添加する水素ガスを減らし、又は殆んど添加し
ないでよい場合もある。またこれらの場合にアルゴン等
の不活性ガスを混合することもできる。In addition to these organic compounds, hydrogen gas is generally used in combination, but if a large amount of hydrogen gas is generated due to the decomposition of the organic compound, the amount of hydrogen gas added may be reduced or may not be added at all. be. In these cases, an inert gas such as argon may also be mixed.
ガスの励起については少なくとも水素ガスはアーク放電
帯を通すことが必要である。有機化合物は水素ガスと混
合してアーク放電帯を通してもよく、またアーク放電帯
を通さずに直接ダイヤモンド析出帯に導き、そこで分解
、メチル基等の生成、ダイヤモンドの析出を行なうこと
もできる。For gas excitation, it is necessary to pass at least hydrogen gas through the arc discharge zone. The organic compound may be mixed with hydrogen gas and passed through the arc discharge zone, or it may be led directly to the diamond precipitation zone without passing through the arc discharge zone, where decomposition, generation of methyl groups, etc., and precipitation of diamond can take place.
通常ダイヤモンド析出帯付近はかなりの高温になってお
り、そこでの有機化合物の分解等は可能である。なお、
有機化合物の分解により生成した水素ガスを励起する場
合は、有機化合物をアーク放電イ１）に通すことが必要
である。Normally, the temperature near the diamond precipitation zone is quite high, and it is possible to decompose organic compounds there. In addition,
When exciting hydrogen gas produced by decomposition of an organic compound, it is necessary to pass the organic compound through an arc discharge (1).
アーク放電によれば相当高い温度にガスを加熱し、プラ
ズマ化等にすることができる。励起水素の濃度は温度の
上昇とともに増す。例えば従来のフィラメント法ではフ
ィラメントの耐熱、寿命の点で事実上２５００°Ｃ以上
に加熱できない、またマイクロ波プラズマは非平衡プラ
ズマ状態にあるので、ガス温度自体は１０００℃以下で
ある。これに対し、アーク放電はガスを３０００〜５０
００℃近くにも加熱することができる０例えば４０００
℃近くになると水素ガスは８０％前後が励起水素になる
。本発明はこの高濃度の励起水素を利用するのが特徴で
あるが、ダイヤモンドの生成速度を早めるためにはその
ほかにメチル基等の濃度を高くしてダイヤモンドの析出
量を増すことが必要であり、それには有機化合物も水素
ガスと共にエネルギーの大きなアーク放電で分解するこ
とが望ましい、アーク放電におけるガスの圧力は１５０
〜２０００Ｔｏｒｒが適当であり、 ７６０Ｔｏｒｒで
もできるのが一つの特徴である。Arc discharge can heat gas to a considerably high temperature and turn it into plasma. The concentration of excited hydrogen increases with increasing temperature. For example, in the conventional filament method, it is virtually impossible to heat the filament above 2500°C due to its heat resistance and lifespan, and since microwave plasma is in a non-equilibrium plasma state, the gas temperature itself is 1000°C or less. On the other hand, arc discharge discharges gas at 3,000 to 50
Can be heated to near 00℃ 0 e.g. 4000
When the temperature approaches ℃, around 80% of the hydrogen gas becomes excited hydrogen. The present invention is characterized by the use of this highly concentrated excited hydrogen, but in order to accelerate the rate of diamond formation, it is also necessary to increase the concentration of methyl groups, etc. to increase the amount of diamond precipitated. For this purpose, it is desirable to decompose organic compounds together with hydrogen gas using a high-energy arc discharge.The pressure of the gas in the arc discharge is 150
~2000 Torr is suitable, and one feature is that it can also be done at 760 Torr.
次に図を用いてアーク放電によりダイヤモンドを合成す
る１例について具体的に説明する。Next, an example of synthesizing diamond by arc discharge will be specifically explained using figures.
第１図にその概略断面図を示す０図で１は反応容器で、
その左右からタングステン系の電極２が設けられている
。電極は先端部分を裸にし、その後は水冷３されている
。゛電極はリード線７を通して電源（図示してない）に
接続される水素ガスとアルゴンガスと有機化合物の混合
ガスはガス導入管４により電極の先端部に導入される。Fig. 1 shows a schematic cross-sectional view of the same, and in Fig. 0, 1 is a reaction vessel;
Tungsten-based electrodes 2 are provided from the left and right sides. The tip of the electrode is exposed, and the rest is water-cooled. The electrode is connected to a power source (not shown) through a lead wire 7. A mixed gas of hydrogen gas, argon gas, and an organic compound is introduced into the tip of the electrode through a gas introduction pipe 4.
５は反応後のガスの排出口である。ダイヤモンドの析出
は基板６の上で行なわれる。基板は図示してないが温度
の調整のためのヒーター又は冷却器が通常内蔵されてい
る。基板はゆっくり回転するようにすればダイヤモンド
の析出が均等になる。基板の材質は通常使用されている
ようにシリコン、シリコンカーバイト、モリブデン、タ
ンタル、タングステンなどである。また粒状の炭化珪素
などを基板上に置けば炭化珪素の粒子の周囲に微粒子状
のダイヤモンドが析出する。5 is a gas outlet after the reaction. Diamond deposition takes place on the substrate 6. Although not shown, the substrate usually has a built-in heater or cooler for temperature adjustment. If the substrate is rotated slowly, the diamond will be deposited evenly. The material of the substrate is commonly used silicon, silicon carbide, molybdenum, tantalum, tungsten, etc. Furthermore, if granular silicon carbide or the like is placed on a substrate, fine diamond particles will precipitate around the silicon carbide particles.
基板の温度は一般的には２００〜９００°Ｃが適する。The temperature of the substrate is generally 200 to 900°C.
アーク放電帯の温度は、測定がむずかしいが、ガスの温
度で高いところで３０００〜５０００℃程度と推定され
る。Although it is difficult to measure the temperature of the arc discharge zone, it is estimated to be around 3000 to 5000°C at the highest gas temperature.
基板等のダイヤモンド析出部はアークの直下が適し、そ
してあまり離さない方がよい。その距離はアーク放電の
条件等にもよるが２ｍ＋ａ〜５ＩＩｆｆｉ程度が望まし
い。It is suitable for the diamond deposited part on the substrate etc. to be directly under the arc, and it is better not to place it too far away. The distance is preferably about 2 m+a to 5 IIffi, although it depends on the arc discharge conditions.
実施例Ｉ
ｉ１図の装置を用い、電極としてｗ −ｇｈ金合金Ｔｈ
１重量％）を用い、直流２２Ｖ、 ３Ａでアークを発生
させた。ガスは気化したアセトン４ｃｃ／分、水素１６
ｃｃ／分、アルゴン１ｏｏｃｃ／分（いずれも標準状態
換算）の混合ガスで、その供給量は１２０ｃｃ／分とし
た。またこのときの反応容器内のガス圧は４００Ｔｏｒ
ｒとした。Example I i1 Using the apparatus shown in Figure 1, w-gh gold alloy Th was used as the electrode.
1% by weight), and an arc was generated at 22 V DC and 3 A. The gas is vaporized acetone 4 cc/min, hydrogen 16
cc/min, argon 1 oocc/min (all converted to standard conditions), and the supply rate was 120 cc/min. Also, the gas pressure inside the reaction vessel at this time was 400 Torr.
It was set as r.
基板はシリコンウェハーを用い、その表面温度は約６５
０°Ｃである。基板とアーク放電の電極先端の距離は約
４ｍｍとした。アークの発生している電極間の距離は５
ｍａ＋である。アーク放電のガス温度は最高部で約３０
００°Ｃと推定される。A silicon wafer is used as the substrate, and its surface temperature is approximately 65°C.
It is 0°C. The distance between the substrate and the tip of the electrode for arc discharge was approximately 4 mm. The distance between the electrodes where the arc is occurring is 5
It is ma+. The gas temperature of arc discharge is approximately 30℃ at the highest point.
Estimated to be 00°C.
上記の条件で１時間操作を＃ｓ、続したところ、基板上
に厚さ８ｇｍのダイヤモンド膜が析出した。When the operation was continued for 1 hour under the above conditions, a diamond film with a thickness of 8 gm was deposited on the substrate.
電子線回折とラマン分光分析によりダイヤモンドである
ことが確認された。It was confirmed to be a diamond by electron diffraction and Raman spectroscopy.
実施例２
実施例１のアセトンの代りにメタンを用いた外は実施例
１と同様の条件でダイヤモンドを析出した。結果は１時
間で厚さ３ｇａ＋のダイヤモンド膜が生成した。Example 2 Diamond was deposited under the same conditions as in Example 1 except that methane was used instead of acetone. As a result, a diamond film with a thickness of 3 ga+ was formed in 1 hour.
実施例３
電極としてタングステン金属を用い、ガスは水素ガスの
みを導入口４より５０ｃｃ／分で供給し、気化したメチ
ルアルコールは第１図の反応容器の側面で電極の上部に
別に設けた導入口より ３ｃｃ／分で供給した。そして
反応容器内の圧力は７８０Ｔｏｒｒとした。アーク電圧
は４０Ｖ、電流は５Ａとした。Example 3 Tungsten metal was used as the electrode, and only hydrogen gas was supplied from the inlet 4 at a rate of 50 cc/min, and the vaporized methyl alcohol was supplied through the inlet separately provided above the electrode on the side of the reaction vessel as shown in Figure 1. It was supplied at a rate of 3 cc/min. The pressure inside the reaction vessel was set at 780 Torr. The arc voltage was 40V and the current was 5A.
アーク放電帯の水素ガスの温度は３５００℃程度と推定
され、基板温度約７５０°Ｃである。The temperature of hydrogen gas in the arc discharge zone is estimated to be about 3500°C, and the substrate temperature is about 750°C.
この条件で１時間操作したところシリコンウェハー基板
上に膜厚的１２ ｇ ｒａのダイヤモンド膜が析出した
。After operating under these conditions for 1 hour, a diamond film with a thickness of 12 gra was deposited on the silicon wafer substrate.
発明の効果
本発明によれば、これまでより一層早い速度でダイヤモ
ンドを析出させることができた。そしてアーク放電は何
ら支障なく継続することができた。アーク放電はガスを
高い温度に上げることができるので、水素ガスの励起に
は極めて有効であることがわかった。Effects of the Invention According to the present invention, diamond could be deposited at a faster rate than ever before. The arc discharge was able to continue without any problems. Arc discharge has been found to be extremely effective for exciting hydrogen gas, as it can raise the gas to high temperatures.
第１図は本発明方法の実施に使用される装置の１例を示
す断面概略図である。FIG. 1 is a schematic cross-sectional view showing one example of an apparatus used to carry out the method of the present invention.
Claims (1)
ダイヤモンドを合成する方法において、ガスをタングス
テン系の電極間に発生させたアーク放電帯を通すことに
より、分解あるいは励起することを特徴とする気相法に
よるダイヤモンド合成法。A method for synthesizing diamond by vapor phase decomposition of an organic compound in an atmosphere containing hydrogen gas, in which the gas is decomposed or excited by passing the gas through an arc discharge zone generated between tungsten electrodes. Diamond synthesis method using phase method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18238086A JPS63139095A (en) | 1986-08-02 | 1986-08-02 | Method for synthesizing diamond by vapor phase process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18238086A JPS63139095A (en) | 1986-08-02 | 1986-08-02 | Method for synthesizing diamond by vapor phase process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63139095A true JPS63139095A (en) | 1988-06-10 |
Family
ID=16117299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18238086A Pending JPS63139095A (en) | 1986-08-02 | 1986-08-02 | Method for synthesizing diamond by vapor phase process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63139095A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992019791A1 (en) * | 1991-05-07 | 1992-11-12 | Houston Advanced Research Center | Halogen-assisted chemical vapor deposition of diamond |
-
1986
- 1986-08-02 JP JP18238086A patent/JPS63139095A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316795A (en) * | 1990-05-24 | 1994-05-31 | Houston Advanced Research Center | Halogen-assisted chemical vapor deposition of diamond |
| WO1992019791A1 (en) * | 1991-05-07 | 1992-11-12 | Houston Advanced Research Center | Halogen-assisted chemical vapor deposition of diamond |
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