Growth of beta-sic thin films and semiconductor devices fabricated thereon

• US 4,912,063 A
• Filed: 10/26/1987
• Issued: 03/27/1990
• Est. Priority Date: 10/26/1987
• Status: Expired due to Term

• Current Assignee: North Carolina State University At Raleigh A Educational Institution of NC
• Original Assignee: North Carolina State University (University of North Carolina System)
• Inventors: Carter, Calvin H. Jr., Kong, Hua-Shuang, Davis, Robert F., Glass, Jeffrey T.
• Primary Examiner(s): Hearn, Brian E.
• Assistant Examiner(s): WILCZEWSKI, MARY A
• Application Number:
  US07/113,921
• Time in Patent Office: 883 Days
• Field of Search: 437/100, 437/105, 437/106, 437/949, 437/970, 148/DIG. 148, 156/610, 156/DIG. 64
• US Class Current: 117/97
• CPC Class Codes: H01L 21/02378 Silicon carbide
• CPC Class Codes: H01L 21/02529 Silicon carbide
• CPC Class Codes: H01L 21/02576 N-type
• CPC Class Codes: H01L 21/02579 P-type
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 21/02658 Pretreatments cleaning in general H01L21/02041
• CPC Class Codes: Y10S 117/904 Laser beam
• CPC Class Codes: Y10S 148/148 Silicon carbide

Abstract

Device quality thin films of Beta-SiC are epitaxially grown on substrates of Alpha-Sic.

Claims

1. A method of producing an electrical grade, high purity, low defect, epitaxially grown film of monocrystalline Beta-SiC on an Alpha-SiC substrate for use in semiconductor devices which will operate at high powers, high frequencies, high radiation densities, and temperatures over 500°

C., the method comprising;

providing an Alpha-SiC crystal with a clean, planar, smooth surface along a basal plane thereof;

removing subsurface damage and/or chemical impurities from the surface of the basal plane; and

epitaxially depositing a thin film of Beta-SiC on the planar surface of the substrate by introducing a vaporized, silicon-containing material and a vaporized carbon containing material into a flowing stream of carrier gas, wherein the substrate is an Alpha-SiC substrate and the basal plane thereof on which epitaxial growth occurs is the (0001)Si face, and wherein the Beta-SiC thin film is epitaxially deposited in the growth direction on the (0001) Si face of the Alpha-SiC substrate such that the (111) crystallography of the Beta-SiC thin film matches the (0001) crystallography of the Alpha-SiC substrate and such that the Beta-Sic (101) face is parallel to the Alpha-SiC (1120) face and the Beta-Sic (111) face is parallel to the Alpha-SiC (0001) face while introducing sufficient energy to insure sufficient decomposition of said silicon- and carbon-containing materials into silicon and carbon species and to insure sufficient surface diffusion of the silicon species and the carbon species at the substrate surface to produce monocrystalline growth of Beta-SiC, but said introduced energy being less than the energy required to form Alpha-Sic, and wherein the energy levels in the growth chamber and the source material to Carrier gas ratio are selected to produce a coherent, low defect Beta-SiC/AlphaSiC interface and a low, device-compatible defect density within the bulk Beta-SiC film.

2. A method of producing an electrical grade, high purity, low defect, epitaxially grown film of monocrystalline Beta-SiC on an Alpha-SiC substrate for use in semiconductor devices which will operate at high powers, high frequencies, high radiation densities, and temperatures over 500°

C., the method comprising;

providing an Alpha-SiC crystal with a clean, planar, smooth surface along a basal plane thereof;

removing subsurface damage and/or chemical impurities from the surface of the basal plane; and

epitaxially depositing a thin film of Beta-SiC on the planar surface of the substrate by introducing a vaporized, silicon-containing material and a vaporized carbon-containing material into a flowing stream of carrier gas, wherein the substrate is an Alpha-SiC substrate and the basal plane thereof on which epitaxial growth occurs is the (0001)C face, and wherein the Beta-SiC thin film is epitaxially deposited in the growth direction on the (0001)C face of the Alpha-SiC substrate such that the (111) crystallography of the Beta-SiC thin film matches the (0001) crystallography of the Alpha-SiC substrate and such that the Beta-SiC (101) face is parallel to the Alpha-SiC (1120) face and the Beta-Sic (111) face is parallel to the Alpha-SiC (0001) face while introducing sufficient energy to insure sufficient decomposition of said silicon- and carbon-containing materials into silicon and carbon species and to insure sufficient surface diffusion of the silicon species and the carbon species at the substrate surface to produce monocrystalline growth of Beta-SiC, but said introduced energy being less than the energy required to form Alpha SiC, and wherein the energy levels in the growth chamber and the source material to carrier gas ratio are selected to produce a coherent, low defect Beta-SiC/Alpha-SiC interface and a low, device-compatible defect density within the bulk Beta-Sic film.

3. A method of producing an electrical grade, high purity, low defect, epitaxially grown film of monocrystalline Beta-SiC on Alpha-SiC substrate for use in semiconductor devices which will operate at high powers, high frequencies, high radiation densities, and temperatures over 500°

C., the method comprising

polishing an Alpha-SiC crystal along a basal plane to provide a planar, smooth surface;

oxidizing the polished surface of the Alpha-SiC substrate crystal;

removing the oxidized layer from the substrate crystal;

introducing the substrate crystal into a CVD system and etching the substrate with a flowing stream of hydrogen gas at a temperature sufficient to remove any native oxide layer thereon; and

epitaxially depositing a film of Beta-SiC on the basal plane of the substrate by introducing a vaporized, silicon-containing material and a vaporized carbon-containing material into the flowing stream of hydrogen gas, while introducing sufficient energy to insure sufficient decomposition of said silicon- and carbon-containing materials into silicon and carbon species and to insure sufficient surface diffusion of the silicon species and carbon species at the substrate surface to produce monocrystalline growth of Beta-SiC, but said introduced energy being less than the energy required to form Alpha-Sic.

4. A method according to claim 3 wherein the step of removing the oxidized layer from the remainder of the substrate comprises etching the oxidized layer with hydrofluoric acid.

5. A method according to claim 3 wherein the step of introducing vaporized silicon-containing material and vaporized carbon-containing material comprises introducing the materials in conjunction with remote plasma assisted chemical vapor deposition.

6. A method according to claim 3 wherein the step of introducing vaporized silicon-containing material and vaporized carbon-containing material comprises introducing the materials in conjunction with immersed plasma assisted chemical vapor deposition.

7. A method according to claim 3 wherein the step of introducing sufficient energy to insure sufficient surface diffusion comprises introducing laser light of a frequency and energy to insure sufficient diffusion of silicon species and carbon species.

8. A method of epitaxially growing a high purity, low defect, device quality film of monocrystalline Beta-SiC on an Alpha-SiC substrate for use in the fabrication of semiconductor devices which will operate at high powers, high frequencies, high radiation densities and at temperatures over 500°

C., the method comprising;

providing a 6H SiC substrate crystal having an exposed, planar (0001)C face or (0001)Si face that is prepared to be receptive to epitaxial growth thereon;

introducing the 6H SiC substrate crystal into the growth chamber of a CVD system;

evacuating the growth chamber of the CYD system to a vacuum of at least 10^-4 Torr;

backfilling the CYD chamber with a flowing stream of H₂ gas in order to purge the system;

continuing the flow of H₂ gas while heating the growth chamber to between about 1400°

C. to about 1600°

C.;

etching the face of the substrate in the flow of H₂ gas for a time sufficient to remove at least a substantial portion of any native oxide layer thereon;

introducing a silicon source gas and a carbon source gas into the H₂ stream, while maintaining the temperature in the growth chamber between about 1400°

C. to about 1600°

C., and maintaining the source gas (silicon source gas+carbon source gas) to carrier gas (H₂) ratio at a level sufficient to effect growth of a monocrystalline Beta-SiC film on the substrate.

9. A method according to claim 8 wherein the silicon source gas is SiH₄ and the carbon source gas is C₂ H₄.

10. A method according to claim 9 wherein the purity of the H₂ carrier gas exceeds 99.99, the SiH₄ source gas contains less than 2 ppm nitrogen impurities and the C₂ H₄ source gas contains less than 10 ppm nitrogen impurities.

11. A method according to claim 9 wherein the source gas (SiH₄ +C₂ H₄) to carrier gas (H₂) ratio is maintained at approximately 1:

3000 during film growth.

12. A method according to claim 11 wherein the temperature in the growth chamber is maintained in the range of about 1450°

C. to about 1550°

C. during film growth.

13. A method according to claim 12 wherein the (0001)C face or (0001)Si face is prepared to be receptive to epitaxial growth by first polishing the face, followed by oxidizing the polished face, followed by etching the face with hydrofluoric acid to remove the oxidized layer.

14. A method according to claim 13 wherein the epitaxial growth is carrier out in cold wall, vertical barrel-type CVD system.