Method of irradiating substrate with gas cluster ion beam formed from multiple gas nozzles

• US 8,304,033 B2
• Filed: 04/23/2009
• Issued: 11/06/2012
• Est. Priority Date: 02/04/2009
• Status: Active Grant

• Current Assignee: TEL Manufacturing and Engineering of America, Inc. (Tokyo Electron Limited)
• Original Assignee: TEL Epion Inc. (Tokyo Electron Limited)
• Inventors: Tabat, Martin D., Gwinn, Matthew C., Becker, Robert K., Freytsis, Avrum, Graf, Michael
• Primary Examiner(s): Padgett, Marianne L
• Application Number:
  US12/428,973
• Publication Number:
  US 20100193708A1
• Time in Patent Office: 1,293 Days
• Field of Search: None
• US Class Current: 427/523
• CPC Class Codes: H01J 2237/061 Construction
• CPC Class Codes: H01J 2237/0812 Ionized cluster beam [ICB] sources
• CPC Class Codes: H01J 2237/0825 for producing different ions simultaneously
• CPC Class Codes: H01J 2237/0827 for producing different ions sequentially
• CPC Class Codes: H01J 37/08 Ion sources; Ion guns
• CPC Class Codes: H01J 37/317 for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation H01J37/36 takes precedence

Abstract

Disclosed are methods of operation to grow, modify, deposit, or dope a layer upon a substrate using a multi-nozzle and skimmer assembly for introducing a process gas mixture, or multiple process gases mixtures, in a gas cluster ion beam (GCIB) system. Also disclosed is a method of forming a shallow trench isolation (STI) structure on a substrate, for example, an SiO₂ STI structure, using a multiple nozzle system with two separate gas supplies, for example providing a silicon-containing gas and an oxygen-containing gas.

Claims

1. A method of irradiating a substrate with a gas cluster ion beam (GCIB), comprising:

providing a GCIB system comprising;

a gas skimmer,

a set of at least two nozzles for forming and emitting gas clusters beams, the set of at least two nozzles arranged in mutual close proximity to at least partially coalesce the gas cluster beams emitted from the set of at least two nozzles into a single gas cluster beam,

a first gas supply in fluid communication with at least a first subset of nozzles, the first subset of nozzles comprising at least one nozzle from the set of at least two nozzles, and

a second gas supply in fluid communication with a second subset of nozzles, the second subset of nozzles being different than the first subset of nozzles and comprising at least one nozzle from the set of at least two nozzles;

loading a substrate to be irradiated with a GCIB;

flowing a first gas mixture from the first gas supply through at least the first subset of nozzles and flowing a second gas mixture from the second gas supply through at least the second subset of nozzles to form the single gas cluster beam, wherein the first gas mixture and second gas mixture are different;

directing the single gas cluster beam through the gas skimmer and then ionizing the single gas cluster beam to form a GCIB;

accelerating the GCIB; and

irradiating at least one region of the substrate with the GCIB to dope, grow, deposit, or modify a layer thereupon.

2. The method of claim 1, wherein the first gas mixture and second gas mixture are incompatible if mixed upstream of the set of at least two nozzles.

3. The method of claim 2, wherein at least one of the first gas mixture and the second gas mixture is pyrophoric in the presence of the other of the at least one of the first gas mixture and the second gas mixture under conditions present upstream of the set of at least two nozzles.

4. The method of claim 1, wherein the first gas mixture comprises at least one gas selected from the group consisting of SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si, SiH₂Cl₂, SiCl₃H, SiCl₄, SiF₄, O₂, CO, CO₂, N₂, NO, NO₂, N₂O, NH₃, NF₃, B₂H₆, GeH₄, Ge₂H₆, GeH₂Cl₂, GeCl₃H, methylgermane, dimethylgermane, trimethylgermane, tetramethylgermane, ethylgermane, diethylgermane, triethylgermane, tetraethylgermane, GeCl₄, GeF₄, BF₃, AsH₃, AsF₅, PH₃, PF₃, PCl₃, or PF₅, and C_xH_y, where x≧

1, and y≧

4; and

an optional dilution gas selected from the group consisting of He, Ne, Ar, Kr, Xe, and Rn.

5. The method of claim 4, wherein the second gas mixture comprises at least one gas selected from the group consisting of SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si, SiH₂Cl₂, SiCl₃H, SiCl₄, SiF₄, O₂, CO, CO₂, N₂, NO, NO₂, N₂O, NH₃, NF₃, B₂H₆, GeH₄, Ge₂H₆, GeH₂Cl₂, GeCl₃H, methylgermane, dimethylgermane, trimethylgermane, tetramethylgermane, ethylgermane, diethylgermane, triethylgermane, tetraethylgermane, GeCl₄, GeF₄, BF₃, AsH₃, AsF₅, PH₃, PF₃, PCl₃, or PF₅, and C_xH_y, where x≧

1, and y≧

4; and

an optional dilution gas selected from the group consisting of He, Ne, Ar, Kr, Xe, and Rn.

6. The method of claim 1, wherein the first gas mixture comprises a Si-containing gas.

7. The method of claim 6, wherein the first gas mixture comprises at least one gas selected from the group consisting of SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si, SiH₂Cl₂, SiCl₃H, SiCl₄, and SiF₄; and

an optional dilution gas selected from the group consisting of He, Ne, Ar, Kr, Xe, and Rn.

8. The method of claim 7, wherein the first gas mixture comprises SiH₄ and He.

9. The method of claim 6, wherein the second gas mixture comprises an oxygen-containing gas.

10. The method of claim 9, wherein the second gas mixture comprises at least one gas selected from the group consisted of O₂, CO, CO₂, NO, NO₂, N₂O;

and an optional dilution gas selected from the group consisted of He, Ne, Ar, Kr, Xe, and Rn.

11. The method of claim 10, wherein the second gas mixture comprises O₂.

12. The method of claim 9, wherein the layer comprises SiO₂.

13. The method of claim 1, wherein the GCIB system further comprises at least one manipulator mechanically coupled to one nozzle from the set of at least two nozzles, the at least one manipulator being configured to position the coupled nozzle with respect to the gas skimmer, independent of other nozzles from the set of at least two nozzles.

14. The method of claim 1, wherein the GCIB system further comprises a manipulator mechanically coupled to each nozzle in the set of at least two nozzles, the manipulator being configured to position the set of at least two nozzles collectively with respect to the gas skimmer.

15. The method of claim 1, wherein the first gas supply and second gas supply are configured to independently control stagnation pressures of the first gas mixture and the second gas mixture.

16. The method of claim 1, wherein the first gas supply and second gas supply each further comprise a temperature control system, to independently control temperatures of the first gas mixture and the second gas mixture.

17. The method of claim 1, wherein the substrate is irradiated with the GCIB to form a shallow trench isolation (STI) structure by growing or depositing said layer in said at least one region of the substrate.

18. The method of claim 17, wherein the first gas mixture comprises a Si-containing gas and the second gas mixture comprises an oxygen-containing gas, and wherein the layer comprises SiO₂.

19. The method of claim 17, further comprising:

annealing the STI structure.

20. The method of claim 17, further comprising:

using the STI structure in a memory device.

21. A method of irradiating a substrate with a gas cluster ion beam (GCIB), comprising:

providing a GCIB system comprising;

a gas skimmer,

a set of at least two nozzles comprising at least a first subset of nozzles and a second subset of nozzles different than the first subset of nozzles, the first and second subset of nozzles each comprising at least one of the at least two nozzles from the set of at least two nozzles, and each nozzle configured for forming and emitting a gas cluster beam having a beam axis, the set of at least two nozzles angled to converge each beam axis toward a single intersecting point to form a set of intersecting gas cluster beams and to direct the intersecting gas cluster beams into the gas skimmer, and

at least one gas supply in fluid communication with the first subset of nozzles and the second subset of nozzles, wherein the at least one gas supply includes a first gas supply configured to supply a first gas mixture and optionally a second gas supply configured to supply a second gas mixture;

loading a substrate to be irradiated with a GCIB;

flowing a first gas mixture from the first gas supply through the first subset of nozzles and flowing either the second gas mixture from the second gas supply or the first gas mixture from the first gas supply through the second subset of nozzles to form the intersecting gas cluster beams;

directing the intersecting gas cluster beams through the gas skimmer and then ionizing the intersecting gas cluster beams to form a GCIB;

accelerating the GCIB; and

irradiating at least one region of the substrate with the GCIB to dope, grow, deposit, or modify a layer thereupon.

22. The method of claim 21, wherein the first gas mixture comprises at least one gas selected from the group consisting of He, Ne, Ar, Kr, Xe, Rn, SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si, SiH₂Cl₂, SiCl₃H, SiCl₄, SiF₄, O₂, CO, CO₂, N₂, NO, NO₂, N₂O, NH₃, NF₃, B₂H₆, GeH₄, Ge₂H₆, GeH₂Cl₂, GeCl₃H, methylgermane, dimethylgermane, trimethylgermane, tetramethylgermane, ethylgermane, diethylgermane, triethylgermane, tetraethylgermane, GeCl₄, GeF₄, BF₃, AsH₃, AsF₅, PH₃, PF₃, PCl₃, or PF₅, and C_xH_y, where x≧

1, and y≧

4.

23. The method of claim 21, wherein the at least one gas supply includes the second gas supply in fluid communication with the second subset of nozzles, and wherein the second gas mixture having the same or different composition than the first gas mixture is flowed through the second subset of nozzles.

24. The method of claim 23, wherein the first gas mixture and second gas mixture are the same.

25. The method of claim 24, wherein the first gas mixture and second gas mixture comprise at least one gas selected from the group consisting of He, Ne, Ar, Kr, Xe, Rn, SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si, SiH₂Cl₂, SiCl₃H, SiCl₄, SiF₄, O₂, CO, CO₂, N₂, NO, NO₂, N₂O, NH₃, NF₃, B₂H₆, GeH₄, Ge₂H₆, GeH₂Cl₂, GeCl₃H, methylgermane, dimethylgermane, trimethylgermane, tetramethylgermane, ethylgermane, diethylgermane, triethylgermane, tetraethylgermane, GeCl₄, GeF₄, BF₃, AsH₃, AsF₅, PH₃, PF₃, PCl₃, or PF₅, and C_xH_y, where x≧

1, and y≧

4.

26. The method of claim 23, wherein the first gas mixture and second gas mixture are different.

27. The method of claim 26, wherein the first gas mixture and second gas mixture are incompatible if mixed upstream of the set of at least two nozzles.

28. The method of claim 27, wherein at least one of the first gas mixture and the second gas mixture is pyrophoric in the presence of the other of the at least one of the first gas mixture and the second gas mixture under conditions present upstream of the set of at least two nozzles.

29. The method of claim 26, wherein the first gas mixture comprises at least one gas selected from the group consisting of SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si SiH₂Cl₂, SiCl₃H, SiCl₄, SiF₄, O₂, CO, CO₂, N₂, NO, NO₂, N₂O, NH₃, NF₃, B₂H₆, GeH₄, Ge₂H₆, GeH₂Cl₂, GeCl₃H, methylgermane, dimethylgermane, trimethylgermane, tetramethylgermane, ethylgermane, diethylgermane, triethylgermane, tetraethylgermane, GeCl₄, GeF₄, BF₃, AsH₃, AsF₅, PH₃, PF₃, PCl₃, or PF₅, and C_xH_y, where x≧

1, and y≧

4; and

an optional dilution gas selected from the group consisting of He, Ne, Ar, Kr, Xe, and Rn.

30. The method of claim 29, wherein the second gas mixture comprises at least one gas selected from the group consisting of SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si, SiH₂Cl₂, SiCl₃H, SiCl₄, SiF₄, O₂, CO, CO₂, N₂, NO, NO₂, N₂O, NH₃, NF₃, B₂H₆, GeH₄, Ge₂H₆, GeH₂Cl₂, GeCl₃H, methylgermane, dimethylgermane, trimethylgermane, tetramethylgermane, ethylgermane, diethylgermane, triethylgermane, tetraethylgermane, GeCl₄, GeF₄, BF₃, AsH₃, AsF₅, PH₃, PF₃, PCl₃, or PF₅, and C_xH_y, where x≧

1, and y≧

4and an optional dilution gas selected from the group consisting of He, Ne, Ar, Kr, Xe, and Rn.

31. The method of claim 26, wherein the first gas mixture comprises a Si-containing gas.

32. The method of claim 31, wherein the first gas mixture comprises at least one gas selected from the group consisting of SiH₄, Si₂H₆, H₃C—

SiH₃, H₃C—

SiH₂—

CH₃, (CH₃)₃—

SiH, (CH₃)₄—

Si, SiH₂Cl₂, SiCl₃H, SiCl₄, and SiF₄; and

an optional dilution gas selected from the group consisting of He, Ne, Ar, Kr, Xe, and Rn.

33. The method of claim 32, wherein the first gas mixture comprises SiH₄ and He.

34. The method of claim 31, wherein the second gas mixture comprises an oxygen-containing gas.

35. The method of claim 34, wherein the second gas mixture comprises at least one gas selected from the group consisted of O₂, CO, CO₂, NO, NO₂, N₂O;

and an optional dilution gas selected from the group consisted of He, Ne, Ar, Kr, Xe, and Rn.

36. The method of claim 35, wherein the second gas mixture comprises O₂.

37. The method of claim 34, wherein the layer comprises SiO₂.

38. The method of claim 21, wherein the GCIB system further comprises at least one manipulator mechanically coupled to one nozzle from the set of at least two nozzles, the at least one manipulator being configured to position the coupled nozzle with respect to the gas skimmer, independent of other nozzles from the set of at least two nozzles.

39. The method of claim 21, wherein the GCIB system further comprises a manipulator mechanically coupled to each nozzle in the set of at least two nozzles, the manipulator being configured to position the set of at least two nozzles collectively with respect to the gas skimmer.

40. The method of claim 26, wherein the first gas supply and second gas supply are configured to independently control stagnation pressures of the first gas mixture and the second gas mixture.

41. The method of claim 26, wherein the first gas supply and second gas supply each further comprise a temperature control system, to independently control temperatures of the first gas mixture and the second gas mixture.

42. The method of claim 21, wherein the substrate is irradiated with the GCIB to form a shallow trench isolation (STI) structure by growing or depositing said layer in said at least one region of the substrate.

43. The method of claim 42, wherein the first gas mixture comprises a Si-containing gas and the second gas mixture comprises an oxygen-containing gas, and wherein the layer comprises SiO₂.

44. The method of claim 42, further comprising:

annealing the STI structure.

45. The method of claim 42, further comprising:

using the STI structure in a memory device.