Amino replacements for arsine, antimony and phosphine

• US 5,124,278 A
• Filed: 09/21/1990
• Issued: 06/23/1992
• Est. Priority Date: 09/21/1990
• Status: Expired due to Term

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Bassner, Sherri L., Muhr, Gregory T., Bohling, David A.
• Primary Examiner(s): KUNEMUND, ROBERT M
• Application Number:
  US07/586,845
• Time in Patent Office: 641 Days
• Field of Search: 148/DIG. 16, 148/41, 148/56, 148/65, 148/110, 148/119, 156/610-615, 556/70, 427/248.1, 427/252, 427/253, 427/255.1, 437/81, 437/85, 437/87, 437/88, 437/133, 437/126, 437/949, 437/945
• US Class Current: 438/514
• CPC Class Codes: C23C 16/301 AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/40 AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
• CPC Class Codes: Y10S 148/016 Catalyst
• CPC Class Codes: Y10S 148/041 Doping control in crystal growth
• CPC Class Codes: Y10S 148/056 Gallium arsenide
• CPC Class Codes: Y10S 148/065 Gp III-V generic compounds-processing

Abstract

The present invention addresses the use of metalorganic amines as metallic donor source compounds in reactive deposition applications. More specifically, the present invention addresses the use of the amino-substituted metallic donor source compounds M(NR₂)_3-x H_x, where R is organic, alkyl or fluoroalkyl, and x is less than or equal to 2, and M=As, Sb or P, in processes requiring deposition of the corresponding element. These uses include a number of different processes; the metalorganic vapor phase epitaxy of compound semiconductor material such as GaAs, InP, AlGaAs, etc.; doping of SiO₂ or borosilicate based glasses to enhance the reflow properties of the glass; in-situ n-type doping of silicon epitaxial material; sourcing of arsenic or phosphorus for ion implantation; chemical beam epitaxy (or MOMBE); and diffusion doping into electronic materials such as silicon dioxide, silicon and polycrystalline silcon. These types of materials generally have high volatilities, low toxicities, labile metal-ligand bonds, and stable decomposition products.

Specifically, the use of tris(dialkylamino) arsenic (As(NR₂)₃) as a substitute for arsine in the manufacture of silicon integrated circuits, Group III-V compound semiconductors, optoelectronics and other electronic devices has been identified.

Claims

1. In a method for the reactive deposition of a Group VA metal to a substrate using a metalorganic as a metallic donor reactant containing arsenic, phosphorus or antimony, the improvement wherein said metallic donor reactant is selected from the group consisting of compounds of the formula:

M(NR₂)_3-x H_x, where R is one or more organic or fluoroorganic radicals, and x is less than or equal to 2, and M=As, Sb or P.

2. The method of claim 1 wherein said organic radicals are selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl or arenyl.

3. The method of claim 1 wherein said metallic donor reactant is tris(dialkylamino) arsenic.

4. The method of claim 1 wherein said metallic donor reactant is tris(dialkylamino) phosphorus.

5. The method of claim 1 wherein said metallic donor reactant is tris(dialkylamino) antimony.

14. The method of claim 1 of said reactive deposition, comprising:

doping silicon dioxide-based glass or borosilicate-based glass with a Group VA metal using a metalorganic as a metallic donor dopant source containing arsenic, phosphorus or antimony as said metallic donor reactant.

15. The method of claim 14 wherein said organic radicals are selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl or arenyl.

16. The method of claim 14 wherein said metallic donor dopant source is tris(dialkylamino) arsenic.

17. The method of claim 14 wherein said metallic donor dopant source is tris(dialkylamino) phosphorus.

18. The method of claim 14 wherein said metallic donor dopant source is tris(dialkylamino) antimony.

19. The method of claim 1 of said reactive deposition, comprising;

n-type doping of silicon epitaxial or polycrystalline material with a Group VA metal using a metalorganic as a metallic donor dopant source containing arsenic, phosphorus or antimony as said metallic donor reactant.

20. The method of claim 19 wherein said organic radicals are selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl or arenyl.

21. The method of claim 19 wherein said metallic donor dopant source is tris(dialkylamino) arsenic.

22. The method of claim 19 wherein said metallic donor dopant source is tris(dialkylamino) phosphorus.

23. The method of claim 19 wherein said metallic donor dopant source is tris(dialkylamino) antimony.

24. The method of claim 1 of said reactive deposition, comprising;

ion implantation of a Group VA metal in a semiconductor substrate using a metalorganic as a metallic donor ion source containing arsenic, phosphorus or antimony as said metallic donor reactant.

25. The method of claim 24 wherein said organic radicals are selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl or arenyl.

26. The method of claim 24 wherein said metallic donor ion source is tris(dialkylamino) arsenic.

27. The method of claim 24 wherein said metallic donor ion source is tris(dialkylamino) phosphorus.

28. The method of claim 24 wherein said metallic donor ion source is tris(dialkylamino) antimony.

29. The method of claim 1 of said reactive deposition, comprising;

diffusing a Group VA metal into an electronic material substrate from a vapor metallic donor source containing arsenic, phosphorus or antimony as said metallic donor reactant to react the diffused metal to the substrate.

30. The method of claim 29 wherein said organic radicals are selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl or arenyl.

31. The method of claim 29 wherein said metallic donor source is tris(dialkylamino) arsenic.

32. The method of claim 29 wherein said metallic donor source is tris(dialkylamino) phosphorus.

33. The method of claim 29 wherein said metallic donor source is tris(dialkylamino) antimony.

6. In a method of metallic donor vapor phase epitaxial deposition of semiconductor materials containing a Group VA metal using at least two reactants in which one of the reactants is a metalorganic used as a metallic donor reactant containing arsenic, phosphorus or antimony, the improvement wherein said metallic donor reactant is selected from the group consisting of compounds of the formula:

M(NR₂)_3-x H_x, where R is one or more organic or fluoroorganic radicals and when only one R is an organic or fluoroorganic radical than the other R is hydrogen, and x is less than or equal to 2, and M=As, Sb or P.

7. The method of claim 6 wherein said organic radicals are selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl or arenyl.

8. The method of claim 6 wherein said metallic donor reactant is tris(dialkylamino) arsenic.

9. The method of claim 6 wherein said metallic donor reactant is tris(dialkylamino) phosphorus.

10. The method of claim 6 wherein said metallic donor reactant is tris(dialkylamino) antimony.

11. The method of claim 6 wherein a second reactant is selected from the group consisting of:

trialkyl gallium, trialkyl indium, trialkyl aluminum and mixtures thereof.

12. The method of claim 11 wherein the second reactant is selected from the group consisting of:

trimethyl gallium, trimethyl indium, trimethyl aluminum and mixtures thereof.

13. The method of claim 6 wherein the resulting epitaxial semiconductor material is selected from the group consisting of:

AlGaAs, InGaAs, InP, GaAs, InSb, InGaAsP, GaAsP, InAsP, InGaAlP, or AlGaP.

34. In a method of chemical beam epitaxy or metalorganic molecular beam epitaxy for deposition and reaction of a Group VA metal with at least one other reactant with an electronic material substrate where one of the reactants is a Group VA metallic donor source, the improvement comprising the use of a Group VA metallic donor source which is selected from the group consisting of compounds of the formula:

M(NR₂)_3-x H_x, where R is one or more organic or fluoroorganic radicals, and x is less than or equal to 2, and M=As, Sb or P.

35. The method of claim 34 wherein said organic radicals are selected from the group consisting of alkyl, cycloalkyl, aryl, alkenyl or arenyl.

36. The method of claim 34 wherein said metallic donor source is tris(dialkylamino) arsenic.

37. The method of claim 34 wherein said metallic donor source is tris(dialkylamino) phosphorus.

38. The method of claim 34 wherein said metallic donor source is tris(dialkylamino) antimony.

39. The method of claim 34 wherein the other reactant is selected from the group consisting of:

trialkyl or hydride gallium, trialkyl or hydride aluminium, trialkyl or hydride indium and mixtures thereof.

40. The method of claim 34 wherein the other reactant is selected from the group consisting of triethyl gallium, tetramethylethylenediamine gallane, triethyl aluminum, tetramethylethylenediamine alane, trimethylamine alane, trimethyl indium, dimethyl aluminum hydride and mixtures thereof.

41. The method of claim 34 wherein the other reactant is triethyl gallium.

42. The method of claim 34 wherein the other reactant is tetramethylethylenediamine gallane.

43. The method of claim 34 wherein the other reactant is triethyl aluminum.

44. The method of claim 34 wherein the other reactant is tetramethylethylenediamine alane.

45. The method of claim 34 wherein the other reactant is trimethylamine alane.

46. The method of claim 34 wherein the other reactant is trimethyl indium.

47. The method of claim 34 wherein the other reactant is dimethyl aluminum hydride.