High resolution resists for next generation lithographies

• US 7,008,749 B2
• Filed: 11/05/2001
• Issued: 03/07/2006
• Est. Priority Date: 03/12/2001
• Status: Expired due to Fees

• Current Assignee: University of Connecticut (State of Connecticut), University of North Carolina At Charlotte (University of North Carolina System)
• Original Assignee: University of North Carolina At Charlotte (University of North Carolina System)
• Inventors: Gonsalves, Kenneth E.
• Primary Examiner(s): Lee, Sin J.
• Application Number:
  US09/992,560
• Publication Number:
  US 20020182541A1
• Time in Patent Office: 1,583 Days
• Field of Search: 430/237.1, 430/296, 430/9, 430/270.1, 430/286.1, 430/311, 430/322, 430/323, 430/966, 430/967, 430/914, 430/921, 430/925, 430/288.1, 430/18, 430/942, 430/313, 430/905, 430/907, 430/910, 430/281.1, 430/319, 430/325, 430/326, 430/945
• US Class Current: 430/270.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: G03F 7/0007 Filters, e.g. additive colour filters; Components for display devices
• CPC Class Codes: G03F 7/0045 with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• CPC Class Codes: G03F 7/0047 characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: G03F 7/0392 the macromolecular compound being present in a chemically amplified positive photoresist composition
• CPC Class Codes: G03F 7/075 Silicon-containing compounds
• CPC Class Codes: G03F 7/0752 in non photosensitive layers or as additives, e.g. for dry lithography
• CPC Class Codes: G03F 7/0755 Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: G03F 7/0757 Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: G03F 7/0758 with silicon- containing groups in the side chains
• CPC Class Codes: Y10S 430/106 Binder containing
• CPC Class Codes: Y10S 430/111 Polymer of unsaturated acid or ester
• CPC Class Codes: Y10S 430/115 Cationic or anionic
• CPC Class Codes: Y10S 430/122 Sulfur compound containing
• CPC Class Codes: Y10S 430/126 Halogen compound containing
• CPC Class Codes: Y10S 430/143 Electron beam
• CPC Class Codes: Y10S 430/167 X-ray

Abstract

The present invention provides new high resolution resists applicable to next generation lithographies, methods of making these novel resists, and methods of using these new resists in lithographic processes to effect state-of-the-art lithographies. New nanocomposite resists comprising nanoparticles in a polymer matrix are provided in this invention. New chemically amplified resists that incorporate inorganic moieties as part of the polymer are presented herein, as are new chemically amplified resists that incorporate photoacid generating groups within the polymeric chain. Novel non-chemically amplified yet photosensitive resists, and new organic-inorganic hybrid resists are also provided herein. This invention and the embodiments described herein constitute fundamentally new architectures for high resolution resists.

Claims

1. A nanocomposite resist comprising:

a nanoparticle component; and

a polymer component wherein the nanoparticle component comprises a polyhedral oligosilsesquioxane and the polymer component comprises poly(α

-chloroacrylate-co-α

-methyl styrene).

2. The nanocomposite resist of claim 1, wherein the polyhedral oligosilsequioxane comprises a compound of formula Si₈O₁₂(OR)₈, Si₈O₁₂R₈, Si₁₂O₁₈(OR)₁₂, or Si₁₂O₁₈R₁₂, wherein R is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, silyl, substituted silyl, aryl, substituted aryl, aralkyl, substituted aralkyl, alkenyl, or substituted alkenyl.

3. A lithographic process comprising:

exposing a lithographic recording medium to radiation to form a pattern; and

developing the pattern;

wherein the lithographic recording medium comprises a nanocomposite resist comprising a nanoparticle component and a polymer component, the nanoparticle component comprising a polyhedral oligosilsesquioxane and the polymer component comprising poly(α

-chloroacrylate-co-α

-methyl styrene).

4. The lithographic process of claim 3, wherein the polymer component further comprises poly(2,2,2-trifluoroethyl-α

-chloroacrylate), poly(methyl methacrylate), poly(butene sulfone), polysilanes, polyacetals, or combinations thereof.

5. An integrated circuit prepared by the lithographic process of claim 3.

6. The lithographic process of claim 3, wherein the radiation comprises an electron beam.

7. The lithographic process of claim 3, wherein the radiation comprises an ion beam.

8. The lithographic process of claim 3, wherein the polymer component comprises a polymer that undergoes chain scission upon exposure to electron beam irradiation.

9. The lithographic process of claim 3, wherein the nanoparticle component comprises a nanoparticle having an average diameter less than about 100 nanometers.

10. The lithographic process of claim 3, wherein the nanoparticle has an average diameter less than about 10 nanometers.

11. The lithographic process of claim 3, wherein the nanoparticle has an average diameter less than about 2 nanometers.

12. The lithographic process of claim 3, wherein the polyhedral oligosilsesquioxane comprises a compound of formula Si₈O₁₂(OR)₈, Si₈O₁₂R₈, Si₁₂O₁₈(OR)₁₂, or Si₁₂O₁₈R₁₂, wherein R is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, silyl, substituted silyl, aryl, substituted aryl, aralkyl, substituted aralkyl, alkenyl, or substituted alkenyl.

13. The lithographic process of claim 3, wherein the resist comprises from about 1% to about 50% by weight of the nanoparticle component.

14. The lithographic process of claim 3, wherein the resist has a glass transition temperature of at least about 160°

C.

15. A polymeric chemically amplified resist comprising:

a methacrylate component;

a polyhedral oligosilsesquioxane component; and

a photoacid generating component;

wherein the methacrylate component does not comprise a polyhedral oligosilsesquioxane moiety.

16. The polymeric chemically amplified resist of claim 15, wherein the methacrylate component comprises methyl methacrylate, t-butyl methacrylate, methacrylic acid, or combinations thereof.

17. The polymeric chemically amplified resist of claim 15, wherein the polyhedral oligosilsesquioxane component comprises 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane-1 -yl)propyl methacrylate;

3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxan-1-yloxy)dimethylsilyl]propyl methacrylate;

1,3,5,7,9,11,13-heptacyclopentyl-15vinylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane, or combinations thereof.

18. The polymeric chemically amplified resist of claim 15, wherein the polymeric resist comprises 1% to about 40% by weight of the polyhedral oligosilsesquioxane component.

19. The polymeric chemically amplified resist of claim 15, wherein the polymeric resist has a glass transition temperature greater than about 165°

C.

20. The polymeric chemically amplified resist of claim 15, wherein the polymeric resist has a weight-average molecular weight greater than about 100,000 g/mol.

21. The polymeric chemically amplified resist of claim 15, wherein the polymeric resist has a polydispersity index between 1 and about 2.

22. A lithographic process comprising:

exposing a lithographic recording medium to radiation to form a pattern; and

developing the pattern;

wherein the lithographic recording medium comprises the polymeric chemically amplified resist of claim 15.

23. The lithographic process of claim 22, wherein the methacrylate component comprises methyl methacrylate, t-butyl methacrylate, methacrylic acid, or combinations thereof.

24. The lithographic process of claim 22, wherein the polyhedral oligosilsesquioxane component comprises 3 -(3,5,7,9,11,13,15 -heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane-1-yl)propyl methacrylate;

3-[(3,5,7,9,11,13,1 5-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxan-1-yloxy)dimethylsilyl]propyl methacrylate;

1,3,5,7,9,11,13-heptacyclopentyl -15vinylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane, or combinations thereof.

25. An integrated circuit prepared by the lithographic process of claim 22.

26. The lithographic process of claim 22 wherein the radiation comprises an electron beam.

27. The lithographic process of claim 22, wherein the radiation comprises an ion beam.

28. The lithographic process of claim 22, wherein the radiation comprises X-ray radiation.

29. A polymeric chemically amplified resist comprising methyl methacrylate, t-butyl methacrylate, methacrylic acid, and 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane- 1-yl)propyl methacrylate.

30. A polymeric chemically amplified resist comprising:

a methacrylate component; and

a polymerizable photoacid generating component;

wherein the methacrylate component does not comprise a photoacid generating moiety and the polymerizable photoacid generating component comprises [p-CH₂═

C(CH₃)C(O)OC₆H₄SMe₂]OSO₂CF₃.

31. The polymeric chemically amplified resist of claim 30, wherein the methacrylate component comprises methyl methacrylate, t-butyl methacrylate, methacrylic acid, or combinations thereof.

32. The polymeric chemically amplified resist of claim 30 further comprising a dissolution promoter.

33. The polymeric chemically amplified resist of claim 32 wherein the dissolution promoter comprises itaconic anhydride.

34. The polymeric chemically amplified resist of claim 30, wherein the photoacid generating component comprises a sulfonium compound, an ionium compound, or combinations thereof.

35. The polymeric chemically amplified resist of claim 30, further comprising a polyhedral oligosilsesquioxane component.

36. The polymeric chemically amplified resist of claim 35, wherein the polyhedral oligosilsesquioxane component comprises 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane-1-yl)propyl methacrylate;

3-[(3,5,7,9,11,13,1 5-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxan-1-yloxy)dimethylsilyl]propyl methacrylate;

1,3,5,7,9,11,13-heptacyclopentyl-15vinylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane, or combinations thereof.

37. The polymeric chemically amplified resist of claim 35, wherein the polymeric resist comprises about 1% to about 35% by weight of the polyhedral oligosilsesquioxane component.

38. The polymeric chemically amplified resist of claim 30, wherein the polymeric resist has a weight-average molecular weight between 20,000 to 100,000 g/mol.

39. The polymeric chemically amplified resist of claim 30, wherein the polymeric resist has a polydispersity index between 1 and about 2.

40. A lithographic process comprising:

exposing a lithographic recording medium to radiation to form a pattern; and

developing the pattern;

wherein the lithographic recording medium comprises the polymeric chemically amplified resist of claim 30.

41. The lithographic process of claim 40, wherein the methacrylate component comprises methyl methacrylate, t-butyl methacrylate, methacrylic acid, or combinations thereof.

42. The lithographic process of claim 40, wherein the polymeric chemically amplified resist further comprises a dissolution promoter.

43. The lithographic process of claim 42, wherein the dissolution promoter comprises itaconic anhydride.

44. The lithographic process of claim 40, wherein the photoacid generating component comprises a sulfonium compound, an ionium compound, or combinations thereof.

45. An integrated circuit prepared by the lithographic process of claim 40.

46. The lithographic process of claim 40, wherein the radiation comprises extreme ultraviolet radiation.

47. The lithographic process of claim 40, wherein the radiation comprises X-ray radiation.

48. A polymeric chemically amplified resist comprising methyl methacrylate, t-butyl methacrylate, methacrylic acid, 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane-1-yl)propyl methacrylate, and [p-CH₂═

C(CH₃)C(O)OC₆H₄SMe₂]OSO₂CF₃.

49. The polymeric chemically amplified resist of claim 48, further comprising itaconic anhydride.

50. A polymeric lithographic resist comprising a photoacid generating component, wherein the photoacid generating component comprises [p-CH₂═

C(CH₃)C(O)OC₆H₄SMe₂]OSO₂CF₃.

51. A polymeric resist comprising:

a polyhedral oligosilsesquioxane disilanol component; and

a polyacetal component.

52. The polymeric resist of claim 51, wherein the polyhedral oligosilsesquioxane disilanol component comprises disilanol cyclopentyl POSS (Si₈O₁₁(c-C₅H₉)₈(OH)₂), disilanol isobutyl POSS (Si₈O₁₁(i-C₄H₉)₈(OH)₂), or dimethylphenyldisilanol cyclopentyl POSS (Si₈O₉(c-C₅H₉)₇(OSiMe₂Ph)(OH)₂), or a combination thereof.

53. The polymeric resist of claim 51, wherein the polyacetal component comprises a polymer of a halogen-substituted ketone or aldehyde.

54. The polymeric resist of claim 51, wherein the polyacetal component comprises a polymer of hexafluoroacetone, trifluoroacetone, hexachloroacetone, trichloroacetone, trifluoroacetaldehyde, trichloroacetaldehyde, thiocarbonylfluoride, hexafluorothioacetone, mixtures thereof, or derivatives thereof.

55. A lithographic process comprising:

exposing a lithographic recording medium to radiation to form a pattern; and

developing the pattern;

wherein the lithographic recording medium comprises the polymeric resist of claim 51.

56. The lithographic process of claim 55, wherein the lithographic process comprises a 157 nm projection optical lithographic process.

57. An integrated circuit prepared by the lithographic process of claim 55.

58. A polymeric chemically amplified resist comprising:

a methacrylate component;

a polymerizable photoacid generating component; and

a polyhedral oligosilsesquioxane component.

59. The polymeric chemically amplified resist of claim 58, wherein the methacrylate component comprises methyl methacrylate, t-butyl methacrylate, methacrylic acid, or combinations thereof.

60. The polymeric chemically amplified resist of claim 58 further comprising a dissolution promoter.

61. The polymeric chemically amplified resist of claim 60 wherein the dissolution promoter comprises itaconic anhydride.

62. The polymeric chemically amplified resist of claim 58, wherein the photoacid generating component comprises a sulfonium compound, an ionium compound, or combinations thereof.

63. The polymeric chemically amplified resist of claim 58, wherein the photoacid generating component comprises [p-CH₂═

C(CH₃)C(O)OC₆H₄SMe₂]OSO₂CF₃.

64. The polymeric chemically amplified resist of claim 58, wherein the polyhedral oligosilsesquioxane component comprises 3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane-1-yl)propyl methacrylate;

3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxan-1-yloxy)dimethylsilyl]propyl methacrylate;

1,3,5,7,9,11,13-heptacyclopentyl-15vinylpentacyclo-[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane, or combinations thereof.

65. The polymeric chemically amplified resist of claim 58, wherein the polymeric resist comprises about 1% to about 35% by weight of the polyhedral oligosilsesquioxane component.

66. The polymeric chemically amplified resist of claim 58, wherein the polymeric resist has a weight-average molecular weight between 20,000 to 100,000 g/mol.

67. The polymeric chemically amplified resist of claim 58, wherein the polymeric resist has a polydispersity index between 1 and about 2.

68. lithographic process comprising:

exposing a lithographic recording medium to radiation to form a pattern; and

developing the pattern;

wherein the lithographic recording medium comprises the polymeric chemically amplified resist of claim 58.

69. The lithographic process of claim 68, wherein the methacrylate component comprises methyl methacrylate, t-butyl methacrylate, methacrylic acid, or combinations thereof.

70. The lithographic process of claim 68, wherein the polymeric chemically amplified resist further comprises a dissolution promoter.

71. The lithographic process of claim 70, wherein the dissolution promoter comprises itaconic anhydride.

72. The lithographic process of claim 68, wherein the photoacid generating component comprises a sulfonium compound, an ionium compound, or combinations thereof.

73. An integrated circuit prepared by the lithographic process of claim 68.

74. The lithographic process of claim 68, wherein the radiation comprises extreme ultraviolet radiation.

75. The lithographic process of claim 68, wherein the radiation comprises X-ray radiation.