JPH06104599B2 - Diamond film manufacturing method - Google Patents
Diamond film manufacturing methodInfo
- Publication number
- JPH06104599B2 JPH06104599B2 JP61226237A JP22623786A JPH06104599B2 JP H06104599 B2 JPH06104599 B2 JP H06104599B2 JP 61226237 A JP61226237 A JP 61226237A JP 22623786 A JP22623786 A JP 22623786A JP H06104599 B2 JPH06104599 B2 JP H06104599B2
- Authority
- JP
- Japan
- Prior art keywords
- discharge
- substrate
- diamond
- diamond film
- 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.)
- Expired - Fee Related
Links
- 239000010432 diamond Substances 0.000 title claims description 33
- 229910003460 diamond Inorganic materials 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000007789 gas Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 230000007423 decrease Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- -1 and in all cases Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000002245 particle Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ダイヤモンド膜の製造方法、更に詳細には中
減圧〜大気圧若しくはそれ以上の炭化水素・水素混合ガ
スをグロー・アーク移行領域の放電下に反応させる新規
なCVD法によるダイヤモンド膜の極めて経済的製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a diamond film, and more specifically, to a hydrocarbon-hydrogen mixed gas at medium to low atmospheric pressure or atmospheric pressure in a glow-arc transition region. The present invention relates to a very economical method for producing a diamond film by a novel CVD method of reacting under discharge.
（従来の技術） 本願発明等は、従来の気相成長法（即ち、CVD法）にお
いて電子シャワーの作用下にダイヤモンド結晶核の生成
成長によりダイヤモンド薄膜が形成されることを見出し
特許出願した（特開昭60−221395号公報、尚この方法は
本願発明者等によりエレクトロン アシスティド ケミ
カル ベーパー デポズィション即ち、EACVDと命名さ
れ、論文アプライドフィズイクス レター 第46巻第２
号 第146〜147頁に受理公開された）。(Prior Art) The inventors of the present invention found that a diamond thin film is formed by the generation and growth of diamond crystal nuclei under the action of an electron shower in the conventional vapor phase growth method (that is, the CVD method) and applied for a patent (Patent application This method is named as Electron Assisted Chemical Vapor Deposition, or EACVD, by the inventors of the present application, and the paper, Applied Physics Letter, Vol. 46, Vol.
No. 146-147 accepted and published).
また、放電空間でダイヤモンドを合成する試みもあり、
イオンビーム法は炭素正イオンを高真空中で加速せしめ
て陰極表面に衝突させ、ダイヤモンド膜を得たと報告さ
れており、プラズマCVD法は高周波プラズマ空間で炭素
正イオンを生成せしめて基体の表面にダイヤモンド膜を
形成せしめるもので、いずれもダイヤモンドは炭素正イ
オンに因り形成されるとしている。There are also attempts to synthesize diamond in the discharge space,
It is reported that the ion beam method accelerates carbon positive ions in a high vacuum and collides them with the cathode surface to obtain a diamond film.The plasma CVD method generates carbon positive ions in a high-frequency plasma space and deposits them on the surface of the substrate. It forms a diamond film, and in all cases, diamond is formed due to carbon positive ions.
更に、直流グロー放電法として知られる方法は、圧力1/
10〜1/100トールの高真空下に基板は常に陰極側に設置
されている。これもダイヤモンドは炭素正イオンによる
効果を前提としたものである。In addition, the method known as the direct current glow discharge method has a pressure of 1 /
The substrate is always placed on the cathode side under a high vacuum of 10 to 1/100 Torr. This is also based on the effect of positive carbon ions on diamond.
（発明が解決しようとする問題点） 従来のCVD法は、特別な装置を必要とし、操作も簡単容
易でなく、反応速度も遅く実用的とは言えない方法であ
った。(Problems to be Solved by the Invention) The conventional CVD method is a method that requires a special apparatus, is not easy and easy to operate, has a slow reaction rate, and is not practical.
そこで、本発明者等は前記EACVD法を更に深く研究した
結果、原料炭化水素の高い濃度下にグロー・アーク移行
領域の放電下、陽極基板にダイヤモンド膜が形成される
という驚くべき事実を見いだし本発明を完成したもので
ある。この場合陰極には黒鉛状炭素又は黒鉛の析出がみ
られるが、従来の観念で炭素正イオンによりダイヤモン
ドが生成するものとして陰極のみに拘泥しておれば、本
発明は見いだし得なかったであろう。Therefore, as a result of a deeper study of the EACVD method, the present inventors have found the surprising fact that a diamond film is formed on an anode substrate under discharge in a glow-arc transition region under a high concentration of a raw material hydrocarbon. The invention has been completed. In this case, graphite-like carbon or graphite is observed to be deposited on the cathode, but the present invention would not have been able to be found if the conventional idea was to limit the production of diamond to carbon positive ions only to the cathode. .
それ故、本発明の目的は、簡単な装置で、容易な操作に
より、実用に堪える経済的ダイヤモンド膜を製造する方
法を提供するにある。Therefore, it is an object of the present invention to provide a method for producing a practical and economical diamond film by a simple apparatus and an easy operation.
（問題点を解決するための手段） 前記目的を達成するため、本発明に係るダイヤモンド膜
の製造方法は、真空の容器中に、陽極に設定した基板と
これに対向する陰極とを配置し、この容器中に、炭化水
素ガス濃度を0.1〜20容量％に設定した炭化水素ガスと
水素ガスとの混合ガスを、100〜1000トールの圧力下に
導入し、前記基板に対し加熱手段による加熱を行うこと
なく、 （ａ）放電維持電圧を正規グローの場合より高くし、 （ｂ）電流密度を0.1〜10A/cm2に設定し、 （ｃ）放電電流の上昇に伴い放電電圧が減少すると共
に、 （ｄ）放電電流の増減に伴い放電面積が減少する 条件を満たすグロー・アーク移行領域の放電を行うこと
により基板表面にダイヤモンドを生成させるを特徴とす
る。(Means for Solving the Problems) In order to achieve the above object, the method for producing a diamond film according to the present invention, in a vacuum container, a substrate set as an anode and a cathode facing the substrate are arranged, In this container, a mixed gas of hydrocarbon gas and hydrogen gas having a hydrocarbon gas concentration set to 0.1 to 20% by volume was introduced under a pressure of 100 to 1000 torr, and the substrate was heated by a heating means. Without performing (a) the discharge sustaining voltage is higher than that of the normal glow, (b) the current density is set to 0.1 to 10 A / cm 2 , and (c) the discharge voltage decreases as the discharge current increases. (D) The discharge area decreases as the discharge current increases / decreases. It is characterized in that diamond is generated on the substrate surface by performing discharge in a glow-arc transition region that satisfies the condition.
混合ガスの炭化水素ガスの濃度は0.1〜20容量％が好適
である。炭化水素としては飽和、不飽和の炭化水素ガス
より選択出来るが、メタンが好適に使用される。The hydrocarbon gas concentration of the mixed gas is preferably 0.1 to 20% by volume. The hydrocarbon can be selected from saturated and unsaturated hydrocarbon gases, but methane is preferably used.
ガス圧は100〜1000トールが好適に適用出来、このよう
な圧力は、従来予想もされないもので、1/10トール程度
の高い減圧下の従来の方法に比較すると、ダイヤモンド
生成速度は約５〜10倍増加され、ダイヤモンド粒子の大
きさを考慮しなければ、恐らくダイヤモンドの最も経済
的な製造方法と思われる。A gas pressure of 100 to 1000 Torr can be suitably applied, and such a pressure is not expected in the past, and the diamond formation rate is about 5 to 5 compared with the conventional method under a high reduced pressure of about 1/10 Torr. It is increased by a factor of 10 and is probably the most economical way to make diamonds without considering the size of the diamond particles.
ガス流量は、反応容器の容積によって決まるもので、反
応により消耗する原料ガスを補充し、生成するガスを除
去し、前記混合ガス組成を保持するため一定流量で原料
ガスを流すのが好適で、実験反応容器の場合10〜1000SC
CMの範囲で選択された。The gas flow rate is determined by the volume of the reaction vessel, and it is preferable to replenish the raw material gas consumed by the reaction, remove the produced gas, and flow the raw material gas at a constant flow rate to maintain the mixed gas composition, 10 to 1000 SC for experimental reaction vessel
Selected in the CM range.
直流印加電圧は0.5〜5KVで好適に実施出来る。A DC applied voltage of 0.5 to 5 KV can be suitably implemented.
基板温度は水冷下又は水冷せずに室温〜800℃で実施さ
れる。前記EACVD法においては原料ガスを熱分解するた
め反応容器中に加熱装置を設置したが、本発明はこの加
熱装置は必要とせず、かつ熱電子発生用の加熱陰極も必
要とせず、実質的に室温で実施可能であって、陽極基板
は反応時に電子衝撃により温度上昇するので水冷するほ
うが好適で、水冷しないと約800℃に上昇する。The substrate temperature is room temperature to 800 ° C. with or without water cooling. In the EACVD method, a heating device was installed in the reaction vessel to thermally decompose the raw material gas, but the present invention does not require this heating device, and does not require a heating cathode for thermionic generation, and is substantially It can be carried out at room temperature, and the temperature of the anode substrate rises due to electron bombardment during the reaction, so water cooling is preferable, and the temperature rises to about 800 ° C. without water cooling.
（実施例） 次に実施例により本発明を具体的に説明するが、これは
好適な例であって、本発明はこれだけに限定されるもの
でないことは勿論である。(Example) Next, although an Example demonstrates this invention concretely, this is a preferable example and it is needless to say that this invention is not limited to this.
実施例１ 第１図に示すように、鉄製の真空反応容器１に原料ガス
導入管２、排気系３、反応容器１の上部にシールド材４
を介してステンレス鋼製の陰極５を配置し、約3cmの距
離を隔てて下部にステンレス鋼製の陽極６をシールド材
７を介して配置する。陽極は水冷出来るよう構成され
る。陽極表面温度測定用の熱電対８が配置される。ダイ
ヤモンド析出用のモリブデン鋼基板を陽極上に配置し
た。陰極と陽極は高電圧直流電源９に接続される。ま
ず、反応容器を真空にして空気を排除し、原料ガス（メ
タンと水素の混合ガスで、メタンの濃度は10容量％）を
導入し、200トールに保持する。原料ガスは100SCCMの割
合で流した。放電電圧1KV、放電電流400mA、陽極表面温
度70℃にて第４図の写真に示すような陽光性が極間の約
60％（約1.8cm）の高さの放物線形をなしてグロー・ア
ーク移行領域の放電を確認し、この状態を保持した。数
分で約５μのダイヤモンド薄膜が生成した。約20時間連
続放電して約1mmのダイヤモンド薄板が容易に得られ
た。得られたダイヤモンド薄膜の表面の走査型電子顕微
鏡写真を第２図にしめす。極めてなだらかな連続膜であ
ることがわかる。また、薄膜体の反射電子回折像写真が
第３図にしめされ、この計算結果を下記表にしめす。Example 1 As shown in FIG. 1, a raw material gas introduction pipe 2, an exhaust system 3, and a shield material 4 on the upper part of the reaction vessel 1 in a vacuum reaction vessel 1 made of iron.
The cathode 5 made of stainless steel is arranged via the shield material, and the anode 6 made of stainless steel is arranged at the lower part with the shield material 7 interposed at a distance of about 3 cm. The anode is configured to be water cooled. A thermocouple 8 for measuring the surface temperature of the anode is arranged. A molybdenum steel substrate for diamond deposition was placed on the anode. The cathode and the anode are connected to a high voltage DC power supply 9. First, the reaction vessel is evacuated to remove air, and a source gas (mixed gas of methane and hydrogen with a methane concentration of 10% by volume) is introduced and maintained at 200 Torr. The raw material gas was made to flow at a rate of 100 SCCM. At a discharge voltage of 1 KV, a discharge current of 400 mA, and an anode surface temperature of 70 ° C, the positive light as shown in the photograph in Fig.
The discharge in the glow-arc transition region was confirmed by forming a parabola with a height of 60% (about 1.8 cm), and this state was maintained. A diamond film of about 5μ was formed in a few minutes. A diamond thin plate of about 1 mm was easily obtained by continuous discharge for about 20 hours. A scanning electron micrograph of the surface of the obtained diamond thin film is shown in FIG. It can be seen that it is an extremely gentle continuous film. Also, a reflection electron diffraction image photograph of the thin film body is shown in FIG. 3, and the calculation result is shown in the following table.
前記表の計算値より第２図の薄膜はダイヤモンド薄膜で
あることが確認された。 From the calculated values in the above table, it was confirmed that the thin film in FIG. 2 was a diamond thin film.
実施例２ 実施例１における原料ガスの圧力が760トール、ガス流
量は500SCCM、放電電圧5KV、以外は同じ条件で実施し、
20時間で約2mmのダイヤモンド厚膜をえた。Example 2 The same conditions as in Example 1 except that the pressure of the raw material gas was 760 Torr, the gas flow rate was 500 SCCM, and the discharge voltage was 5 KV,
A thick diamond film of about 2 mm was obtained in 20 hours.
（発明の効果） 本発明に係るダイヤモンド膜の製造方法によると、簡単
な設備、容易な操作で安定したダイヤモンド膜が安価に
得られ、薄膜としてはエレクトロニクス方面の半導体製
造原料に、厚膜はダイヤモンド板又は粉末として、例え
ば研磨剤などの工業原料として重要である。(Effects of the Invention) According to the method for producing a diamond film of the present invention, a stable diamond film can be obtained at low cost with simple equipment and easy operation. It is important as a plate or powder, for example, as an industrial raw material such as an abrasive.
第１図は本発明に係るダイヤモンド膜の製造装置の説明
図、第２図はダイヤモンド薄膜の走査型電子顕微鏡によ
る表面写真、第３図はダイヤモンド薄膜の反射電子回折
像写真、第４図は放電状態を示す写真である。 １……反応容器、２……ガス導入管 ３……排気系、４……シールド材 ５……陰極、６……陽極 ７……シールド材、８……熱電対 ９……高電圧直流電源FIG. 1 is an explanatory view of a diamond film manufacturing apparatus according to the present invention, FIG. 2 is a surface photograph of a diamond thin film by a scanning electron microscope, FIG. 3 is a backscattered electron diffraction image photograph of a diamond thin film, and FIG. It is a photograph showing a state. 1 ... Reactor container, 2 ... Gas inlet tube 3 ... Exhaust system, 4 ... Shield material 5 ... Cathode, 6 ... Anode 7 ... Shield material, 8 ... Thermocouple 9 ... High-voltage DC power supply
Claims (3)
れに対向する陰極とを配置し、この容器中に、炭化水素
ガス濃度を0.1〜20容量％に設定した炭化水素ガスと水
素ガスとの混合ガスを、100〜1000トールの圧力下に導
入し、前記基板に対し加熱手段による加熱を行うことな
く、 （ａ）放電維持電圧を正規グローの場合より高くし、 （ｂ）電流密度を0.1〜10A/cm2に設定し、 （ｃ）放電電流の上昇に伴い放電電圧が減少すると共
に、 （ｄ）放電電流の増減に伴い放電面積が減少する 条件を満たすグロー・アーク移行領域の放電を行うこと
により基板表面にダイヤモンドを生成させることを特徴
とするダイヤモンド膜の製造方法。1. A substrate set as an anode and a cathode facing the substrate are placed in a vacuum vessel, and a hydrocarbon gas and hydrogen having a hydrocarbon gas concentration set to 0.1 to 20% by volume are placed in this vessel. A mixed gas with a gas is introduced under a pressure of 100 to 1000 torr, without heating the substrate by a heating means, (a) the discharge sustaining voltage is made higher than in a normal glow, and (b) the current is increased. The density is set to 0.1 to 10 A / cm 2 , and (c) the discharge voltage decreases as the discharge current increases, and (d) the discharge area decreases as the discharge current increases and decreases. The method for producing a diamond film, wherein diamond is generated on the surface of the substrate by performing the electric discharge of.
してなる特許請求の範囲第１項記載のダイヤモンド膜の
製造方法。2. The method for producing a diamond film according to claim 1, wherein a direct current voltage of 0.5 to 5 KV is applied as a discharge voltage.
ることなく室温〜800℃に維持してなる特許請求の範囲
第１項記載のダイヤモンド膜の製造方法。3. The method for producing a diamond film according to claim 1, wherein the substrate is water-cooled and held, or is kept at room temperature to 800 ° C. without being water-cooled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61226237A JPH06104599B2 (en) | 1986-09-26 | 1986-09-26 | Diamond film manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61226237A JPH06104599B2 (en) | 1986-09-26 | 1986-09-26 | Diamond film manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6385094A JPS6385094A (en) | 1988-04-15 |
| JPH06104599B2 true JPH06104599B2 (en) | 1994-12-21 |
Family
ID=16842039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61226237A Expired - Fee Related JPH06104599B2 (en) | 1986-09-26 | 1986-09-26 | Diamond film manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06104599B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0729875B2 (en) * | 1987-12-12 | 1995-04-05 | 富士通株式会社 | Diamond film synthesis method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60118693A (en) * | 1983-11-25 | 1985-06-26 | Mitsubishi Metal Corp | Method for synthesizing diamond under low pressure |
| JPS60221395A (en) * | 1984-04-19 | 1985-11-06 | Yoshio Imai | Manufacture of diamond thin film and its use |
-
1986
- 1986-09-26 JP JP61226237A patent/JPH06104599B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6385094A (en) | 1988-04-15 |
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