Methods of forming metal layers using metallic precursors

• US 20030017697A1
• Filed: 07/17/2002
• Published: 01/23/2003
• Est. Priority Date: 07/19/2001
• Status: Abandoned Application

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Choi, Gil-Heyun, Kim, Byung-Hee, Choi, Kyung-In, Kang, Sang-Bum
• Application Number:
  US10/196,814
• Publication Number:
  US 20030017697A1
• Time in Patent Office: Days
• US Class Current: 438/679
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76862 Bombardment with particles, e.g. treatment in noble gas plasmas; UV irradiation

Abstract

Methods of forming metal layers include techniques to form metal layers using atomic layer deposition techniques that may be repeated in sequence to build up multiple atomic metal layers into a metal thin film. The methods include forming a metal layer by chemisorbing a metallic precursor comprising a metal element and at least one non-metal element that is ligand-bonded to the metal element, on a substrate. The metal element may include tantalum. The chemisorbed metallic precursor is then converted into the metal layer by removing the at least one non-metal element from the metallic precursor through ligand exchange. This removal of the non-metal element may be achieved by exposing the chemisorbed metallic precursor to an activated gas that is established by a remote plasma, which reduces substrate damage. The activated gas may be selected from the group consisting of H₂, NH₃, SiH₄ and Si₂H₆ and combinations thereof. These steps may be performed at a temperature less than about 650° C.

Claims

1. A method of forming a metal layer, comprising the steps of:

chemisorbing a metallic precursor on a substrate, said metallic precursor comprising a metal element and at least one non-metal element that is ligand-bonded to the metal element; and

converting the chemisorbed metallic precursor into the metal layer by removing the at least one non-metal element from the metallic precursor.

2. The method of claim 1, wherein said chemisorbing step comprises exposing the substrate to a metallorganic precursor comprising tantalum or exposing the substrate to a tantalum halide precursor.

3. The method of claim 1, wherein said chemisorbing step comprises exposing the substrate to a tantalum amine derivative.

4. The method of claim 1, wherein said converting step comprises exposing the chemisorbed metallic precursor to an activated gas that is established by a remote plasma.

5. The method of claim 4, wherein the activated gas is selected from the group consisting of H₂, NH₃, SiH₄ and Si₂H₆ and combinations thereof.

6. The method of claim 1, wherein the substrate comprises a semiconductor substrate;

and wherein said chemisorbing step comprises;

exposing the substrate to reactants comprising a metal element and at least one non-metal element that is ligand-bonded to the metal element; and

removing reactants that have not be chemisorbed to the substrate by exposing the substrate to an inert gas.

7. The method of claim 1, wherein said chemisorbing step and said converting step are performed at a temperature less than about 650°

C.

8. The method of claim 1, wherein said converting step comprises removing the at least one non-metal element from the metallic precursor by ligand exchange.

9. A method of forming a metal layer, comprising the steps of:

chemisorbing a first metallic precursor comprising a metal element and at least one non-metal element that is ligand-bonded to the metal element, on a substrate;

converting the chemisorbed first metallic precursor into a first atomic metal layer by removing the at least one non-metal element from the first metallic precursor;

chemisorbing a second metallic precursor that comprises the metal element and the at least one non-metal element that is ligand-bonded to the metal element, on the first atomic metal layer; and

converting the chemisorbed second metallic precursor into a second atomic metal layer by removing the at least one non-metal element from the second metallic precursor;

10. The method of claim 9, wherein the first metallic precursor comprises a tantalum-based metallorganic precursor or a tantalum halide precursor.

11. The method of claim 9, wherein said step of chemisorbing a first metallic precursor comprises exposing the substrate to a tantalum amine derivative.

12. The method of claim 9, wherein said step of converting the chemisorbed first metallic precursor comprises exposing the chemisorbed first metallic precursor to an activated gas that is established by a remote plasma.

13. The method of claim 12, wherein the activated gas is selected from the group consisting of H₂, NH₃, SiH₄ and Si₂H₆ and combinations thereof.

14. The method of claim 9, wherein the substrate comprises a semiconductor substrate;

and wherein step of chemisorbing a first metallic precursor comprises;

exposing the substrate to reactants comprising a metal element and at least one non-metal element that is ligand-bonded to the metal element; and

removing reactants that have not be chemisorbed to the substrate by exposing the substrate to an inert gas.

15. The method of claim 9, wherein said step of converting the chemisorbed first metallic precursor comprises removing the at least one nonmetal element from the first metallic precursor by ligand exchange.

16. The method of claim 9, further comprising depositing a conductive layer on the second atomic layer, said conductive layer comprising copper, aluminum, ruthenium and silicon.

18. The method as claimed in claim 17, wherein the metal element included in the reactant is Ta.

19. The method as claimed in claim 17, wherein the reactants include a metallorganic precursor or tantalum halide precursor.

20. The method as claimed in claim 19, wherein the metallorganic precursor is a tantalum amine derivative.

21. The method as claimed in claim 20, wherein the tantalum amine derivative includes terbutylimido-tris-diethylamido-tantalum ((NEt₂)₃Ta=Nbu^t), Ta(NR₁)(NR₂R₃)₃, (wherein, R₁, R₂, and R₃ are H or C₁-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁R₂)₅, (wherein, R₁ and R₂, are H or C₁-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁ R₂) _x(NR₃R₄)₅₋

x, (wherein, R₁, R₂, R₃ and R₄ are H or C₁-C₆ alkyl-radical and are the same or different from each other), or tertiaryamylimido-tris-diethylamido-tantalum (Ta(=NC(CH₃)₂C₂H₅)(N(CH₃)₂)₃).

22. The method as claimed in claim 19, wherein the tantalum halide precursor is at least any one selected from the group consisting of TaF₅, TaCl₅, TaBr₅, and Tal₅.

23. The method as claimed in claim 17, wherein the reactants are introduced in a gaseous state.

24. The method as claimed in claim 17, wherein the non-chemisorbed reactants are removed by using an inert gas.

25. The method as claimed in claim 24, wherein the inert gas includes Ar or N₂.

26. The method as claimed in claim 17, wherein the ligand-bonded element is removed by using any one selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆, and combinations thereof.

27. The method as claimed in claim 17, wherein the ligand-bonded element is removed by using an activated gas selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆, and combinations thereof.

28. The method as claimed in claim 27, wherein the activated gas is prepared through a remote plasma process.

29. The method as claimed in claim 17, wherein the solid is TaN.

30. The method as claimed in claim 17, wherein steps a) to d) are carried out at a temperature no more than 650°

C.

31. The method as claimed in claim 17, wherein steps a) to d) are carried out at a constant pressure in a range of 0.3 to 10 Torr.

17. A method for depositing an atomic layer, the method comprising the steps of:

a) introducing a metallorganic precursor onto a substrate, the metallorganic precursor including a metal element and bonding elements as reactants, the bonding elements being chemically bonded to the metal element, a part of the bonding elements including a ligand bonding element which is ligand-bonded to the metal element;

b) chemisorbing a part of the reactants on the substrate;

c) removing non-chemisorbed reactants from the substrate; and

d) removing the ligand bonded element of the bonded elements from the chemisorbed reactants, thereby forming a metal-containing solid on the substrate.

32. A method for forming a thin film by atomic layer deposition, the method comprising the steps of:

a) introducing gaseous tantalum amine derivative or tantalum halide precursor as reactants onto a substrate;

b) chemisorbing a part of the reactants on the substrate;

c) introducing an inert gas onto the substrate to remove non-chemisorbed reactants from the substrate;

d) introducing any one gas selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆ and combinations thereof onto the substrate to remove a ligand-bonded element from the chemisorbed reactants, thereby forming a TaN-containing solid on the substrate; and

e) repeating steps a) to d) in sequence at least once to form a TaN thin film including the TaN-containing solid.

33. The method as claimed in claim 32, wherein the tantalum amine derivative includes terbutylimido-tris-diethylamido-tantalum ((NEt₂)₃Ta=Nbu^t), Ta(NR₁)(NR₂R₃)₃, (wherein, R₁, R₂, and R₃ are H or C-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁R₂)₅, (wherein, R₁ and R₂, are H or C₁-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁R₂) _x(NR₃R₄)₅₋

x, (wherein, R₁, R₂, R₃ and R₄ are H or C₁-C₆ alkyl-radical and are the same or different from each other), or tertiaryamylimido-tris-diethylamido-tantalum (Ta(=NC(CH₃)₂C₂H₅)(N(CH₃)₂)₃)₃).

34. The method as claimed in claim 32, wherein the tantalum halide precursor includes TaF₅, TaCl₅, TaBr₅, or Tal₅.

35. The method as claimed in claim 32, wherein the gases H₂, NH₃, SiH₄, or Si₂H₆, or combinations thereof, are activated through a remote plasma process.

36. The method as claimed in claim 32, wherein steps a) to d) are carried out at a temperature no more than 650°

C.

37. The method as claimed in claim 32, wherein steps a) to d) are carried out at a constant pressure in a range of 0.3 to 10 Torr.

38. The method as claimed in claim 32, wherein, before carrying out step e), steps c) and d) are repeated at least once.

39. The method as claimed in claim 32, wherein, after carrying out step e), a post treatment process for the TaN film is carried out by using any one selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆, and a combination thereof, which are activated through a remote plasma process.

40. A method for forming a thin film by using an atomic layer deposition, the method comprising the steps of:

a) forming an insulating layer on a substrate;

b) etching a predetermined portion of the insulating layer to form an opening for exposing a surface portion of the substrate;

c) continuously introducing gaseous tantalum amine derivative or tantalum halide precursor as reactants onto the surface portion of the substrate, the insulating layer and a sidewall of the opening;

d) continuously chemisorbing a part of the reactants on the surface portion of the substrate, the insulating layer and a sidewall of the opening;

e) continuously introducing an inert gas onto the surface portion of the substrate, the insulating layer and a sidewall of the opening to remove the non-chemisorbed reactants from the surface portion of the substrate, the insulating layer and a sidewall of the opening;

f) introducing any one selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆, and a combination thereof onto the surface portion of the substrate, the insulating layer and the sidewall of the opening so as to remove a ligand bonded element from the chemisorbed reactants, there by forming a TaN-containing solid; and

g) repeating steps c) to f) at least once to continuously form a TaN thin film from the TaN-containing solid on the surface of the substrate, the insulating layer and the sidewall of the opening.

41. The method as claimed in claim 40, wherein the tantalum amine derivative includes terbutylimido-tris-diethylamido-tantalum ((NEt₂)₃Ta=Nbu^t, Ta(NR₁)(NR₂R₃)₃, (wherein, R₁, R₂, and R₃ are H or C₁-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁R₂)₅, (wherein, R₁ and R₂ are H or C₁-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁ R₂) _x(NR₃R₄)₅₋

x, (wherein, R₁, R₂, R₃ and R₄ are H or C₁-C₆ alkyl-radical and are the same or different from each other), or tertiaryamylimido-tris-diethylamido-tantalum (Ta(=NC(CH₃)₂C₂H₅)(N(CH₃)₂)₃).

42. The method as claimed in claim 40, wherein the tantalum halide precursor includes TaF₅, TaCl₅, TaBr₅, or Tal₅.

43. The method as claimed in claim 40, wherein the insulating layer is a thin film including oxide material, and NH₃, SiH₄, Si₂H₆, and a combination thereof are activated through a remote plasma process.

44. The method as claimed in claim 40, wherein, before carrying out step g), steps e) and f) are repeated at least once.

45. The method as claimed in claim 40, wherein, after carrying out step g), a post treatment process for the TaN film is carried out by using any one selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆, and a combination thereof, which are activated through a remote plasma process.

47. The method as claimed in claim 46, wherein the tantalum amine derivative includes terbutylimido-tris-diethylamido-tantalum ((NEt₂)₃Ta=N but), Ta(NR₁)(NR₂R₃)₃, (wherein, R₁, R₂, and R₃ are H or C₁-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁R₂)₅, (wherein, R₁ and R₂, are H or C₁-C₆ alkyl-radical and are the same or different from each other), Ta(NR₁ R₂) _x(NR₃R₄)₅₋

x, (wherein, R₁, R₂, R₃ and R₄ are H or C₁-C₆ alkyl-radical and are the same or different from each other), or tertiaryamylimido-tris-diethylamido-tantalum (Ta(=NC(CH₃)₂C₂H₅)(N(CH₃)₂)₃).

48. The method as claimed in claim 46, wherein the tantalum halide precursor includes TaF₅, TaCl₅, TaBr₅, or Tal₅.

49. The method as claimed in claim 46, wherein the metal layer is comprised of any one selected from the group consisting of Cu, Al, Ru and Si, and H₂, NH₃, SiH₄, Si₂H₆, and a combination thereof, which are activated through a remote plasma process.

50. The method as claimed in claim 46, wherein, before carrying out step g), steps e) and f) are repeated at least once.

51. The method as claimed in claim 40, wherein, between steps g) and h), a post treatment process for the TaN film is carried out by using any one selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆, and a combination thereof, which are activated through a remote plasma process.

46. A method for forming a metal layer, the method comprising the steps of:

a) forming an insulating layer on a lower structure formed on the substrate;

b) forming an opening for exposing a surface portion of the lower structure by etching a predetermined portion of the insulating layer;

c) continuously introducing gaseous tantalum amine derivative or tantalum halide precursor as reactants onto the surface portion of the lower structure, the insulating layer and a sidewall of the opening;

d) continuously chemisorbing a part of the reactants on the surface portion of the lower structure, the insulating layer and the sidewall of the opening;

e) removing non-chemisorbed reactants from the surface of the lower structure, the insulating layer and the sidewall of the opening by continuously introducing an inert gas onto the surface portion of the lower structure, the insulating layer, and the sidewall of the opening;

f) introducing any one selected from the group consisting of H₂, NH₃, SiH₄, Si₂H₆, and a combination thereof onto the surface portion of the substrate, the insulating layer and the sidewall of the opening so as to remove a ligand-bonded element from the chemisorbed reactants, thereby forming a TaN-containing solid;

g) repeating steps c) to f) at least once to continuously form a TaN thin film from the TaN containing solid on the lower structure, the insulating layer and the sidewall of the opening; and

h) forming a metal layer including the metal on the TaN thin film filling, the metal layer filling up the opening.