Dopant precursors and processes

• US 6,743,738 B2
• Filed: 11/13/2002
• Issued: 06/01/2004
• Est. Priority Date: 02/12/2001
• Status: Expired due to Term

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM America Incorporated (ASM International NV)
• Inventors: Todd, Michael A.
• Primary Examiner(s): LE, DUNG ANH
• Application Number:
  US10/294,233
• Publication Number:
  US 20030068869A1
• Time in Patent Office: 566 Days
• Field of Search: 438/255-257, 438/398, 438/396, 438/665, 438/664, 438/778
• US Class Current: 438/778
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/22 characterised by the deposition of inorganic material, other than metallic material
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/325 Silicon carbide
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/06 Silicon
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/02422 Non-crystalline insulating materials, e.g. glass, polymers
• CPC Class Codes: H01L 21/0243 Surface structure
• CPC Class Codes: H01L 21/0245 Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/0251 Graded layers
• CPC Class Codes: H01L 21/02529 : Silicon carbide
• CPC Class Codes: H01L 21/02532 : Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/02576 : N-type
• CPC Class Codes: H01L 21/02579 : P-type
• CPC Class Codes: H01L 21/02592 : amorphous
• CPC Class Codes: H01L 21/02595 : polycrystalline
• CPC Class Codes: H01L 21/02598 : monocrystalline
• CPC Class Codes: H01L 21/0262 : Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 21/02667 : Crystallisation or recrystallisation of non-monocrystalline semiconductor materials, e.g. regrowth
• CPC Class Codes: H01L 21/2257 : the applied layer being silicon or silicide or SIPOS, e.g. polysilicon, porous silicon
• CPC Class Codes: H01L 21/28035 : the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities H01L21/28105 takes precedence
• CPC Class Codes: H01L 21/28044 : the conductor comprising at least another non-silicon conductive layer
• CPC Class Codes: H01L 21/28194 : by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/28525 : the conductive layers comprising semiconducting material H01L21/28518, H01L21/28537 take precedence
• CPC Class Codes: H01L 21/28556 : by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/3185 : of siliconnitrides
• CPC Class Codes: H01L 21/32055 : Deposition of semiconductive layers, e.g. poly - or amorphous silicon layers
• CPC Class Codes: H01L 28/84 : being a rough surface, e.g. using hemispherical grains
• CPC Class Codes: H01L 29/127 : Quantum box structures
• CPC Class Codes: H01L 29/51 : Insulating materials associated therewith for MIS structures on thin film semiconductor H01L29/4908
• CPC Class Codes: H01L 29/517 : the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence
• CPC Class Codes: H01L 29/518 : the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material
• CPC Class Codes: H01L 29/66181 : Conductor-insulator-semiconductor capacitors, e.g. trench capacitors
• CPC Class Codes: H01L 29/66242 : Heterojunction transistors [HBT] with an active layer made of a group 13/15 material H01L29/66318
• CPC Class Codes: H01L 31/1804 : comprising only elements of Group IV of the Periodic Table
• CPC Class Codes: H01L 31/182 : Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
• CPC Class Codes: H01L 31/202 : including only elements of Group IV of the Periodic Table
• CPC Class Codes: Y02E 10/546 : Polycrystalline silicon PV cells
• CPC Class Codes: Y02E 10/547 : Monocrystalline silicon PV cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 438/933 : Germanium or silicon or Ge-Si on III-V

Abstract

Silicon alloys and doped silicon films are prepared by chemical vapor deposition and ion implantation processes using Si-containing chemical precursors as sources for Group III and Group V atoms. Preferred dopant precursors include (H₃Si)_3-xMR_x, (H₃Si)₃N, and (H₃Si)₄N₂, wherein R is H or D, x=0, 1 or 2, and M is selected from the group consisting of B, P, As, and Sb. Preferred deposition methods produce non-hydrogenated silicon alloy and doped Si-containing films, including crystalline films.

Claims

1. A deposition process for making a non-hydrogenated Si-containing film, comprising:

providing a vapor deposition chamber having a substrate disposed therein;

introducing a dopant precursor compound to the chamber, wherein the dopant precursor compound comprises at least one silicon atom and at least one Group III or Group V atom; and

depositing a non-hydrogenated Si-containing film onto the substrate.

2. The process of claim 1, wherein the dopant precursor compound has the form (H₃Si)_3-xMR_x, and wherein R is H or D, x=0, 1 or 2, and M is selected from the group consisting of B, Al, Ga, In, P, As, and Sb.

3. The process of claim 2, further comprising introducing a silicon source to the chamber.

4. The process of claim 3, wherein the silicon source is selected from the group consisting of silane, disilane and trisilane.

5. The process of claim 2, wherein M is selected from the group consisting of P, As, and Sb.

6. The process of claim 5, wherein the Si-containing film is an alloy comprising an amount of silicon in the range of about 50 atomic % to about 99.9 atomic %.

7. The process of claim 5, wherein the Si-containing film comprises an amount of arsenic or phosphorous in the range of about 1 part per billion to about 1,000 parts per million.

8. The process of claim 2, wherein the Si-containing film is a crystalline film.

9. The process of claim 8, wherein the Si-containing film is an epitaxial film.

10. The process of claim 2, wherein the Si-containing film is a solid diffusion source.

11. The process of claim 1, wherein the Si-containing film is deposited by thermal chemical vapor deposition.

12. The process of claim 11, wherein the dopant precursor compound is (H₃Si)₃N.

13. The process of claim 12, further comprising introducing a carbon source and a silicon source to the chamber to thereby deposit a nitrogen-doped SiC film as the non-hydrogenated Si-containing film.

14. The process of claim 11, wherein the dopant precursor compound is (H₃Si)₂N₂.

15. The process of claim 1, further comprising introducing an oxygen-containing pulse to the chamber, wherein the dopant precursor compound is tetrasilylhydrazine, and wherein the non-hydrogenated Si-containing film is deposited by atomic layer deposition.

16. The process of claim 1, wherein the Si-containing film is deposited by plasma-enhanced chemical vapor deposition.

17. The process of claim 1, wherein the Si-containing film is deposited at a temperature of about 400°

C. or greater.

18. The process of claim 1, wherein the Si-containing film is deposited at a temperature in the range of about 450°

C. to about 700°

C.

19. The process of claim 1, wherein the Si-containing film contains about 5 atomic % hydrogen or less.

20. The process of claim 1, wherein the Si-containing film contains about 2 atomic % hydrogen or less.

21. The process of claim 1, further comprising introducing an oxygen-containing pulse to the chamber, wherein the dopant precursor compound is trisilylamine, and wherein the non-hydrogenated Si-containing film is deposited by atomic layer deposition.

22. The process of claim 1, further comprising introducing a germanium source to the chamber.

23. The process of claim 1, wherein the Si-containing film comprises a material selected from the group consisting of doped amorphous silicon, doped polysilicon, doped epitaxial silicon, doped SiC, doped SiGe, and doped SiGeC.

24. A chemical vapor deposition process for making an at least partially crystalline Si-containing film, comprising

providing a chemical vapor deposition chamber having a substrate disposed therein:

introducing a silicon source and a dopant precursor compound to the chamber, wherein the dopant precursor compound is comprised of at least one silicon atom and at least one Group III or Group V atom; and

(depositing a doped Si-containing film onto the substrate.

25. The process of claim 24, wherein the substrate is maintained at a temperature between about 550°

C. and about 700°

C. and the film is at least partially crystalline as deposited.

26. The process of claim 24, wherein the silicon source is selected from the group consisting of silane, disilane and trisilane.

27. The process of claim 26, wherein the dopant precursor compound has the form (H₃Si)_3-xMR_x, and wherein R is H or D, x=0, 1 or 2, and M is selected from the group consisting of B, Al, Ga, In, P, As, and Sb.

28. The process of claim 27, wherein the doped Si-containing film comprises an amount of arsenic or phosphorous in the range of about 1 part per billion to about 1,000 parts per million.

29. The process of claim 24, further comprising introducing a carbon source to the chamber to thereby deposit a nitrogen-doped SiC film as the doped Si-containing film.

30. The process of claim 29, wherein the dopant precursor compound is a nitrogen-containing chemical precursor compound that is free of N—

H bonds.

31. The process of claim 30, wherein the chemical vapor deposition chamber is a single-wafer, horizontal gas flow reactor.

32. The process of claim 24, wherein the doped Si-containing film is a single crystal.

33. The process of claim 24, further comprising introducing a germanium source to the chamber.

34. The process of claim 24, wherein the doped Si-containing film is amorphous as deposited, further comprising:

heating the doped amorphous Si-containing film to a temperature in the range of about 550°

C. to about 700°

C. for a period of time effective to at least partially crystallize the doped amorphous Si-containing film.

35. The process of claim 34, wherein the doped amorphous Si-containing film is deposited by plasma-enhanced chemical vapor deposition.

36. The process of claim 34, wherein the doped amorphous Si-containing film is non-hydrogenated.

37. The process of claim 34, wherein the dopant precursor compound has the form (H₃Si)_3-xMR_x, and wherein R is H or D, x=0, 1 or 2, and M is selected from the group consisting of B, Al, Ga, In, P, As, and Sb.

38. The process of claim 37, wherein the silicon source is selected from the group consisting of silane, disilane and trisilane.

39. The process of claim 37, wherein the doped Si-containing film comprises an amount of arsenic or phosphorous in the range of about 1 part per billion to about 1,000 parts per million.

40. The process of claim 34, wherein the period of time for the heating of the doped Si-containing film is in the range of about 2 minutes to about 1 hour.