Process for atomic layer deposition of metal films

• US 6,869,876 B2
• Filed: 12/20/2002
• Issued: 03/22/2005
• Est. Priority Date: 11/05/2002
• Status: Expired due to Fees

• Current Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Boze, Melanie Anne, Roberts, David Allen, Norman, John Anthony Thomas
• Primary Examiner(s): GURLEY, LYNNE ANN
• Application Number:
  US10/324,781
• Publication Number:
  US 20040087143A1
• Time in Patent Office: 823 Days
• Field of Search: 438/680, 438685-687
• US Class Current: 438/680
• CPC Class Codes: C23C 10/60 After-treatment
• CPC Class Codes: C23C 16/08 from metal halides
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: C23C 26/00 Coating not provided for in groups C23C2/00 - C23C24/00
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76846 Layer combinations
• CPC Class Codes: H01L 21/76862 Bombardment with particles, e.g. treatment in noble gas plasmas; UV irradiation
• CPC Class Codes: H01L 21/76871 Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers

Abstract

In the present invention, a metal halide film is grown which is then reduced to the metal film rather than growing the metal film directly on the substrate surface. In certain embodiments, a metal halide film is grown from at least two precursors: a halogen-containing precursor and a metal-containing precursor. The metal halide film is then exposed to a reducing agent to form the metal film. In certain preferred embodiments, the metal halide film is exposed to the reducing agent prior to the completion of the growing step.

Claims

1. A method of depositing a metal layer on a semiconductor substrate surface, the method comprising:

growing a metal halide layer from a halogen-containing precursor and a metal-containing precursor on at least a portion of the surface; and

exposing the metal halide layer to a reducing agent to provide the metal layer.

2. The method of claim 1 wherein the growing step comprises:

chemisorbing the halogen-containing precursor on at least a portion of the surface; and

chemisorbing the metal-containing precursor on at least a portion of the surface wherein the metal and the halogen within the precursors react to form the metal halide layer.

3. The method of claim 1 wherein the halogen-containing precursor and the metal-containing precursor are delivered sequentially to form the metal halide layer.

4. The method of claim 1 wherein the halogen-containing precursor and the metal-containing precursor are co-reacted to form the metal halide layer.

5. The method of claim 1 wherein the halogen-containing precursor is at least one from the group consisting of halogen-containing acids, halogen-containing silanes, alkylchlorosilanes, alkylbromosilanes, alkyliodosilanes, silicon halide compounds, halogenated tin compounds, germane compounds, boron trihalide compounds, alkylaluminum halide compounds, aluminum halide compounds, gallium halide compounds, or combinations thereof.

6. The method of claim 5 wherein the halogen-containing precursor is a halogen-containing acid.

7. The method of claim 6 wherein the halogen-containing precursor is HCI.

8. The method of claim 1 wherein the metal-containing precursor comprises copper.

9. The method of claim 8 wherein the metal-containing precursor is at least one from the group consisting of Cu(I) β

-diketonate (L) wherein (L) is stabilizing ligand such as an olefin, diene, silyl olefin, alkyne of silylalkyne, isonitrile, carbon monoxide, trialkyphospine;

Cu(II)bis(β

-diketonates);

Cu(II)bis(β

-diimines);

Cu(I)β

-diimine (L) where (L) is a stabilizing ligand such as an olefin, silyl olefin, alkyne of silylalkyne, dienes, isonitrile, carbon monoxide, trialkyphospine;

Cu(I) alkoxides;

Cu(I) amides;

Cu(II) β

-ketoimines;

Cu(I)β

-ketoimine(L) where (L) is a stabilizing ligand such as an olefin, silyl olefin, alkyne of silylalkyne, dienes, isonitrile, carbon monoxide, trialkyphospine;

Cu(II) bis(alkoxyamines);

Cu(I) alkyls;

Cu(I) aryls;

or Cu(I) phenoxides.

10. The method of claim 1 wherein the metal-containing precursor comprises at least one compound represented by the structure:

wherein M and M′

are each Cu, Ag, Au, Os, or Ir;

X and X′

are each N or O;

Y and Y′

are each Si, C, Sn, Ge, B, or Al;

Z and Z′

are each C, N, or O;

R1, R2, R1′

, and R2′

are each independently an alkyl, an alkenyl, an alkynyl, a partially fluorinated alkyl, an aryl, an alkyl-substituted aryl, a partially, fluorinated aryl, fluoralkyl-substituted aryl, a trialkylsilyl, or a triarylsilyl when X and X′

are N;

R1 and R1′

are each independently an alkyl, an alkenyl, are alkynyl, a partially fluorinated alkyl, an aryl, an alkyl-substituted aryl, a partially fluorinated aryl, a fluoralkyl-substituted aryl, a trialkylsilyl, or a triarylsilyl when X and X′

are O;

R3, R4, R3′

, and R4′

are each independently a hydrogen, an alkyl, a partially fluorinated alkyl, a trialkylsilyl, a triarylsilyl, a trialkylsiloxy, a triarylsiloxy, an aryl, an alkyl-substituted aryl, a partially fluorinated aryl, a fluoroalkyl-substituted aryl, or an alkoxy; and

R5, R6, R5′

, and R6′

are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, a partially fluorinated alkyl, an aryl, an alkyl-substituted aryl, partially fluorinated aryl, a fluoralkyl-substituted aryl, a trialkylsiloxy, a triarylsiloxy, a trialkylsilyl, a triarylsilyl, or an alkoxy, a SiR7R8N(R9R10) group, or a SiR7R8OR11 group where R7, R8, R9, R10, and R11 can be an alkyl;

provided that when X and X′

are each O, there is no substitution at R2 and R2′

;

further provided that when Z and Z′

are each N, there is no substitution at R6 and R6′

;

further provided that when Z and Z′

are each O, there is no substitution at R5, R6, R5′

, or R6′

;

said alkyl and alkoxide having 1 to 8 carbons;

said alkenyl and alkynyl having 2 to 8 carbons;

and said aryl having 6 carbons.

11. The method of claim 1 wherein the semiconductor substrate has a barrier layer to which the metal halide layer is grown thereupon.

12. The method of claim 11 wherein the barrier layer is at least one selected from the group consisting of titanium nitride compounds, titanium compounds, tantalum nitride compounds, tungsten carbon nitride compounds, tantalum compounds, silicide compounds of the foregoing, or mixtures thereof.

13. The method of claim 1 wherein the reducing agent is at least one from the group consisting of hydrogen, silanes, boranes, alanes, germanes, hydrazines, or mixtures thereof.

14. The method of claim 13 wherein the reducing agent is a silane.

15. The method of claim 14 wherein the reducing agent is diethylsilane.

16. The method of claim 1 wherein the exposing step is conducted prior to the completion of the growing step.

17. The method of claim 1 wherein the exposing step is conducted after the completion of the growing step.

18. A method for forming a metal layer on a surface of a substrate, the method comprising:

growing a metal halide layer on the surface by contacting the surface with a halogen-containing precursor and a metal-containing precursor wherein the halogen and the metal within the precursors react to form the metal halide layer; and

exposing the metal halide layer to a reducing agent to provide the metal layer.

19. The method of claim 18 further comprising forming an alloy metal halide layer from an alloy metal-containing precursor wherein the metal in the alloy metal-containing precursor is different from the metal of the metal-containing precursor.

20. The method of claim 19 wherein the alloy metal-containing precursor is at least one from the group consisting of Ag, Au, Os, Ir, Pt, Pd, Rh, Re, Ni, Co, Ru, or combinations thereof.

21. The method of claim 19 wherein the forming step is conducted prior to the exposing step.

22. The method of claim 18 wherein the exposing step occurs prior to the completion of the growing step.

23. The method of claim 18 wherein the exposing step occurs after the completion of the growing step.

24. A method of depositing a metal layer on semiconductor substrate surface, the method comprising:

growing a metal halide layer from a halogen-containing precursor comprising an acid and a metal-containing precursor on at a least a portion of the surface wherein the semiconductor substrate has a barrier layer to which the metal halide layer is grown thereupon; and

exposing the metal halide layer to a reducing agent to provide the metal layer.

25. The method of claim 24 wherein the acid is at least one selected from the group consisting of hydrohalic acids or fluorinated acids.

26. The method of claim 24 wherein the barrier layer is at least one compound selected from the group consisting of titanium nitride compounds, titanium compounds, tantalum nitride compounds, tungsten carbon nitride compounds, tantalum compounds, silicide compounds of the foregoing or mixtures thereof.

27. A method of depositing a metal layer on at least a portion of a substrate surface, comprising:

alternately introducing vapor phase pulses of a halogen-containing precursor and a metal-containing precursor into a reaction chamber having the substrate contained therein to provide a metal halide layer and exposing the metal halide layer to a reducing agent to provide the metal layer.

28. A method of depositing a metal layer on a surface of an article, the method comprising:

growing a metal halide layer on at least a portion of the surface from plurality of precursors comprising;

a halogen-containing precursor and a metal-containing precursor wherein the halogen-containing precursor is substantially free of metal or contains metal that differs from that in the metal layer; and

exposing the metal halide layer to a reducing agent to provide the metal layer.

29. The method of claim 28 wherein the plurality of precursors within the growing step further comprises an alloy metal-containing precursor.

30. A method for forming a metal layer comprising at least one metal on a surface of an article, the method comprising:

growing a metal halide layer on the surface by contacting the surface with a halogen-containing precursor, a metal-containing precursor, and optionally an alloy metal-containing precursor wherein the halogen, the metal, and optionally the alloy metal within the precursors react to form the metal halide layer and wherein the halogen-containing precursor is substantially free of metal or contains metal that differs from that in the metal layer; and

exposing the metal halide layer to a reducing agent to provide the metal layer.