JPH0481552B2 - - Google Patents
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- Publication number
- JPH0481552B2 JPH0481552B2 JP61264718A JP26471886A JPH0481552B2 JP H0481552 B2 JPH0481552 B2 JP H0481552B2 JP 61264718 A JP61264718 A JP 61264718A JP 26471886 A JP26471886 A JP 26471886A JP H0481552 B2 JPH0481552 B2 JP H0481552B2
- Authority
- JP
- Japan
- Prior art keywords
- phase synthesis
- diamond
- substrate
- carbon
- 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.)
- Expired - Lifetime
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 239000010432 diamond Substances 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 29
- 229910003460 diamond Inorganic materials 0.000 claims description 29
- 238000003786 synthesis reaction Methods 0.000 claims description 28
- 239000012808 vapor phase Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 description 29
- 239000000758 substrate Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 27
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 238000010586 diagram Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 hydrocarbon ions Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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気相合成法に関し、詳
細にはダイヤモンド粒子や薄膜を安価に得ること
のできる気相合成法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for vapor phase synthesis of diamond, and more particularly to a method for vapor phase synthesis that allows diamond particles and thin films to be obtained at low cost.
［従来の技術］
ダイヤモンドは、高硬度であることを利用して
古くは切削工具用途を中心に広く使用されてき
た。一方近年では、熱伝導度が大きいこと、不純
物ドーピングにより半導体として利用可能性があ
ること等に着目され、前者の特性を利用するもの
としてIC（集積回路）基板のヒートシンク（冷却
用放熱器）への適用が検討され、また後者の特性
を利用するものとして半導体素子等の電子技術分
野にも応用されるに至り、ダイヤモンドを形成す
る為の技術が急速に開発されつつある。[Prior Art] Diamond has long been widely used mainly in cutting tools because of its high hardness. On the other hand, in recent years, attention has been focused on its high thermal conductivity and its potential to be used as a semiconductor by doping with impurities, and the former is being used as a heat sink (cooling radiator) for IC (integrated circuit) boards. The application of diamond has been studied, and the latter property has also been applied to the field of electronic technology such as semiconductor devices, and techniques for forming diamond are being rapidly developed.
ダイヤモンドの合成法としては、黒鉛を炭素原
料とし、Ni，Cr，Mn等を触媒として４〜７万気
圧、1000〜2000℃の高温・高圧で行なう高圧法が
知られているが、その他気体状炭化水素を炭素原
料として低圧条件下で行なう気相合成法も開発さ
れている。気相合成法によるダイヤモンドの合成
は、高圧法と比べてダイヤモンドの結晶が小さく
なるという欠点が従来より指摘されてきたが、上
述した様な電子技術分野への応用が進められる
と、却つて薄膜の形成が容易であるという利点が
着目され、有用な技術であると位置付けられてい
る。 A known method for synthesizing diamond is the high-pressure method in which graphite is used as a carbon raw material and Ni, Cr, Mn, etc. are used as catalysts at high temperatures and pressures of 40,000 to 70,000 atm and 1,000 to 2,000°C. A gas phase synthesis method using hydrocarbons as a carbon feedstock under low pressure conditions has also been developed. It has been pointed out that the disadvantage of diamond synthesis using the vapor phase synthesis method is that the diamond crystals are smaller compared to the high-pressure method. The advantage of easy formation has attracted attention, and it has been positioned as a useful technology.
第２図は従来の気相合成装置の一例を示す概略
説明図である。当該装置はマイクロ波を応用した
技術であり、その概略は下記の如くである。 FIG. 2 is a schematic explanatory diagram showing an example of a conventional vapor phase synthesis apparatus. The device is a technology that applies microwaves, and its outline is as follows.
２図において、マグネトロン発振機１から発振
されたマイクロ波（2.45GHz）は、アイソレータ
２、パワーモニタ３、チユーナ４及び導波管５を
この記載順序で導かれ、前記導波管５を貫通して
設けられる石英製の反応管６内に設置された基板
７に照射される。前記基板７としてはTa，Co，
Ｗ，Mo等の金属材料が用いられる場合もある
が、一般的にはSiウエハが用いられ、該基板７は
石英製の支持台９によつて所定位置に配置されて
いる。そして反応管６内には反応管入口１１側か
ら、H2ガスとCH4ガスを所定割合に混合（例え
ばCH41％−H299％）した混合ガスが約
100SCCM（Standard Cubic Centimeters per
Minute）の流量で導入される。導入された混合
ガスは排気口１３側から所定量吸引排気され、反
応管６内は予め定めた圧力（例えば40〜50Torr）
とされる。 In Figure 2, the microwave (2.45 GHz) oscillated from the magnetron oscillator 1 is guided through the isolator 2, power monitor 3, tuner 4, and waveguide 5 in the order shown, and passes through the waveguide 5. A substrate 7 placed in a quartz reaction tube 6 is irradiated with light. The substrate 7 is made of Ta, Co,
Although metal materials such as W and Mo may be used, generally a Si wafer is used, and the substrate 7 is placed at a predetermined position by a support base 9 made of quartz. In the reaction tube 6, from the reaction tube inlet 11 side, a mixed gas of H 2 gas and CH 4 gas mixed at a predetermined ratio (for example, CH 4 1% - H 2 99%) is supplied.
100SCCM (Standard Cubic Centimeters per
It is introduced at a flow rate of 1 minute). A predetermined amount of the introduced mixed gas is sucked and exhausted from the exhaust port 13 side, and the pressure inside the reaction tube 6 is maintained at a predetermined pressure (for example, 40 to 50 Torr).
It is said that
この様にして混合ガスが供給された反応管６内
にマイクロ波の様な振動電波（約300W）が導入
されると、高エネルギー電子によつて混合ガス成
分分子が原子・イオン・ラジカルに分解され、反
応管６内には定常的なプラズマが発生する。前記
基板７はプラズマ発生領域１４に配置されてお
り、当該基板７上には混合ガス中の炭素を原料と
してダイヤモンド結晶が析出する。そして基板７
の種類や処理条件に応じて微結晶又は薄膜等の様
に異なつた形態のダイヤモンドが得られる。 When oscillating radio waves (approximately 300 W) such as microwaves are introduced into the reaction tube 6 into which the mixed gas is supplied in this way, the mixed gas component molecules are decomposed into atoms, ions, and radicals by high-energy electrons. As a result, a steady plasma is generated within the reaction tube 6. The substrate 7 is placed in the plasma generation region 14, and diamond crystals are deposited on the substrate 7 using carbon in the mixed gas as a raw material. and board 7
Diamonds can be obtained in different forms, such as microcrystals or thin films, depending on the type of diamond and processing conditions.
第２図に示したダイヤモンド気相合成装置にお
いて、例えば基板としてSiウエハを用いた場合に
は、上述した処理条件で基板温度が約850℃とな
り、基板７上に約0.3μm／時間の成長速度で結晶
性ダイヤモンドが析出する。尚第２図中の参照符
号１はプランジヤーであり、基板７が正確にプラ
ズマ発生領域１４の中央に位置する様にマイクロ
波の反射を調整する為のものである。又参照符号
２０で示されている部材はアプリケーターであ
り、冷却水を供給管２１から供給しつつ排出管２
２から排出して反応管６が過度に加熱されるのを
防ぐ機能を果たす。 In the diamond vapor phase synthesis apparatus shown in FIG. 2, if a Si wafer is used as the substrate, the substrate temperature will be approximately 850°C under the above-mentioned processing conditions, and the growth rate on the substrate 7 will be approximately 0.3 μm/hour. Crystalline diamond is precipitated. Reference numeral 1 in FIG. 2 is a plunger, which is used to adjust the reflection of microwaves so that the substrate 7 is accurately located at the center of the plasma generation region 14. Further, a member indicated by the reference numeral 20 is an applicator, which supplies cooling water from the supply pipe 21 and discharges it from the discharge pipe 2.
2 to prevent the reaction tube 6 from being excessively heated.
［発明が解決しようとする問題点］
第２図に示した気相合成装置における炭素原料
としては、上述したメタン（CH4）の他、アセチ
レン、エチレン、エタン、ベンゼン等の様な気体
状炭化水素が一般的に用いられていた。[Problems to be Solved by the Invention] In addition to the above-mentioned methane (CH 4 ), carbonized gases such as acetylene, ethylene, ethane, and benzene are used as carbon raw materials in the gas phase synthesis apparatus shown in FIG. Hydrogen was commonly used.
しかしながらこれらの気体状炭化水素を炭素原
料として用いた場合には、炭素濃度の制御が比較
的容易であるという点で好ましい結果を得ること
ができるが、次の様な欠点があることも事実であ
る。即ち上述した様な気体状炭化水素を炭素原料
として用いた場合には、これらの炭化水素は比
較的高価である、炭化水素を供給する為の設備
（図示していない）を反応装置に付加する必要が
あり、流量制御用配管やバルブ等の装置価格が高
価となる、ダイヤモンドの気相合成の開始・終
了時に、炭化水素が供給される配管内を不活性ガ
スで置換する手間が必要である、等の問題点があ
つた。 However, when these gaseous hydrocarbons are used as carbon raw materials, favorable results can be obtained in that the carbon concentration can be controlled relatively easily, but it is also true that there are the following drawbacks. be. That is, when gaseous hydrocarbons such as those mentioned above are used as carbon raw materials, these hydrocarbons are relatively expensive, and equipment (not shown) for supplying the hydrocarbons must be added to the reactor. The cost of equipment such as flow rate control piping and valves is expensive, and it is time-consuming to replace the inside of the piping that supplies hydrocarbons with inert gas at the start and end of diamond vapor phase synthesis. , and other problems arose.
本発明はこれらの問題点を解決する為になされ
たものであつて、その目的とするところは、ダイ
ヤモンドを安価に合成し得ると共に、合成装置を
比較的簡単な構成にし得る様な気相合成法を提供
することにある。 The present invention was made in order to solve these problems, and its purpose is to synthesize diamond at a low cost and to provide a gas phase synthesis method that allows a synthesis apparatus to be constructed with a relatively simple structure. It is about providing law.
［問題点を解決する為の手段］
上記目的を達成し得た本発明とは、ダイヤモン
ドの気相合成に当たり、炭素原料として固体炭素
を用い、該固体炭素を水素プラズマ雰囲気中で高
温に保ちつつ気相合成を行なう点に要旨を有する
ダイヤモンドの気相合成法である。[Means for Solving the Problems] The present invention, which has achieved the above object, uses solid carbon as a carbon raw material in vapor phase synthesis of diamond, and maintains the solid carbon at a high temperature in a hydrogen plasma atmosphere. This is a vapor phase synthesis method for diamond, which has the gist of performing vapor phase synthesis.
［作用］
本発明は上述の如く構成されるが、要は炭素原
料としてCH4ガスその他の気体状炭化水素を用い
る代りに、固体炭素を用いる点に最大の特徴を有
するものである。用いる固体炭素の種類や形状に
ついては何ら限定されないが、例えばグラフアイ
ト（黒鉛）や粉末炭素等は比較的容易に入手でき
且つ安価であり、最も好都合である。また表面積
を増大すると共に水素ガスの侵入を助ける為に多
孔質としたものが推奨される。[Function] The present invention is constructed as described above, but its main feature is that solid carbon is used instead of CH 4 gas or other gaseous hydrocarbons as the carbon raw material. There are no restrictions on the type or shape of the solid carbon used, but graphite, powdered carbon, etc. are most convenient, as they are relatively easily available and inexpensive. In addition, it is recommended that the material be porous to increase the surface area and to help hydrogen gas penetrate.
この様な固体炭素をプラズマ発生領域に予め設
置しておき、H2単独ガスを供給して気相合成を
行なうことによつて、前記固体炭素は水素プラズ
マ雰囲気中で高温に保たれ、恐らくは炭化水素等
を発生して基板上にダイヤモンド粒子や薄膜が得
られるのである。 By placing such solid carbon in the plasma generation area in advance and performing vapor phase synthesis by supplying H 2 gas alone, the solid carbon is kept at a high temperature in the hydrogen plasma atmosphere and is likely to become carbonized. Hydrogen and other gases are generated to form diamond particles and a thin film on the substrate.
本発明方法ではCH4ガスその他の炭化水素ガス
の様な比較的高価な炭素原料を用いることなく、
グラフアイトや粉末炭素等の比較的安価な炭素原
料を用いる様にしたので、従来よりも更に安価に
ダイヤモンドを合成することが可能となる。また
供給するガスはH2ガス単独でよく、気体状炭化
水素を供給していた為に必要とされていた気体原
料混合制御機構や複雑な配管・バルブ類が不要と
なり、本発明方法を実施する為の気相合成装置自
体も簡単な構成となり、生産コストの低減に寄与
し得るところが大きい。更に上述の理由によつ
て、炭化水素ガス配管内を不活性ガスで置換する
手間も省ける。 The method of the present invention does not use relatively expensive carbon raw materials such as CH 4 gas or other hydrocarbon gases.
Since relatively inexpensive carbon raw materials such as graphite and powdered carbon are used, it becomes possible to synthesize diamond at a lower cost than before. In addition, the gas to be supplied may be H 2 gas alone, eliminating the need for a gaseous raw material mixing control mechanism and complicated piping and valves that were required when gaseous hydrocarbons were supplied, making it possible to carry out the method of the present invention. The vapor phase synthesis apparatus itself has a simple configuration, which greatly contributes to reducing production costs. Furthermore, for the above-mentioned reasons, it is also possible to save the effort of replacing the inside of the hydrocarbon gas pipe with an inert gas.
尚本発明方法においては、プラズマ雰囲気中の
炭素濃度の制御は、気体状炭化水素を用いた場合
と比べて多少困難さを増すが、固体炭素原料の表
面性状や温度、H2ガスの圧力や流量及びマイク
ロ波の出力等の条件を独立変数として予め合成ダ
イヤモンドの性状に与える影響を調査しておけ
ば、実操業におけるダイヤモンド粒子・薄膜の形
態制御は比較的簡単に実施できる。 In the method of the present invention, controlling the carbon concentration in the plasma atmosphere is somewhat more difficult than in the case of using gaseous hydrocarbons, but it is difficult to control the carbon concentration in the plasma atmosphere depending on the surface properties and temperature of the solid carbon raw material, the pressure of H2 gas, etc. If the effects of conditions such as flow rate and microwave output on the properties of synthetic diamond are investigated in advance as independent variables, it is relatively easy to control the morphology of diamond particles and thin films in actual operations.
［実施例］
第１図は本発明方法を実施する為に構成される
気相合成装置例の要部を示す概略説明図である。
第１図に示した装置における構成は基本的には第
２図に示した装置の構成と同様であり、対応する
部分には同一の参照番号を付すことにより重複説
明を回避する。尚前記第２図に示したマグネトロ
ン発振機１、アイソレータ２、パワーモニタ３、
チユーナ４は説明の便宜上第１図では省略した
が、これらの部材は本発明方法を実施する際にも
必要であるのは言う迄もない。[Example] FIG. 1 is a schematic explanatory diagram showing the main parts of an example of a vapor phase synthesis apparatus configured to carry out the method of the present invention.
The configuration of the apparatus shown in FIG. 1 is basically the same as the configuration of the apparatus shown in FIG. 2, and corresponding parts are given the same reference numerals to avoid redundant explanation. Furthermore, the magnetron oscillator 1, isolator 2, power monitor 3, shown in FIG.
Although the tuner 4 is omitted in FIG. 1 for convenience of explanation, it goes without saying that these members are necessary when carrying out the method of the present invention.
第１図において石英製の反応管６内のブラズマ
発生領域１４内には支持台９上に基板７が配置さ
れると共に、該基板７の近傍（第１図では上方）
には炭素原料としての炭素板２５が同じく前記支
持台９によつて配置される。 In FIG. 1, a substrate 7 is placed on a support stand 9 within a plasma generation region 14 in a reaction tube 6 made of quartz, and near the substrate 7 (in the upper part in FIG. 1).
A carbon plate 25 as a carbon raw material is also placed on the support base 9.
第１図に示した装置において、入口１１側から
反応管６内にH2ガスを導入すると共に、導波管
５からマイクロ波を導入する。そうすると反応管
６内は水素プラズマ雰囲気となり炭素−水素プラ
ズマ反応が進行して高温に保たれる。その結果、
炭化水素ス、炭化水素イオン、炭化水素ラジカル
等が発生すると共に、分子状水素の分解により原
子状水素が発生し、これらが基板７上に移送され
ることにより、基板７上にダイヤモンド粒子やダ
イヤモンド薄膜が析出する。 In the apparatus shown in FIG. 1, H 2 gas is introduced into the reaction tube 6 from the inlet 11 side, and microwaves are introduced from the waveguide 5. Then, the inside of the reaction tube 6 becomes a hydrogen plasma atmosphere, and a carbon-hydrogen plasma reaction progresses to maintain a high temperature. the result,
Hydrocarbons, hydrocarbon ions, hydrocarbon radicals, etc. are generated, and atomic hydrogen is generated by the decomposition of molecular hydrogen, and these are transferred onto the substrate 7, so that diamond particles and diamonds are formed on the substrate 7. A thin film is deposited.
第３図は本発明方法を実施する為に構成される
気相合成装置の他の例を示す概略説明図である。
この装置では、図示する様に反応管６が水平に配
置されると共に、該反応管６内には支持台９が設
置され、この支持台９上に炭素粉末２６が載置さ
れ、更に炭素粉末よりも反応管６の下流側（第３
図における右側）には基板７が設置される。この
様な装置においても、前記第１図と同様の原理で
基板７上にダイヤモンド粒子やダイヤモンド薄膜
を析出することができる。 FIG. 3 is a schematic explanatory diagram showing another example of a vapor phase synthesis apparatus configured to carry out the method of the present invention.
In this device, as shown in the figure, a reaction tube 6 is arranged horizontally, a support stand 9 is installed inside the reaction tube 6, carbon powder 26 is placed on this support stand 9, and carbon powder 26 is placed on the support stand 9. downstream of the reaction tube 6 (third
A substrate 7 is installed on the right side in the figure. Even in such an apparatus, diamond particles or a diamond thin film can be deposited on the substrate 7 using the same principle as shown in FIG. 1.
本発明者らは、前記第３図の気相合成装置を用
いて実験を行なつた。即ちマイクロの出力を
700Wとし、基板７を導波管６の中央部よりも少
しずらせて置き基板７の温度が800℃となる様に
し、反応管６の入口１１側からH2ガスを
100SCCMの流量で供給した。尚反応管６内の圧
力は、H2ガスを排気口１３側から所定量排気す
ることによつて70Torrに調整した。そして反応
を７時間進行させたところ、基板７上に直径約
2μmのダイヤモンド微粒子が析出した。 The present inventors conducted an experiment using the vapor phase synthesis apparatus shown in FIG. 3 above. In other words, the output of the micro
700W, the substrate 7 was placed slightly offset from the center of the waveguide 6 so that the temperature of the substrate 7 was 800℃, and H 2 gas was introduced from the inlet 11 side of the reaction tube 6.
It was supplied at a flow rate of 100 SCCM. The pressure inside the reaction tube 6 was adjusted to 70 Torr by exhausting a predetermined amount of H 2 gas from the exhaust port 13 side. When the reaction was allowed to proceed for 7 hours, a diameter of approximately
Diamond fine particles of 2 μm were precipitated.
本発明方法と実施する為の気相合成装置は前記
第１図及び第３図に示した構成に限られず、その
他各種の構成を採用することもできる。例えば下
記第４〜８図はその一例であり以下これらの図面
を参照しつつ説明するが、基本的な原理は第１，
３図の場合と同様であるので構成の違いを簡単に
説明するにとどめる。 The vapor phase synthesis apparatus for carrying out the method of the present invention is not limited to the configuration shown in FIGS. 1 and 3, and various other configurations may also be adopted. For example, Figures 4 to 8 below are examples of this, and will be explained below with reference to these figures, but the basic principles are as follows:
Since this is the same as the case shown in FIG. 3, the difference in configuration will only be briefly explained.
まず第４図に示した気相合成装置は、反応室２
７内に基板７及び炭素板２５を対向して配置した
例である。この装置においては、H2ガスは供給
管２８から反応室２７内に供給されると共に排気
管２９から排気され、一方マイクロ波が導波管５
から導入され、反応室２７内には基板７及び炭素
板２５を包む様にして水素プラズマを発生させる
ものである。尚第４図中参照符号３０はマイクロ
波導入用ウインドウである。 First, the gas phase synthesis apparatus shown in FIG.
This is an example in which the substrate 7 and the carbon plate 25 are arranged facing each other in the carbon plate 7. In this device, H2 gas is supplied into the reaction chamber 27 from a supply pipe 28 and exhausted from an exhaust pipe 29, while microwaves are emitted from a waveguide 5.
Hydrogen plasma is introduced into the reaction chamber 27 so as to surround the substrate 7 and the carbon plate 25. Note that reference numeral 30 in FIG. 4 is a window for introducing microwaves.
次に第５図に示した気相合成装置は第４図に示
した装置とほぼ同様であり、相違点は炭素板２５
の代りに炭素粉末２６を用いた点である。 Next, the vapor phase synthesis apparatus shown in FIG. 5 is almost the same as the apparatus shown in FIG. 4, and the difference is that the carbon plate 25
The point is that carbon powder 26 was used instead of.
更に、第６図に示した気相合成装置は、導波管
５を２箇所設けた例である。即ち、反応管６の上
流側に配置した導波管５ａによつて炭素粉末２６
を加熱して水素プラズマと反応させると共に、反
応管６の下流側に配置した導波管５ｂによつて基
板７の周囲を水素プラズマ雰囲気とするものであ
る。そして生じた炭化水素・ラジカル・イオン種
等がH2ガスによつて基板７上に移送され、基板
７上にダイヤモンドが析出する。 Furthermore, the vapor phase synthesis apparatus shown in FIG. 6 is an example in which waveguides 5 are provided at two locations. That is, the carbon powder 26 is
is heated to react with hydrogen plasma, and a hydrogen plasma atmosphere is created around the substrate 7 by means of a waveguide 5b disposed downstream of the reaction tube 6. The generated hydrocarbons, radicals, ion species, etc. are transferred onto the substrate 7 by the H 2 gas, and diamond is deposited on the substrate 7.
第７図に示した気相合成装置では、炭素粉末２
６をプラズマ発生領域１４中におき、H2ガスが
導入される反応管６の下流側を比較的大きな容量
を有する反応室２７ａとし、この反応室２７ａ内
に面積を広くした基板７を設置し、この基板７上
にダイヤモンドを析出させるものである。尚この
際基板７は補助加熱用ヒータ３３で800〜1000℃
に加熱される。 In the vapor phase synthesis apparatus shown in Fig. 7, carbon powder 2
6 is placed in the plasma generation region 14, the downstream side of the reaction tube 6 into which H 2 gas is introduced is made into a reaction chamber 27a having a relatively large capacity, and a substrate 7 with a wide area is installed within this reaction chamber 27a. , diamond is deposited on this substrate 7. At this time, the substrate 7 is heated to 800 to 1000°C by the auxiliary heater 33.
is heated to.
第８図に示した気相合成装置では、反応室２７
の内壁に断熱材３４を内張りすると共に、該断熱
材３４上に炭素板２５を配置するものである。そ
してH2ガスを供給管２８から反応室２７内に供
給すると共に、導波管５からマイクロ波を導入す
ることによつて、反応室２７内を高温の水素プラ
ズマ雰囲気として基板７上にダイヤモンドを析出
させる。 In the gas phase synthesis apparatus shown in FIG.
A heat insulating material 34 is lined on the inner wall of the heat insulating material 34, and a carbon plate 25 is placed on the heat insulating material 34. Then, by supplying H 2 gas into the reaction chamber 27 from the supply pipe 28 and introducing microwaves from the waveguide 5, the inside of the reaction chamber 27 is made into a high-temperature hydrogen plasma atmosphere, and diamond is deposited on the substrate 7. Let it precipitate.
［発明の効果］
以上述べた如く本発明方法によれば、炭素原料
として安価な固体炭素を用いる様にしたので、ダ
イヤモンドが安価に合成できると共に、気相合成
装置の構成も比較的簡単なものとすることがで
き、従来の問題点を一挙に解決し得た。[Effects of the Invention] As described above, according to the method of the present invention, cheap solid carbon is used as the carbon raw material, so diamond can be synthesized at low cost, and the configuration of the vapor phase synthesis apparatus is relatively simple. It was possible to solve all the problems of the conventional method in one fell swoop.
第１図は本発明方法を実施する為に構成される
気相合成装置例の要部を示す概略説明図、第２図
は従来の気相合成装置の一例を示す概略説明図、
第３図は本発明方法を実施する為に構成される気
相合成装置の他の例を示す概略説明図、第４〜８
図は本発明方法を実施する為に構成される気相合
成装置の各種の例を示す概略説明図である。
１…マグネトロン発振機、５，５ａ，５ｂ…導
波管、６…反応管、７…基板、９…支持台、１４
…プラズマ発生領域、１５…プランジヤー、２５
…炭素板、２６…炭素粉末、２７，２７ａ…反応
室。
FIG. 1 is a schematic explanatory diagram showing the main parts of an example of a vapor phase synthesis apparatus configured to carry out the method of the present invention, FIG. 2 is a schematic explanatory diagram showing an example of a conventional vapor phase synthesis apparatus,
FIG. 3 is a schematic explanatory diagram showing another example of a vapor phase synthesis apparatus configured to carry out the method of the present invention;
The figures are schematic explanatory diagrams showing various examples of vapor phase synthesis apparatus configured to carry out the method of the present invention. 1... Magnetron oscillator, 5, 5a, 5b... Waveguide, 6... Reaction tube, 7... Substrate, 9... Support stand, 14
...Plasma generation area, 15...Plunger, 25
...Carbon plate, 26...Carbon powder, 27, 27a...Reaction chamber.
Claims (1)
として固体炭素を用い、該固体炭素を水素プラズ
マ雰囲気中で高温に保ちつつ気相合成を行なうこ
とを特徴とするダイヤモンドの気相合成法。1. A method for vapor phase synthesis of diamond, which is characterized by using solid carbon as a carbon raw material and performing vapor phase synthesis while maintaining the solid carbon at a high temperature in a hydrogen plasma atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61264718A JPS63117993A (en) | 1986-11-05 | 1986-11-05 | Device for synthesizing diamond in vapor phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61264718A JPS63117993A (en) | 1986-11-05 | 1986-11-05 | Device for synthesizing diamond in vapor phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63117993A JPS63117993A (en) | 1988-05-21 |
| JPH0481552B2 true JPH0481552B2 (en) | 1992-12-24 |
Family
ID=17407217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61264718A Granted JPS63117993A (en) | 1986-11-05 | 1986-11-05 | Device for synthesizing diamond in vapor phase |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63117993A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635254A (en) * | 1993-01-12 | 1997-06-03 | Martin Marietta Energy Systems, Inc. | Plasma spraying method for forming diamond and diamond-like coatings |
| US5560897A (en) * | 1993-10-07 | 1996-10-01 | The Regents Of The University Of California Office Of Technology Transfer | Plasma-assisted conversion of solid hydrocarbon to diamond |
| US5578901A (en) * | 1994-02-14 | 1996-11-26 | E. I. Du Pont De Nemours And Company | Diamond fiber field emitters |
| US6020677A (en) * | 1996-11-13 | 2000-02-01 | E. I. Du Pont De Nemours And Company | Carbon cone and carbon whisker field emitters |
| JP4744118B2 (en) * | 2004-09-30 | 2011-08-10 | 株式会社神戸製鋼所 | Single crystal diamond synthesis substrate and method for producing single crystal diamond film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62158195A (en) * | 1985-12-27 | 1987-07-14 | Natl Inst For Res In Inorg Mater | Synthesizing method of diamond |
-
1986
- 1986-11-05 JP JP61264718A patent/JPS63117993A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63117993A (en) | 1988-05-21 |
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