Method for arc discharge plasma vapor deposition of diamond

• US 5,368,897 A
• Filed: 04/04/1988
• Issued: 11/29/1994
• Est. Priority Date: 04/03/1987
• Status: Expired due to Fees

• Current Assignee: Fujitsu Limited
• Original Assignee: Fujitsu Limited
• Inventors: Kurihara, Kazuaki, Sasaki, Kenichi, Koshino, Nagaaki, Kawarada, Motonobu
• Primary Examiner(s): Silverman, Stanley
• Application Number:
  US07/177,504
• Time in Patent Office: 2,430 Days
• Field of Search: 427/38, 427/37, 427/577, 427/580, 427/450, 423/446, 219/121.11, 219/121.15, 118/724, 118/723 R, 118/723 E, 118/723 ER, 156/DIG. 68
• US Class Current: 427/450
• CPC Class Codes: C23C 16/276 using plasma jets
• CPC Class Codes: C23C 16/277 using other elements in the gas phase besides carbon and hydrogen; using other elements besides carbon, hydrogen and oxygen in case of use of combustion torches; using other elements besides carbon, hydrogen and inert gas in case of use of plasma jets
• CPC Class Codes: C23C 16/513 using plasma jets
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/04 Diamond

Abstract

A method for vapor deposition of diamond by effecting an arc discharge while feeding a discharge gas between an anode and a cathode of a thermal plasma chemical vapor deposition device, radicalizing a gaseous carbon compound by feeding the gaseous carbon compound into a generated plasma jet, and permitting the radicalized plasma jet to impinge on a substrate to be treated, whereby a film of diamond is formed on the substrate.

Claims

1. A method of vapor deposition of diamond comprising the steps of:

effecting an arc discharge while feeding a discharge gas containing hydrogen between an anode and a cathode of a thermal plasma chemical vapor deposition device to thereby generate a plasma jet containing dissociated hydrogen atoms;

radicalizing a gaseous carbon compound by feeding the gaseous compound into the hydrogen atom containing generated plasma jet; and

permitting said radicalized plasma jet to impinge on a substrate to be treated, to thereby form a film of diamond on said substrate.

2. A method of vapor deposition of diamond by direct current arc discharge comprising the steps of:

feeding a hydrogen containing gas and a gaseous carbon compound into a thermal plasma generating device having an anode and a cathode;

radicalizing the gas by direct current arc discharge between the anode and cathode to thereby dissociate hydrogen molecules into hydrogen atoms;

jetting the thermal plasma as a plasma jet containing dissociated hydrogen atoms into a reduced pressure chamber; and

quenching the plasma jet by permitting said plasma jet to impinge on a cooled substrate, to thereby deposit a diamond film on the substrate.

3. A method according to claim 2, wherein the gaseous carbon compound is a hydrocarbon, or a hydrocarbon containing oxygen, nitrogen or halogen in the molecule.

4. A method according to claim 2, wherein the gas containing hydrogen and the gaseous carbon compound further contains an inert gas, an oxidative gas or a mixture thereof.

5. A method according to claim 4, wherein the oxidative gas is oxygen, water, hydrogen peroxide or carbon monooxide.

6. A method according to claim 2, wherein the gas containing hydrogen and the gaseous carbon compound is fed between the electrodes of the thermal plasma generating device.

7. A method according to claim 2, wherein the hydrogen containing gas is fed between the electrodes of the thermal plasma generating device, and the gaseous carbon compound is fed to the plasma jet jetted from the electrodes.

8. A method according to claim 2, wherein the direct arc discharge is effected by using a carbon electrode or a tungsten electrode containing a rare earth element oxide as the electrode.

9. A method of vapor deposition of diamond comprising the steps of:

effecting an arc discharge by applying a direct current to an arc discharge device comprising an enclosed hollow body having a plurality of openings therefrom, each said opening being defined by an inner wall, said device including a respective corresponding electrode member located adjacent each opening in spaced relationship to the inner wall thereof, said inner walls and said members presenting a plurality of nozzles opening from the enclosed body, each said inner wall comprising an electrode of one polarity, and each corresponding member comprising an electrode of the opposite polarity;

feeding hydrogen into said body;

providing a gas containing a gaseous carbon compound;

radicalizing hydrogen and said gas containing a gaseous carbon compound to form a thermal plasma containing dissociated hydrogen atoms;

jetting out the thermal plasma as a plasma jet containing dissociated hydrogen atoms into a reduced pressure chamber;

and

quenching the plasma jet by permitting said plasma jet to impinge on a cooled substrate, to thereby deposit a diamond film on the substrate.

10. A method according to claim 9, wherein the gaseous carbon compound is a hydrocarbon, or a hydrocarbon containing oxygen, nitrogen or halogen in the molecule.

11. A method according to claim 9, wherein the hydrogen or the gaseous carbon compound further contains an inert gas, an oxidative gas or a mixture thereof.

12. A method according to claim 11, wherein the oxidative gas is oxygen, water, hydrogen peroxide or carbon monooxide.

13. A method according to claim 9, wherein the gas containing hydrogen and a gaseous carbon compound is fed between the electrodes of the thermal plasma generating device.

14. A method according to claim 9, wherein the hydrogen is fed between said electrodes, and the gas containing a gaseous carbon compound is fed to the plasma jet jetted out from between the electrodes.

15. A method according to claim 9, wherein the direct current arc discharge is effected by using a carbon electrode or a tungsten electrode containing a rare earth element oxide as the electrode.

16. A method of vapor deposition of diamond comprising the steps of:

feeding a gas containing hydrogen to a thermal plasma generating device in the form of a torch having an anode and a cathode,

radicalizing the gas by a direct current arc discharge between electrodes to form a thermal plasma containing dissociated hydrogen atoms,

jetting the thermal plasma formed as a plasma jet containing dissociated hydrogen atoms through a nozzle at the tip end of the torch, blowing a cooling gas into the plasma jet to quench the thermal plasma and form an active non-equilibrium plasma containing at least radical products formed by a radicalization of a gaseous carbon compound fed to the plasma jet and having a concentration of radicals, and bringing a substrate into contact with the non-equilibrium plasma, whereby a diamond film is deposited from a vapor phase on the substrate.

17. A method according to claim 16, wherein hydrogen is contained in the feeding gas, the cooling gas or both.

18. A method according to claim 16, wherein the gaseous carbon compound is contained in the feeding gas, the cooling gas or both thereof.

19. A method according to claim 16, wherein the gaseous carbon compound is a hydrocarbon or a hydrocarbon containing oxygen, nitrogen or halogen in the molecule.

20. A method according to claim 16, wherein an inert gas is contained in the feeding gas, the cooling gas or both thereof.

21. A method according to claim 20, wherein an inert gas or an oxidative gas is contained in the feed gas, the cooling gas, or both thereof fed to the plasma jet jetted from the nozzle.

22. A method according to claim 21, wherein the oxidative gas is oxygen, water, hydrogen peroxide, or carbon monooxide.

23. A method according to claim 21, wherein the direct current arc discharge is effected by using a carbon electrode or a tungsten electrode containing a rare earth element oxide as the electrode.

24. A method of vapor deposition of a diamond film by effecting an arc discharge by DC plasma torches having a cathode and an anode while feeding a discharge gas containing hydrogen between the cathode and the anode and irradiating the plasma jet formed onto a substrate to be treated to form a film of diamond on said substrate to be treated, which comprises using at least two plasma torches, forming a gas with a higher discharge voltage into a plasma in one torch, forming a reactive gaseous carbon compound with a lower discharge voltage into a plasma in another torch and permitting both plasmas to impinge as a jet onto the substrate, to thereby form a diamond film thereon.

25. A method according to claim 24, wherein the gas with the higher discharge voltage is hydrogen.

26. A method according to claim 24, wherein the gaseous carbon compound is a hydrocarbon or a hydrocarbon containing oxygen, nitrogen, or halogen in the molecule.

27. A method of vapor deposition of diamond according to claim 25, wherein the plasma jets generated from the plasma torches are mutually allowed to impinge on each other before impinging onto the substrate.

28. A method according to claim 27, wherein the plasma containing a carbon compound is quenched in said plasma jets and irradiated on the substrate to prepare a uniform and smooth diamond film on the substrate.

29. A method of vapor deposition of diamond, comprising the steps of:

forming a discharge gas containing hydrogen and a starting material containing at least a gaseous carbon compound into a thermal plasma containing dissociated hydrogen atoms by arc discharge;

jetting the thermal plasma as a plasma jet containing dissociated hydrogen atoms; and

quenching the plasma jet to deposit a diamond film on a substrate, at least the gaseous carbon compound being fed to a center of the initiation end of said plasma jet, without passing through said arc discharge portion.

30. A method according to claim 29, wherein the discharge gas is hydrogen, an inert gas, or a mixture thereof.

31. A method according to claim 29, wherein the starting material contains at least one gas selected from the group consisting of hydrogen, an inert gas, and an oxidative gas. .

32. A method according to claim 29, wherein the starting material including a hydride of boron, nitrogen or phosphorus.

33. A method according to claim 29, wherein the substrate is a diamond substrate and the diamond film is epitaxially grown on said diamond substrate by permitting the plasma jet to impinge on the diamond substrate.

34. A method of vapor deposition of diamond, comprising the steps of:

providing a carbon source;

using a plural number of plasma torches to form a plural number of hot plasma jets containing hydrogen in the form of dissociated hydrogen atoms; and

permitting the plasma jets to mutually impinge on each other and the carbon source to form the carbon source into plasma in said plasma jets to deposit diamond on a substrate.

35. A method of vapor deposition of diamond comprising the steps of:

effecting an arc discharge while feeding a discharge gas between an anode and a cathode of a thermal plasma chemical vapor deposition device to thereby generate an arc plasma jet having a temperature of about 5000°

C. of higher;

radicalizing a gaseous carbon compound by feeding the gaseous compound into the generated plasma jet; and

permitting the plasma jet containing the radicalized gaseous carbon compound to impinge on a substrate to be treated, to thereby form a film of diamond on said substrate

36. A method of vapor deposition of diamond by direct current arc discharge comprising the steps of:

feeding a gas containing hydrogen and a gaseous carbon compound into a thermal plasma generating device having an anode and cathode to thereby generate an arc plasma having a temperature of 5000°

C. or higher;

radicalizing the gas by direct current arc discharge between the electrodes;

jetting the thermal plasma as a plasma jet into a reduced pressure chamber; and

quenching the plasma jet by permitting said plasma jet to impinge on a cooled substrate, to thereby deposit a diamond film on the substrate.

37. A method of vapor deposition of diamond by direct current arc discharge comprising the steps of:

feeding a gas containing hydrogen and a gaseous carbon compound selected from the group consisting of gaseous hydrocarbons and gaseous hydrocarbons containing oxygen, nitrogen, or halogen in the molecule into at least one thermal plasma generating device in the form of a torch having an anode and a cathode;

radicalizing the gas by direct current arc discharge between the anode and cathode to form a thermal plasma, at least one of said anode and said cathode being comprised of carbon or of tungsten containing a rare earth element oxide, whereby the hydrogen molecules are substantially dissociated into hydrogen atoms;

jetting the thermal plasma as a plasma jet through a nozzle at the tip end of the torch into a reduced pressure chamber; and

quenching the plasma jet by permitting said plasma jet to impinge on a cooled substrate, to thereby deposit a diamond film on the substrate.