Metal nitride formation

• US 20030224217A1
• Filed: 10/21/2002
• Published: 12/04/2003
• Est. Priority Date: 05/31/2002
• Status: Abandoned Application

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Zhang, Hui, Xi, Ming, Yoon, Hyungsuk Alexander, Mak, Alfred W., Byun, Jeong Soo, Jackson, Robert L., Gelatos, Avgerinos V., Thakur, Randhir P.S.
• Application Number:
  US10/278,179
• Publication Number:
  US 20030224217A1
• Time in Patent Office: Days
• US Class Current: 428/698
• CPC Class Codes: C04B 2235/421 Boron
• CPC Class Codes: C04B 35/58007 based on refractory metal nitrides
• CPC Class Codes: C23C 16/38 Borides
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/76846 Layer combinations
• CPC Class Codes: H01L 21/76856 by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner
• CPC Class Codes: H01L 21/76864 Thermal treatment
• CPC Class Codes: H01L 28/75 comprising two or more layers, e.g. comprising a barrier layer and a metal layer

Abstract

A process for treating refractory metal-boron layers deposited by atomic layer deposition resulting in the formation of a ternary amorphous refractory metal-nitrogen-boron film is disclosed. The resulting ternary film remains amorphous following thermal annealing at temperatures up to 800° C. The ternary films are formed following thermal annealing in a reactive nitrogen-containing gas. Subsequent processing does not disrupt the amorphous character of the ternary film. arrangement where a blended solution is supplied to a remote point of use.

Claims

1. A process for formation of a nitrogen-containing refractory metal film comprising the steps of depositing a refractory metal-boron layer on the substrate;

and

annealing a substrate in a nitrogen-containing atmosphere at a temperature of at least 400°

C.

2. The process of claim 1 wherein said refractory metal-boron layer is deposited by atomic layer deposition.

3. The process of claim 1 wherein said refractory metal-boron layer comprises more than one refractory metals.

4. The process of claim 1 wherein the one or more refractory metal is selected from the group of tungsten (W), titanium (Ti), tantalum (Ta), molybdenum (Mo), zirconium (Zr), hafnium (Hf), cobalt (Co), ruthenium (Ru), platinum (Pt), iridium (Ir), palladium (Pd) or combinations thereof.

5. The process of claim 1 wherein said nitrogen-containing atmosphere comprises one or more gases from the group of ammonia, hydrazine, derivatives of hydrazine or nitrogen gas.

6. The process of claim 1 wherein said nitrogen-containing atmosphere comprises one or more gases from the group of ammonia, hydrazine, derivatives of hydrazine or nitrogen gas which has been activated by a plasma.

7. The process of claim 1 wherein the annealing step is performed at a temperature in a range from about 400°

C. to about 500°

C.

8. The process of claim 1 wherein the annealing step is performed at a temperature in a range from about 500°

C. to about 800°

C.

9. The process of claim 1 wherein the annealing step is performed for a time in a range of about 10 seconds to about 100 seconds.

10. A process for treating a substrate on which a tungsten-boron layer has been deposited comprising the step of annealing said substrate in the presence of ammonia ambient.

11. The process of claim 10 wherein the annealing step occurs at an ambient temperature between about 400°

C. and about 500°

C.

12. The process of claim 10 wherein the annealing step occurs at an ambient temperature between about 500°

C. and about 800°

C.

13. A process for forming a device, comprising the steps of:

depositing a refractory metal-boron layer on a substrate having a dielectric layer thereon, wherein the dielectric layer has one or more via holes therein; and

annealing the substrate in a reactive nitrogen-containing gas.

15. The process of claim 13 wherein the refractory metal-boron layer is tungsten boride.

16. The process of claim 13 wherein the reactive nitrogen-containing gas is ammonia.

18. A process for fabrication of a MIM structured capacitor comprising the steps of:

depositing a refractory metal-boron layer on a substrate having a dielectric layer thereon and having a storage node communicating through a portion of said substrate, wherein the dielectric layer has a via hole therein and wherein a top surface of said storage node communicates with said via hole; and

annealing said substrate in a reactive nitrogen-containing gas.

14. The process for forming a device of claim 20 further comprising the step of depositing a conductive layer on the substrate, wherein the conductive layer fills said via holes.

17. The process of claim 14 wherein the conductive layer is copper.

19. The process for fabrication of a MIM structured capacitor of claim 18 further comprising the step of depositing a high dielectric constant insulator on the substrate.

20. The process for fabrication of a MIM structured capacitor of claim 19 further comprising the step of depositing an upper electrode layer on said substrate, said upper electrode layer filling said via holes.

21. The process of claim 18 wherein the refractory metal-boron layer is tungsten boride.

22. The process of claim 18 wherein the reactive nitrogen-containing gas is ammonia.

24. The process of claim 20 wherein said upper electrode layer is titanium nitride.

25. An interconnect device comprising:

(a) a substrate having a dielectric layer thereon, wherein the dielectric layer has one or more via holes therein;

(b) a refractory metal-nitrogen-boron layer deposited on said substrate; and

(c) a conductive layer on said substrate overlying said refractory metal-nitrogen-boron layer and wherein said conductive layer fills said via holes.

23. The process of claim 26 wherein said high dielectric constant insulator is tantalum dioxide.

26. The interconnect device of claim 25 wherein said refractory metal-nitrogen-boron layer is tungsten-nitrogen-boron.

27. The interconnect device of claim 25 wherein said conductive layer is copper.

28. A MIM structured capacitor comprising:

(a) a substrate having a dielectric layer thereon and having a storage node communicating through a portion of the substrate, wherein the dielectric layer has a via hole therein and wherein a top surface of the storage node communicates with the via hole;

(b) a refractory metal-nitrogen-boron layer deposited on the substrate;

(c) a high dielectric constant insulator layer deposited on the substrate overlying the refractory metal-nitrogen-boron layer; and

(d) an upper electrode layer on said substrate overlying the refractory metal-nitrogen-boron layer, the upper electrode layer filling said via holes.

29. The MIM structured capacitor of claim 28 wherein the substrate is silicon.

30. The MIM structured capacitor of claim 28 wherein the dielectric layer is silicon dioxide.

31. The MIM structured capacitor of claim 28 wherein the high dielectric constant insulator layer is tantalum dioxide.

32. The MIM structured capacitor of claim 28 wherein the upper electrode layer is titanium nitride.

33. A barrier film for use in the fabrication of wafers comprising:

a ternary phase comprising tungsten nitride and tungsten boride.

34. The barrier film of claim 33 wherein the atomic percentage of nitrogen is between about 2.5% and about 15%.

36. A barrier film for use in the fabrication of wafer comprising:

a surface layer comprising tungsten nitride and boron nitride; and

a lower layer comprising tungsten boride and tungsten nitride.

35. The barrier of film of claim 40 wherein the atomic percentage of boron is about 20%.

37. The barrier film of claim 36 wherein said surface layer is about 7.5 nm thick.

38. The barrier film of claim 36 wherein the atomic percentage of nitrogen in said surface layer is between about 40% and 18%.

39. The barrier film of claim 36 wherein the atomic percentage of nitrogen in said lower layer is between about 5% and 18%.

40. The barrier film of claim 36 wherein the atomic percentage of boron in said surface layer is between about 10% and 20%.

41. The barrier film of claim 36 wherein the atomic percentage of boron is said lower layer is between about 20% and 25%.

42. A barrier film for use in the fabrication of wafer comprising:

a surface layer consisting essentially of tungsten, boron and nitrogen; and

a lower layer consisting essentially of tungsten, boron and nitrogen.

43. The barrier film of claim 42 wherein said surface layer is about 7.5 nm thick.

44. The barrier film of claim 42 wherein the atomic percentage of nitrogen in said surface layer is between about 40% and 18%.

45. The barrier film of claim 42 wherein the atomic percentage of nitrogen in said lower layer is between about 5% and 18%.

46. The barrier film of claim 42 wherein the atomic percentage of boron in said surface layer is between about 10% and 20%.

47. The barrier film of claim 42 wherein the atomic percentage of boron is said lower layer is between about 20% and 25%.

48. A barrier film for use in the fabrication of wafers comprising:

a ternary phase consisting essentially of tungsten, nitrogen, and boron.

49. The barrier film of claim 48 wherein the atomic percentage of nitrogen is between about 2.5% and about 15%.

50. The barrier of film of claim 48 wherein the atomic percentage of boron is about 20%.