Methods for manufacturing monocrystalline diamond films

• US 5,814,149 A
• Filed: 11/17/1995
• Issued: 09/29/1998
• Est. Priority Date: 11/25/1994
• Status: Expired due to Term

• Current Assignee: Klaus Schmidt
• Original Assignee: Klaus Schmidt
• Inventors: Nishimura, Kozo, Miyata, Koichi, Yokota, Yoshihiro, Tachibana, Takeshi, Kobashi, Koji, Shintani, Yoshihiro
• Primary Examiner(s): KUNEMUND, ROBERT M
• Application Number:
  US08/560,077
• Time in Patent Office: 1,047 Days
• Field of Search: 117/104, 117/108, 117/929, 423/446
• US Class Current: 117/104
• CPC Class Codes: C23C 16/0263 Irradiation with laser or particle beam
• CPC Class Codes: C23C 16/0281 of metallic sub-layers C23C16/029 takes precedence
• CPC Class Codes: C23C 16/271 using hot filaments
• CPC Class Codes: C23C 16/272 using DC, AC or RF discharges
• CPC Class Codes: C23C 16/274 using microwave discharges
• CPC Class Codes: C23C 16/275 using combustion torches
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/04 Diamond

Abstract

A method is related to grow monocrystalline diamond films by chemical vapor deposition on large area at low cost. The substrate materials are either bulk single crystals of Pt or its alloys, or thin films of those materials deposited on suitable supporting materials. The surfaces of those substrates must be either (111) or (001), or must have domain structures consisting of (111) or (001) crystal surfaces. Those surfaces can be inclined within ±10 degree angles from (111) or (001). In order to increase the nucleation density of diamond, the substrate surface can be scratched by buff and/or ultrasonic polishing, or carbon implanted. Monocrystalline diamond films can be grown even though the substrate surfaces have been roughened. Plasma cleaning of substrate surfaces and annealing of Pt or its alloy films are effective in growing high quality monocrystalline diamond films.

Claims

1. A method for forming monocrystalline diamond films by chemical vapor deposition (CVD) on substrates which are made of platinum or its alloys and have either (111) or (001) crystal surfaces and/or inclined crystal surfaces with angular deviations within ±

10 degrees from (111) or (001), respectively, on the substrate surfaces entirely or at least partly.

5. A method for forming monocrystalline diamond films according to claim 1, wherein the surface of said substrate consists of domains of said crystal surface, whereby monocrystalline diamond films with (111) or (001) crystal surfaces grow on the corresponding domains of the substrate.

10. A method for forming monocrystalline diamond films according to claim 1, wherein the surfaces of said substrates have been buff and/or ultrasonically polished with diamond powder or paste prior to diamond CVD.

11. A method for forming monocrystalline diamond films according to claim 1, wherein the surfaces of said substrates have been ion-implanted with carbon using the conditions that the acceleration voltage is between 40 and 120 keV and the carbon implantation density is between 10¹⁶ -10²⁰ cm^-2.

12. A method for forming monocrystalline diamond films according to claim 1, wherein prior to diamond CVD, said substrate is treated in a vacuum better than 10^-6 Torr above 300°

C. for more than 15 minutes, and then cleaned in a plasma which comprises at least one gas selected from the group consisting of hydrogen, oxygen, chlorine and fluorine, or at least one inert gas selected from the group consisting of helium neon and argon, or a mixture of both.

13. A method for forming monocrystalline diamond films according to claim 12, wherein after cleaning said substrate the surface of said substrate is treated by a plasma which comprises a carbon-containing gas and, optionally, at least one gas selected from the group consisting of hydrogen, oxygen, chlorine and fluorine, and at least one inert gas selected from the group consisting of helium neon and argon, or a mixture of both.

14. A method for forming monocrystalline diamond films according to claim 1, wherein said substrate is applied with a bias voltage in a plasma of carbon-containing gas.

15. A method for forming monocrystalline diamond films according to claim 14, wherein the reaction gas is free of hydrogen atoms.

16. A method for forming monocrystalline diamond films according to claim 14, wherein the nuclei are formed from a carbon-containing gas diluted by hydrogen to a concentration of 0.1 to 10 vol % under the conditions that the gas pressure is 1 to 100 Torr, the substrate temperature is 400°

to 1100°

C., the DC voltage is -70 to -30 V or +70 to +350 V and the biasing time is 1 to 90 minutes.

17. A method for forming monocrystalline diamond films according to claim 1, wherein diamond CVD is undertaken using a source gas which is free of hydrogen atoms.

18. A method for forming monocrystalline diamond films according to claim 1, wherein diamond CVD is done using a mixture of methane, oxygen and hydrogen, where the methane concentration is between 0.1 and 5%, and the oxygen concentration is between 0.1 and 3%, at a substrate temperature higher than 750°

C., whereby a monocrystalline diamond film with (111) crystal surface is deposited on the (111) crystal surface of said substrate.

19. A method for forming monocrystalline diamond films according to claim 1, wherein diamond CVD is done using a mixture of methane, oxygen and hydrogen, where the methane concentration is between 5 and 15%, and the oxygen concentration is between 1 and 7%, at a substrate temperature lower than 850°

C., whereby a monocrystalline diamond film with (001) crystal surface is deposited on the (001) crystal surface of said substrate.

2. A method for forming monocrystalline diamond films by CVD on substrates each of which comprises of a film of platinum or its alloys deposited on the entire or at least part of the supporting material surface, where the film has either (111) or (001) crystal surfaces and/or inclined crystal surfaces with angular deviations within ±

10 degrees from (111) or (001), respectively.

3. A method for forming monocrystalline diamond films according to claim 2, wherein the thicknesses of the said films of Pt or Pt alloys are more than about 1000 Å

and less than about 0.5 mm.

4. A method for forming monocrystalline diamond films according to claim 2, wherein the minority components of the said Pt alloys comprise of single or plural elements selected from the group of the VIA elements, the VIIIA elements, and the IB elements, and the total concentration of the minority components is not greater than 50 atomic %.

6. A method for forming monocrystalline diamond films according to claim 2, wherein said supporting material is made of a single crystal of at least one member selected from the group consisting of lithium fluoride, calcium fluoride, magnesium oxide, nickel oxide, zirconium oxide, aluminum oxide, strontium titanate, barium titanate, lead titanate, potassium tantalate and lithium niobate.

7. A method for forming monocrystalline diamond films according to claim 2, wherein said supporting material is made of single crystal silicon, quartz or glass.

8. A method for forming monocrystalline diamond films according to claim 2, wherein said film is annealed at a temperature not lower than 300°

C. during and/or after the deposition.

9. A method for forming monocrystalline diamond films according to claim 8, wherein said film is annealed in an oxidation atmosphere.

20. A method for forming monocrystalline diamond films according to claim 2, wherein the surface of said substrate consists of domains of said crystal surface, whereby monocrystalline diamond films with (111) or (001) crystal surfaces grow on the corresponding domains of the substrate.

21. A method for forming monocrystalline diamond films according to claim 2, wherein the surface of said substrates have been buff and/or ultrasonically polished with diamond powder or paste prior to diamond CVD.

22. A method for forming monocrystalline diamond films according to claim 2, wherein the surfaces of said substrates have been ion-implanted with carbon using the conditions that the acceleration voltage is between 40 and 120 keV and the carbon implantation density is between 10¹⁶ -10²⁰ cm^-2.

23. A method for forming monocrystalline diamond films according to claim 2, wherein prior to diamond CVD, said substrate is treated in a vacuum better than 10^-6 Torr above 300°

C. for more than 15 minutes, and then cleaned in a plasma which comprises at least one gas selected from the group consisting of hydrogen, oxygen, chlorine and fluorine, or at least one inert gas selected from the group consisting of helium, neon and argon, or a mixture of both.

24. A method for forming monocrystalline diamond films according to claim 23, wherein after cleaning said substrate the surface of said substrate is treated by a plasma which comprises a carbon-containing gas and, optionally, at least one gas selected from the group consisting of hydrogen, oxygen, chlorine and fluorine, and at least one inert gas selected from the group consisting of helium, neon and argon, or a mixture of both.

25. A method for forming monocrystalline diamond films according to claim 2, wherein said substrate is applied with a bias voltage in a plasma of carbon-containing gas.

26. A method for forming monocrystalline diamond films according to claim 25, wherein the reaction gas is free of hydrogen atoms.

27. A method for forming monocrystalline diamond films according to claim 25, wherein the nuclei are formed from a carbon-containing gas diluted by hydrogen to a concentration of 0.1 to 10 vol % under the conditions that the gas pressure is 1 to 100 Torr, the substrate temperature is 400°

to 1100°

C., the DC voltage is -70 to -30 V or +70 to +350 V and the biasing time is 1 to 90 minutes.

28. A method for forming monocrystalline diamond films according to claim 2, wherein diamond CVD is undertaken using a source gas which is free of hydrogen atoms.

29. A method for forming monocrystalline diamond films according to claim 2, wherein diamond CVD is done using a mixture of methane, oxygen and hydrogen, where the methane concentration is between 0.1 and 5%, and the oxygen concentration is between 0.1 and 3%, at a substrate temperature higher than 750°

C., whereby a monocrystalline diamond film with (111) crystal surface is deposited on the (111) crystal surface of said substrate.

30. A method for forming monocrystalline diamond films according to claim 2, wherein diamond CVD is done using a mixture of methane, oxygen and hydrogen, where the methane concentration is between 5 and 15%, and the oxygen concentration is between 1 and 7%, at a substrate temperature lower than 850°

C., whereby a monocrystalline diamond film with (001) crystal surface is deposited on the (001) crystal surface of said substrate.