APPARATUS AND PROCESS FOR PLASMA-ENHANCED ATOMIC LAYER DEPOSITION

• US 20070128864A1
• Filed: 11/06/2006
• Published: 06/07/2007
• Est. Priority Date: 11/04/2005
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: GANGULI, SESHADRI, WU, DIEN-YEH, MA, PAUL, SHAH, KAVITA, CHU, SCHUBERT, MARCADAL, CHRISTOPHE, WU, FREDERICK
• Granted Patent: US 7,682,946 B2
• Time in Patent Office: Days
• US Class Current: 438/680
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• CPC Class Codes: C23C 16/45544 characterized by the apparatus
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/45563 Gas nozzles
• CPC Class Codes: C23C 16/45565 Shower nozzles
• CPC Class Codes: C23C 16/509 using internal electrodes
• CPC Class Codes: C23C 16/5096 Flat-bed apparatus
• CPC Class Codes: H01J 37/32082 Radio frequency generated discharge H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence
• CPC Class Codes: H01J 37/3244 Gas supply means
• CPC Class Codes: H01J 37/32449 Gas control, e.g. control of the gas flow
• CPC Class Codes: H01J 37/32522 Temperature
• CPC Class Codes: H01J 37/32623 Mechanical discharge control means
• CPC Class Codes: H01J 37/32633 Baffles
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/76844 Bottomless liners
• CPC Class Codes: H01L 21/76846 Layer combinations
• CPC Class Codes: H01L 21/76873 for electroplating
• CPC Class Codes: H01L 2221/1089 Stacks of seed layers
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 : Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

Embodiments of the invention provide a method for forming a material on a substrate during an atomic layer deposition (ALD) process, such as a plasma-enhanced ALD (PE-ALD) process. In one embodiment, a method is provided which includes flowing at least one process gas through at least one conduit to form a circular gas flow pattern, exposing a substrate to the circular gas flow pattern, sequentially pulsing at least one chemical precursor into the process gas and igniting a plasma from the process gas to deposit a material on the substrate. In one example, the circular gas flow pattern has circular geometry of a vortex, a helix, a spiral, or a derivative thereof. Materials that may be deposited by the method include ruthenium, tantalum, tantalum nitride, tungsten or tungsten nitride. Other embodiments of the invention provide an apparatus configured to form the material during the PE-ALD process.

Claims

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

positioning a substrate on a substrate support within a process chamber containing a chamber lid assembly comprising;

a showerhead assembly having an inner region and an outer region;

a plasma screen disposed above the showerhead assembly and configured to direct a first process gas to the inner region and a second process gas to the outer area;

a first gas region located above the inner region and between the showerhead assembly and the plasma screen; and

a second gas region located above the outer region;

flowing at least one carrier gas through at least one conduit to form a circular directional gas;

exposing the substrate to the circular directional gas;

pulsing at least one precursor into the at least one carrier gas; and

depositing a material containing at least one element from the at least one precursor onto the substrate.

2. The method of claim 1, wherein the circular directional gas has circular direction selected from the group consisting of vortex, helix, spiral, twirl, twist, coil, whirlpool, and derivatives thereof.

3. The method of claim 2, wherein the material deposited comprises an element selected from the group consisting of ruthenium, tantalum, tungsten, alloys thereof, nitrides thereof, and combinations thereof.

4. The method of claim 3, wherein the material comprises ruthenium.

5. The method of claim 4, wherein the at least one precursor is selected from the group consisting of bis(tetramethylpyrrolyl)ruthenium, bis(2,5-dimethylpyrrolyl)ruthenium, bis(2,5-diethylpyrrolyl)ruthenium, bis(tetraethylpyrrolyl)ruthenium, pentadienyl tetramethylpyrrolyl ruthenium, pentadienyl 2,5-dimethylpyrrolyl ruthenium, pentadienyl tetraethylpyrrolyl ruthenium, pentadienyl 2,5-diethylpyrrolyl ruthenium, 1,3-dimethylpentadienyl pyrrolyl ruthenium, 1,3-diethylpentadienyl pyrrolyl ruthenium, methylcyclopentadienyl pyrrolyl ruthenium, ethylcyclopentadienyl pyrrolyl ruthenium, 2-methylpyrrolyl pyrrolyl ruthenium, 2-ethylpyrrolyl pyrrolyl ruthenium, derivatives thereof, and combinations thereof.

6. The method of claim 5, wherein a plasma and the at least one precursor is sequentially exposed to the substrate during an atomic layer deposition process.

7. The method of claim 6, wherein the plasma comprises a member selected from the group consisting of ammonia, nitrogen, hydrogen, radicals thereof, derivatives thereof, and combinations thereof.

8. The method of claim 3, wherein the material comprises tantalum or tantalum nitride.

9. The method of claim 8, wherein the at least one precursor is selected from the group consisting of pentakis(dimethylamido)tantalum, pentakis(ethylmethylamido)tantalum, pentakis(diethylamido)tantalum, ethylimido-tris(dimethylamido)tantalum, ethylimido-tris(diethylamido)tantalum, ethylimido-tris(ethylmethylamido)tantalum, tertiarybutylimido-tris(dimethylamido)tantalum, tertiarybutylimido-tris(diethylamido)tantalum, tertiarybutylimido-tris(ethylmethylamido)tantalum, tertiaryamylimido-tris(dimethylamido)tantalum, tertiaryamylimido-tris(diethylamido)tantalum, tertiaryamylimido-tris(ethylmethylamido)tantalum, tantalum fluoride, tantalum chloride, derivatives thereof, and combinations thereof.

10. The method of claim 9, wherein a plasma and the at least one precursor is sequentially exposed to the substrate during an atomic layer deposition process.

11. The method of claim 10, wherein the plasma comprises a member selected from the group consisting of ammonia, nitrogen, hydrogen, radicals thereof, derivatives thereof, and combinations thereof.

12. The method of claim 10, wherein the plasma comprises nitrogen and hydrogen.

13. The method of claim 3, wherein the material comprises tungsten or tungsten nitride.

14. The method of claim 13, wherein the at least one precursor is selected from the group consisting of bis(tertiarybutylimido) bis(tertiarybutylamido)tungsten, bis(tertiarybutylimido) bis(dimethylamido)tungsten, bis(tertiarybutylimido) bis(diethylamido)tungsten, bis(tertiarybutylimido) bis(ethylmethylamido)tungsten, tungsten hexafluoride, derivatives thereof, and combinations thereof.

15. The method of claim 14, wherein a plasma and the at least one precursor is sequentially exposed to the substrate during an atomic layer deposition process.

16. The method of claim 15, wherein the plasma comprises a member selected from the group consisting of ammonia, nitrogen, hydrogen, radicals thereof, derivatives thereof, and combinations thereof.

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

positioning a substrate on a substrate support within a process chamber containing a gas delivery system capable of forming a gas flow in a circular direction;

flowing at least one carrier gas into the process chamber to form a circular directional gas; and

exposing the substrate to the circular directional gas during a plasma-enhanced atomic layer deposition process comprising sequentially igniting a plasma and pulsing at least one precursor into the at least one carrier gas to deposit a material onto the substrate.

18. The method of claim 17, wherein the circular directional gas has circular direction selected from the group consisting of vortex, helix, spiral, twirl, twist, coil, whirlpool, and derivatives thereof.

19. The method of claim 18, wherein the material deposited comprises an element selected from the group consisting of ruthenium, tantalum, tungsten, alloys thereof, nitrides thereof, and combinations thereof.

20. The method of claim 19, wherein the material comprises ruthenium.

21. The method of claim 20, wherein the at least one precursor is selected from the group consisting of bis(tetramethylpyrrolyl)ruthenium, bis(2,5-dimethylpyrrolyl)ruthenium, bis(2,5-diethylpyrrolyl)ruthenium, bis(tetraethylpyrrolyl)ruthenium, pentadienyl tetramethylpyrrolyl ruthenium, pentadienyl 2,5-dimethylpyrrolyl ruthenium, pentadienyl tetraethylpyrrolyl ruthenium, pentadienyl 2,5-diethylpyrrolyl ruthenium, 1,3-dimethylpentadienyl pyrrolyl ruthenium, 1,3-diethylpentadienyl pyrrolyl ruthenium, methylcyclopentadienyl pyrrolyl ruthenium, ethylcyclopentadienyl pyrrolyl ruthenium, 2-methylpyrrolyl pyrrolyl ruthenium, 2-ethylpyrrolyl pyrrolyl ruthenium, derivatives thereof, and combinations thereof.

22. The method of claim 21, wherein the plasma and the at least one precursor are sequentially exposed to the substrate during the atomic layer deposition process.

23. The method of claim 22, wherein the plasma comprises a member selected from the group consisting of ammonia, nitrogen, hydrogen, radicals thereof, derivatives thereof, and combinations thereof.

24. The method of claim 19, wherein the material comprises tantalum or tantalum nitride.

25. The method of claim 24, wherein the at least one precursor is selected from the group consisting of pentakis(dimethylamido)tantalum, pentakis(ethylmethylamido)tantalum, pentakis(diethylamido)tantalum, ethylimido-tris(dimethylamido)tantalum, ethylimido-tris(diethylamido)tantalum, ethylimido-tris(ethylmethylamido)tantalum, tertiarybutylimido-tris(dimethylamido)tantalum, tertiarybutylimido-tris(diethylamido)tantalum, tertiarybutylimido-tris(ethylmethylamido)tantalum, tertiaryamylimido-tris(dimethylamido)tantalum, tertiaryamylimido-tris(diethylamido)tantalum, tertiaryamylimido-tris(ethylmethylamido)tantalum, tantalum fluoride, tantalum chloride, derivatives thereof, and combinations thereof.

26. The method of claim 25, wherein the plasma and the at least one precursor are sequentially exposed to the substrate during the atomic layer deposition process.

27. The method of claim 26, wherein the plasma comprises a member selected from the group consisting of ammonia, nitrogen, hydrogen, radicals thereof, derivatives thereof, and combinations thereof.

28. The method of claim 26, wherein the plasma comprises nitrogen and hydrogen.

29. The method of claim 26, wherein the material comprises tungsten or tungsten nitride.

30. The method of claim 29, wherein the at least one precursor is selected from the group consisting of bis(tertiarybutylimido) bis(tertiarybutylamido)tungsten, bis(tertiarybutylimido) bis(dimethylamido)tungsten, bis(tertiarybutylimido) bis(diethylamido)tungsten, bis(tertiarybutylimido) bis(ethylmethylamido)tungsten, tungsten hexafluoride, derivatives thereof, and combinations thereof.

31. The method of claim 30, wherein the plasma and the at least one precursor are sequentially exposed to the substrate during the atomic layer deposition process.

32. The method of claim 31, wherein the plasma comprises a member selected from the group consisting of ammonia, nitrogen, hydrogen, radicals thereof, derivatives thereof, and combinations thereof.

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

positioning a substrate on a substrate support within a process chamber containing a showerhead assembly having an inner region and an outer region;

flowing at least one carrier gas through the inner region to form a circular directional gas;

exposing the substrate to the circular directional gas; and

exposing the substrate sequentially to at least one precursor and a plasma to deposit a material on the substrate.

34. The method of claim 33, wherein the circular directional gas has circular direction selected from the group consisting of vortex, helix, spiral, twirl, twist, coil, whirlpool, and derivatives thereof.

35. The method of claim 34, wherein the material deposited comprises an element selected from the group consisting of ruthenium, tantalum, tungsten, alloys thereof, nitrides thereof, and combinations thereof.

36. The method of claim 35, wherein the plasma comprises a compound selected from the group consisting of hydrogen, nitrogen, ammonia, derivatives thereof, and combinations thereof.