Atomic layer deposition of barrier materials

• US 20050009325A1
• Filed: 06/18/2004
• Published: 01/13/2005
• Est. Priority Date: 06/18/2003
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Chung, Hua, Wang, Rongjun, Maity, Nirmalya
• Granted Patent: US 7,211,508 B2
• Time in Patent Office: Days
• US Class Current: 438/637
• CPC Class Codes: C23C 16/02 Pretreatment of the material to be coated C23C16/04 takes precedence
• CPC Class Codes: C23C 16/0281 of metallic sub-layers C23C16/029 takes precedence
• CPC Class Codes: C23C 16/14 Deposition of only one other metal element
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• 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
• CPC Class Codes: H01L 21/76871 Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
• CPC Class Codes: H01L 21/76876 for deposition from the gas phase, e.g. CVD

Abstract

Methods for processing substrate to deposit barrier layers of one or more material layers by atomic layer deposition are provided. In one aspect, a method is provided for processing a substrate including depositing a metal nitride barrier layer on at least a portion of a substrate surface by alternately introducing one or more pulses of a metal containing compound and one or more pulses of a nitrogen containing compound and depositing a metal barrier layer on at least a portion of the metal nitride barrier layer by alternately introducing one or more pulses of a metal containing compound and one or more pulses of a reductant. A soak process may be performed on the substrate surface before deposition of the metal nitride barrier layer and/or metal barrier layer.

Claims

1. A method for processing a substrate, comprising:

exposing the substrate to a soak process comprising a tungsten precursor; and

depositing a tantalum barrier layer on the substrate by an atomic layer deposition process, comprising exposing the substrate to sequential pulses of a tantalum precursor and a reductant.

2. The method of claim 1, wherein the reductant comprises a nitrogen free reductant selected from the group consisting of silane, disilane, silane derivatives, borane, diborane, borane derivatives, hydrogen, and combinations thereof, and the tantalum precursor comprises tantalum pentafluoride, pentakis(dimethylamino)tantalum, or combinations thereof.

3. The method of claim 2, wherein the tungsten precursor comprises tungsten hexafluoride.

4. The method of claim 1, further comprising depositing a tantalum nitride barrier layer on a substrate surface prior to exposing the substrate to the soak process by alternately introducing one or more pulses of a nitrogen containing compound and one or more pulses of a metal containing compound.

5. The method of claim 4, wherein the tantalum nitride barrier layer is deposited by one or more pulses of an amine containing compound and a tantalum containing compound.

6. The method of claim 1, further comprising exposing the tantalum barrier layer to a plasma treatment.

7. A method for processing a substrate, comprising:

depositing a tantalum nitride barrier layer on the substrate by an atomic layer deposition process, comprising exposing the substrate to sequential pulses of a first tantalum precursor and a nitrogen precursor;

exposing the substrate to a soak process comprising a tungsten-containing compound; and

depositing a tantalum barrier layer on the tantalum nitride barrier layer by a second atomic layer deposition process, comprising exposing the substrate to sequential pulses of a second tantalum precursor and a reductant.

8. The method of claim 7, wherein the nitrogen precursor comprises a compound selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, and combinations thereof, and the reductant comprises a nitrogen free reductant selected from the group consisting of silane, disilane, silane derivatives, borane, diborane, borane derivatives, hydrogen, and combinations thereof.

9. The method of claim 8, wherein the first tantalum precursor comprises pentakis(dimethylamino)tantalum, the second tantalum precursor comprises tantalum pentafluoride, and the tungsten containing precursor comprises tungsten hexafluoride.

10. The method of claim 9, further comprising exposing the tantalum barrier layer to a plasma treatment.

11. A method for processing a substrate, comprising:

depositing a metal nitride layer on at least a portion of a substrate surface by alternately introducing one or more pulses of a first metal containing compound and one or more pulses of a nitrogen containing compound;

exposing the metal nitride layer to a first nitrogen free reductant;

exposing the metal nitride layer to a tungsten containing compound; and

depositing a metal containing barrier layer on at least a portion of the metal nitride layer by alternately introducing one or more pulses of a second metal containing compound and one or more pulses of a second nitrogen free reductant.

12. The method of claim 11, further comprising exposing the substrate surface to a plasma treatment.

13. The method of claim 11, wherein the metal nitride layer comprises tantalum nitride and the metal containing barrier comprises tantalum, tantalum boride, or tantalum silicide.

14. The method of claim 11, wherein the first and second metal containing compounds are independently selected from a group consisting of t-butylimino-tris(diethylamino)tantalum, pentakis(ethylmethylamino)tantalum, pentakis(dimethylamino)tantalum, pentakis(diethylamino)tantalum, t-butylimino-tris(ethylmethylamino)tantalum, t-butylimino-tris(dimethylamino)tantalum, bis(cyclopentadienyl)tantalum trihydride, bis(methylcyclopentadienyl)tantalum trihydride, tantalum pentafluoride, tantalum pentachloride, tantalum pentabromide, tantalum pentaiodide, and combinations thereof, and the tungsten containing compound comprises tungsten hexafluoride.

15. The method of claim 14, wherein the nitrogen containing compound is selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, derivatives thereof, and combinations thereof, and the first and second nitrogen free reductants are selected from the group consisting of silane, disilane, dichlorosilane, hexachlorodisilane, borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nanoborane, and decaborane, triethylborane, and combinations thereof.

16. The method of claim 15, wherein the first and second metal containing compounds independently comprise pentakis(dimethylamino)tantalum or tantalum pentafluoride, the nitrogen containing compound comprises ammonia, and the tungsten containing compound comprises tungsten hexafluoride.

17. The method of claim 11, wherein depositing the metal nitride layer, exposing the metal nitride layer to the tungsten containing compound, exposing the metal nitride layer to the reductant, and depositing the metal containing barrier layer are performed in the same chamber or processing apparatus without breaking vacuum.

18. A method for processing a substrate, comprising:

depositing a tantalum nitride barrier layer on a substrate surface by alternately introducing one or more pulses of a first tantalum containing compound and one or more pulses of a nitrogen containing compound into a processing chamber;

depositing a tantalum containing barrier layer on at least a portion of the tantalum nitride barrier layer by alternately introducing into the processing chamber one or more pulses of a second tantalum containing compound and one or more pulses of a reductant into a processing chamber; and

exposing the tantalum containing barrier layer to a plasma treatment process.

19. The method of claim 18, wherein the plasma treatment process comprises a reducing gas.

20. The method of claim 19, wherein the reducing gas comprises hydrogen.

21. The method of claim 18, wherein the first and second tantalum containing compounds independently comprise pentakis(dimethylamino)tantalum or tantalum pentafluoride, the nitrogen containing compound comprises ammonia, and the reductant comprises diborane or silane.

22. The method of claim 19, wherein depositing the tantalum nitride barrier layer, depositing the tantalum containing barrier layer, and exposing the tantalum containing barrier to the plasma treatment is performed in the same chamber or processing apparatus without breaking vacuum.

23. The method of claim 18, wherein the tantalum containing barrier layer comprises tantalum, tantalum boride, or tantalum silicide.

24. A method for processing a substrate, comprising:

exposing the substrate to a first soak process, wherein the soak process includes a first reductant for a predetermined time;

depositing a tantalum nitride barrier layer on the substrate by an atomic layer deposition process in a process chamber, comprising;

exposing the substrate to a tantalum precursor;

purging the process chamber with a purge gas;

exposing the substrate to a nitrogen precursor; and

purging the process chamber with the purge gas;

exposing the substrate to a second soak process; and

depositing a tantalum barrier layer on the tantalum nitride barrier layer.

25. The method of claim 24, wherein the predetermined time comprises one or more seconds.

26. The method of claim 25, wherein the nitrogen precursor s selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, derivatives thereof, and combinations thereof.

27. The method of claim 25, wherein the tantalum precursor comprises a material selected from the group consisting of t-butylimino-tris(diethylamino)tantalum, pentakis(ethylmethylamino)tantalum, pentakis(dimethylamino)tantalum, pentakis(diethylamino)tantalum, t-butylimino-tris(ethylmethylamino)tantalum, t-butylimino-tris(dimethylamino)tantalum, bis(cyclopentadienyl)tantalum trihydride, bis(methylcyclopentadienyl)tantalum trihydride, tantalum pentafluoride, tantalum pentachloride, tantalum pentabromide, tantalum pentaiodide, and combinations thereof, and the second soak process comprises tungsten hexafluoride.

28. The method of claim 27, wherein the purge gas comprises a gas selected from the group consisting of helium, argon, hydrogen, nitrogen, or combinations thereof.

29. The method of claim 28, wherein the second soak process comprises:

exposing the tantalum nitride barrier layer to a first nitrogen free reductant; and

exposing the tantalum nitride layer to the tungsten hexafluoride.

30. The method of claim 29, further comprising exposing the tantalum barrier layer to a plasma treatment process.

31. A method for processing a substrate, comprising:

depositing a tantalum nitride barrier layer on the substrate by an atomic layer deposition process in a process chamber, comprising;

exposing the substrate to a first tantalum precursor;

purging the process chamber with a purge gas;

exposing the substrate to a nitrogen precursor; and

purging the process chamber with the purge gas;

exposing the substrate to a soak process; and

depositing a tantalum barrier layer on the tantalum nitride barrier layer by a second atomic layer deposition process, comprising;

exposing the substrate to a second tantalum precursor;

purging with the purge gas;

exposing the substrate with a nitrogen free reductant; and

purging with the purge gas.

32. The method of claim 31, wherein the nitrogen precursor comprises a nitrogen containing compound selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, derivatives thereof, and combinations thereof, and the nitrogen free reductant comprises a compound selected from the group consisting of silane, disilane, dichlorosilane, hexachlorodisilane, borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nanoborane, decaborane, triethylborane, and combinations thereof.

33. The method of claim 32, wherein the first and second tantalum precursors independently comprise a material selected from the group consisting of t-butylimino-tris(diethylamino)tantalum, pentakis(ethylmethylamino)tantalum, pentakis(dimethylamino)tantalum, pentakis(diethylamino)tantalum, t-butylimino-tris(ethylmethylamino)tantalum, t-butylimino-tris(dimethylamino)tantalum, bis(cyclopentadienyl)tantalum trihydride, bis(methylcyclopentadienyl)tantalum trihydride, tantalum pentafluoride, tantalum pentachloride, tantalum pentabromide, tantalum pentaiodide, and combinations thereof, and the tungsten containing compound comprises tungsten hexafluoride.

34. The method of claim 33, wherein the purge gas comprises a gas selected from the group consisting of helium, argon, hydrogen, nitrogen, or combinations thereof.

35. The method of claim 34, further comprising exposing the tantalum barrier layer to a plasma treatment process.

36. A method for processing a substrate, comprising:

depositing a tantalum nitride barrier layer on the substrate by an atomic layer deposition process in a process chamber, comprising;

exposing the substrate to an organometallic tantalum precursor;

purging the process chamber with a purge gas;

exposing the substrate to a nitrogen precursor; and

purging the process chamber with the purge gas; and

depositing a tantalum barrier layer on the tantalum nitride barrier layer by a second atomic layer deposition process, comprising exposing the substrate to sequential pulses of a tantalum halide precursor and a reductant.

37. The method of claim 36, wherein the nitrogen precursor comprises a nitrogen containing compound selected from the group consisting of ammonia, hydrazine, methylhydrazine, dimethylhydrazine, t-butylhydrazine, phenylhydrazine, azoisobutane, ethylazide, derivatives thereof, and combinations thereof, and the reductant comprises a nitrogen free compound selected from the group consisting of silane, disilane, dichlorosilane, hexachlorodisilane, borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nanoborane, decaborane, triethylborane, and combinations thereof.

38. The method of claim 36, wherein the organometallic tantalum precursor comprises a compound selected from the group consisting of t-butylimino-tris(diethylamino)tantalum, pentakis(ethylmethylamino)tantalum, pentakis(dimethylamino)tantalum, pentakis(diethylamino)tantalum, t-butylimino-tris(ethylmethylamino)tantalum, t-butylimino-tris(dimethyl amino)tantalum, bis(cyclopentadienyl)tantalum trihydride, bis(methylcyclopentadienyl)tantalum trihydride, and the tantalum halide precursor is selected from the group consisiting of tantalum pentafluoride, tantalum pentachloride, tantalum pentabromide, tantalum pentaiodide, and combinations thereof, and the tungsten containing compound comprises tungsten hexafluoride.

39. The method of claim 38, wherein the purge gas comprises a gas selected from the group consisting of helium, argon, hydrogen, nitrogen, or combinations thereof.

40. The method of claim 39, further comprising exposing the tantalum barrier layer to a plasma treatment process.

41. A method for processing a substrate, comprising:

depositing a nitride layer containing a first metal by a first atomic layer deposition process;

exposing the nitride layer to a soak process comprising a second metal different than the first metal; and

depositing a metal layer on the nitride layer by a second atomic layer deposition process, wherein the metal layer comprises the first metal.

42. The method of claim 41, wherein the first metal is selected from the group consisting of tantalum, titanium, ruthenium, and combinations thereof.

43. The method of claim 42, wherein the first metal is tantalum and the second metal is tungsten.

44. The method of claim 43, wherein the first atomic layer deposition process comprises an organometallic tantalum precursor and the second atomic layer deposition process comprises a tantalum halide precursor.

45. The method of claim 43, wherein the soak process comprises tungsten hexafluoride.

46. The method of claim 44, further comprising exposing the metal layer to a plasma treatment.