Electroless deposition process on a silicon contact

• US 7,659,203 B2
• Filed: 03/20/2006
• Issued: 02/09/2010
• Est. Priority Date: 03/18/2005
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Eaglesham, David J., Weidman, Timothy W., Shanmugasundram, Arulkumar, Stewart, Michael P.
• Primary Examiner(s): Kebede; Brook
• Application Number:
  US11/385,043
• Publication Number:
  US 20060264043A1
• Time in Patent Office: 1,422 Days
• Field of Search: 438618-630, 438641-644, 438648-658, 438674-678, 438/683, 438685-688, 257/E21.006
• US Class Current: 438/678
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C23C 18/1651 Two or more layers only obtained by electroless plating
• CPC Class Codes: C23C 18/1893 with use of organic or inorganic compounds other than metals, first
• CPC Class Codes: C23C 18/32 Coating with nickel, cobalt or mixtures thereof with phosphorus or boron C23C18/50 takes precedence
• CPC Class Codes: C23C 18/34 using reducing agents
• CPC Class Codes: H01L 21/02063 the processing being the formation of vias or contact holes
• CPC Class Codes: H01L 21/28518 the conductive layers comprising silicides H01L21/28537 takes precedence
• CPC Class Codes: H01L 21/288 from a liquid, e.g. electrolytic deposition
• CPC Class Codes: H01L 21/76802 by forming openings in dielectrics
• CPC Class Codes: H01L 21/76814 post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76847 the layer being positioned within the main fill metal
• CPC Class Codes: H01L 21/76855 After-treatment introducing at least one additional element into the layer
• CPC Class Codes: H01L 21/76856 by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner
• CPC Class Codes: H01L 21/76867 characterized by methods of formation other than PVD, CVD or deposition from a liquids PVD H01L21/2855; CVD H01L21/28556; deposition from liquids H01L21/288
• CPC Class Codes: H01L 21/76874 for electroless plating
• CPC Class Codes: H01L 21/76879 by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating plating on semiconductors in general H01L21/288
• CPC Class Codes: H01L 21/76889 by forming silicides of refractory metals

Abstract

Embodiments as described herein provide methods for depositing a material on a substrate during electroless deposition processes, as well as compositions of the electroless deposition solutions. In one embodiment, the substrate contains a contact aperture having an exposed silicon contact surface. In another embodiment, the substrate contains a contact aperture having an exposed silicide contact surface. The apertures are filled with a metal contact material by exposing the substrate to an electroless deposition process. The metal contact material may contain a cobalt material, a nickel material, or alloys thereof. Prior to filling the apertures, the substrate may be exposed to a variety of pretreatment processes, such as preclean processes and activations processes. A preclean process may remove organic residues, native oxides, and other contaminants during a wet clean process or a plasma etch process. Embodiments of the process also provide the deposition of additional layers, such as a capping layer.

Claims

1. A method for depositing a material on a substrate, comprising:

positioning a substrate within a process chamber, wherein the substrate comprises an aperture containing an exposed silicon contact surface;

exposing the substrate to a preclean process to remove native oxides or contaminants from the exposed silicon contact surface; and

exposing the substrate to a first electroless deposition process to form a metal-containing layer on the exposed silicon contact surface, wherein the metal-containing layer comprises cobalt, nickel, derivatives thereof, alloys thereof, or combinations thereof.

2. The method of claim 1, wherein the aperture is filled with the metal-containing layer during the first electroless deposition process.

3. The method of claim 1, wherein the aperture is filled with a metal contact material during a second electroless deposition process.

4. The method of claim 1, wherein the substrate is exposed to a plasma to remove native oxides or contaminants from the exposed silicon contact surface during the preclean process.

5. The method of claim 4, wherein a thin film is formed on the substrate by the plasma and the thin film is removed by a vacuum sublimation process.

6. The method of claim 4, further comprising exposing the substrate to the plasma and a process gas comprising a gas mixture of ammonia and nitrogen trifluoride.

7. The method of claim 6, wherein the gas mixture has a molar ratio of the ammonia to the nitrogen trifluoride within a range from about 1:

1 to about 30;

1.

8. The method of claim 1, wherein the preclean process is a wet clean process.

9. The method of claim 8, wherein the wet clean process comprises exposing the substrate to a wet clean solution comprising hydrogen fluoride and a basic compound selected from the group consisting of ammonium hydroxide, tetramethylammonium hydroxide, ethanolamine, diethanolamine, triethanolamine, derivatives thereof, salts thereof, and combinations thereof.

10. The method of claim 9, wherein the wet clean solution comprises an EA-HF complex, a DEA-HF complex, a TEA-HF complex, a DEA-EA-HF complex, a DEA-TEA-HF complex, a TEA-EA-HF complex, derivatives thereof, salts thereof, and combinations thereof.

11. The method of claim 8, wherein the wet clean process comprises exposing the substrate to a wet clean solution comprising hydrogen peroxide and a basic compound selected from the group consisting of ammonium hydroxide, tetramethylammonium hydroxide, ethanolamine, diethanolamine, triethanolamine, derivatives thereof, salts thereof, and combinations thereof.

12. The method of claim 8, wherein the wet clean process comprises exposing the substrate to a wet clean solution comprising hydrogen peroxide and hydrogen chloride.

13. The method of claim 1, wherein the substrate is exposed to an activation solution prior to forming the metal-containing layer.

14. The method of claim 13, wherein the activation solution comprises a cobalt source, a fluoride source, and a hypophosphite source.

15. The method of claim 14, wherein the activation solution comprises:

a cobalt source at a concentration within a range from about 1 mM to about 100 mM;

a fluoride source at a concentration within a range from about 10 mM to about 400 mM; and

a hypophosphite source at a concentration within a range from about 5 mM to about 150 mM.

16. The method of claim 15, wherein the hypophosphite source is selected from the group consisting of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, tetramethylammonium hypophosphite, salts thereof, derivatives thereof, and combinations thereof.

17. The method of claim 16, wherein the fluoride source is selected from the group consisting of ethanolammonium fluoride, diethanolammonium fluoride, triethanolammonium fluoride, tetramethylammonium fluoride, ammonium fluoride, hydrogen fluoride, salts thereof, derivatives thereof, and combinations thereof.

18. The method of claim 13, wherein the activation solution comprises a reducing agent comprising a metal selected from the group consisting of titanium, iron, chromium, alloys thereof, and combinations thereof.

19. The method of claim 18, wherein the reducing agent comprises a variable-valence metal selected from the group consisting of Ti³⁺/Ti⁴⁺, Fe²⁺/Fe³⁺, Cr²⁺/Cr³⁺, and combinations thereof.

20. The method of claim 18, wherein the reducing agent comprises a ligand selected from the group consisting of a halide, a complexing agent, and combinations thereof.

21. The method of claim 20, wherein the reducing agent comprises a complexing agent selected from the group consisting of carboxylic acids, dicarboxylic acids, polycarboxylic acids, amino acids, amines, diamines, polyamines, alkylamines, alkanolamines, alkoxyamines, and combinations thereof.

22. The method of claim 20, wherein the ligand is citrate.

23. The method of claim 13, wherein the activation solution comprises titanium citrate.

24. The method of claim 3, wherein a self assembled monolayer is deposited within the aperture prior to forming the metal contact material.

25. A method for depositing a material on a substrate, comprising:

positioning a substrate within a process chamber, wherein the substrate comprises an aperture containing an exposed silicon contact surface;

exposing the substrate to a preclean process to remove native oxides or contaminants from the exposed silicon contact surface;

exposing the substrate to an activation solution to form a metal silicide layer on the exposed silicon contact surface; and

filling the aperture with a metal contact material during an electroless deposition process, wherein the metal contact material comprises cobalt, nickel, derivatives thereof, alloys thereof, and combinations thereof.

26. The method of claim 25, wherein the substrate is exposed to a plasma to remove native oxides or contaminants from the exposed silicon contact surface during the preclean process.

27. The method of claim 26, wherein a thin film is formed on the substrate by the plasma and the thin film is removed by a vacuum sublimation process.

28. The method of claim 26, further comprising exposing the substrate to the plasma and a process gas comprising a gas mixture of ammonia and nitrogen trifluoride.

29. The method of claim 25, wherein the preclean process is a wet clean process that provides exposing the substrate to a wet clean solution comprising hydrogen fluoride and a basic compound selected from the group consisting of ammonium hydroxide, tetramethylammonium hydroxide, ethanolamine, diethanolamine, triethanolamine, derivatives thereof, salts thereof, and combinations thereof.

30. The method of claim 29, wherein the wet clean solution comprises an EA-HF complex, a DEA-HF complex, a TEA-HF complex, a DEA-EA-HF complex, a DEA-TEA-HF complex, a TEA-EA-HF complex, derivatives thereof, salts thereof, and combinations thereof.

31. The method of claim 25, wherein the preclean process is a wet clean process that provides exposing the substrate to a wet clean solution comprising hydrogen peroxide and a basic compound selected from the group consisting of ammonium hydroxide, tetramethylammonium hydroxide, ethanolamine, diethanolamine, triethanolamine, derivatives thereof, salts thereof, and combinations thereof.

32. The method of claim 25, wherein the activation solution comprises a cobalt source, a fluoride source, and a hypophosphite source.

33. The method of claim 32, wherein the activation solution comprises:

a cobalt source at a concentration within a range from about 1 mM to about 100 mM;

a fluoride source at a concentration within a range from about 10 mM to about 400 mM; and

a hypophosphite source at a concentration within a range from about 5 mM to about 150 mM.

34. The method of claim 33, wherein the hypophosphite source is selected from the group consisting of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, tetramethylammonium hypophosphite, salts thereof, derivatives thereof, and combinations thereof.

35. The method of claim 34, wherein the fluoride source is selected from the group consisting of ethanolammonium fluoride, diethanolammonium fluoride, triethanolammonium fluoride, tetramethylammonium fluoride, ammonium fluoride, hydrogen fluoride, salts thereof, derivatives thereof, and combinations thereof.

36. The method of claim 25, wherein the metal contact material comprises a cobalt-nickel stack material deposited within the aperture during the electroless deposition process.

37. The method of claim 36, wherein the electroless deposition process comprises sequentially exposing the substrate to a first electroless solution containing a cobalt source and to a second electroless solution containing a nickel source.

38. The method of claim 37, wherein the substrate is exposed to at least one rinse process between each sequential exposures of the first and second electroless solutions.

39. The method of claim 38, wherein a process cycle of the sequential exposures of the first and second electroless solutions is repeated to form the cobalt-nickel stack material having a predetermined thickness.

40. A method for depositing a material on a substrate, comprising:

positioning a substrate within a process chamber, wherein the substrate comprises an aperture containing an exposed silicon contact surface;

exposing the substrate to a plasma to remove native oxides or contaminants from the exposed silicon contact surface during a preclean process, wherein the preclean process comprises forming a thin film on the substrate by the plasma and removing the thin film by a vacuum sublimation process; and

exposing the substrate to a first electroless deposition process to form a metal-containing layer on the exposed silicon contact surface, wherein the metal-containing layer comprises cobalt, nickel, derivatives thereof, alloys thereof, and combinations thereof.

41. The method of claim 40, wherein the preclean process further comprises exposing the substrate to a process gas with the plasma, the process gas comprises a gas mixture of ammonia and nitrogen trifluoride.