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KR-20260064495-A - Radiation-sensitive resist composition including the same and method of forming pattern using the same

KR20260064495AKR 20260064495 AKR20260064495 AKR 20260064495AKR-20260064495-A

Abstract

An ionic salt (A) comprising an anion (a) and an organic cation (b) having a metal chalcogenide cluster structure; and a solvent (B); A radioactive resist composition comprising, wherein the anion (a) comprises one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo, and W, and the organic cation (b) comprises one or more selected from the group consisting of a secondary ammonium cation having 2 to 30 carbon atoms, a tertiary ammonium cation having 2 to 30 carbon atoms, a quaternary ammonium cation having 2 to 30 carbon atoms, a phosphonium cation having 1 to 30 carbon atoms, a sulfonium cation having 1 to 30 carbon atoms, an iodine cation having 1 to 30 carbon atoms, a pyridinium cation having 5 to 30 carbon atoms, an imidazolium cation having 3 to 30 carbon atoms, a diazonium cation having 1 to 30 carbon atoms, a guanidinium cation having 1 to 30 carbon atoms, and a hydrazinium cation having 1 to 30 carbon atoms. A radiation-sensitive resist composition and a pattern-forming method using the same are provided, wherein the content of the ionic salt (A) in the total solid content of the radiation-sensitive resist composition is 20 mass% to 100 mass%.

Inventors

  • 우치다 사야카
  • 오기와라 나오키
  • 미요시 타로
  • 야마가 히데오미
  • 사카이 노부지
  • 카마쿠라 요시노부
  • 하마노 미츠마사

Assignees

  • 삼성전자주식회사
  • 일본국(동경대학장소관)

Dates

Publication Date
20260507
Application Date
20250818
Priority Date
20241030

Claims (20)

  1. An ionic salt (A) comprising an anion (a) and an organic cation (b) having a metal chalcogenide cluster structure; and A radioactive resist composition comprising a solvent (B); The above anion (a) comprises one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo and W, and The above organic cation (b) is one or more selected from the group consisting of a secondary ammonium cation having 2 to 30 carbon atoms, a tertiary ammonium cation having 2 to 30 carbon atoms, a quaternary ammonium cation having 2 to 30 carbon atoms, a phosphonium cation having 1 to 30 carbon atoms, a sulfonium cation having 1 to 30 carbon atoms, an iodine cation having 1 to 30 carbon atoms, a pyridinium cation having 5 to 30 carbon atoms, an imidazolium cation having 3 to 30 carbon atoms, a diazonium cation having 1 to 30 carbon atoms, a guanidinium cation having 1 to 30 carbon atoms, and a hydrazinium cation having 1 to 30 carbon atoms. A radiation-sensitive resist composition in which the content of the ionic salt (A) in the total solid content of the radiation-sensitive resist composition is 20 mass% to 100 mass%.
  2. In paragraph 1, A radiation-sensitive resist composition in which the anion (a) comprises one or more metal atoms selected from the group consisting of V, Mo, and W.
  3. In paragraph 1, A radiation-sensitive resist composition in which the total number of metal atoms in the above anions (a) is 4 to 50.
  4. In paragraph 1, A radiation-reducing resist composition having a content of at least one metal atom selected from the group consisting of V, Nb, Ta, Mo, and W, with respect to 100 at% of the total number of metal atoms in the anions (a), such that the content is 20 at% or more.
  5. In paragraph 1, A radiation-sensitive resist composition having a molecular weight of 600 to 9000 of the anion (a).
  6. In paragraph 1, A radiation-sensitive resist composition having an average diameter of the anion (a) of 0.5 nm to 10 nm.
  7. In paragraph 1, A radioactive resist composition wherein the above anion (a) is one or more selected from the group consisting of anions represented by the following chemical formulas a-1 to a-6: <Chemical formula a-1> Among the above chemical formula a-1, M1 is one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo, and W, and m1 is an integer from 4 to 60, and multiple M1s may be identical or different from each other, and X 1 is one or more selected from the group consisting of O, OH, S, and Se, and n1 is an integer from 10 to 200, and multiple X 1s may be identical or different from each other, and q1 is an integer from 2 to 40 and: <Chemical Formula a-2> Among the above chemical formula a-2, M 2-1 is one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo, and W, and m2-1 is an integer from 4 to 60, and multiple M2-1s may be identical or different from each other, and M 2-2 is one or more atoms selected from the group consisting of P, As, Si, Ge, Sn, B, Al, Ga, In, Fe, Zn, Co, Te, Cu, Ag, and Mn, and m2-2 is an integer from 1 to 10, and if m2-2 is 2 or more, multiple M2-2s may be identical or different from each other, and X 2 is one or more selected from the group consisting of O, OH, S, and Se, and n2 is an integer from 10 to 200, and multiple X 2 may be identical or different from each other, and q2 is an integer from 2 to 40 and: <Chemical formula a-3> Among the above chemical formula a-3, M3 is one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo, and W, and m3 is an integer from 4 to 60, and multiple M3 may be identical or different from each other, and X 3 is one or more selected from the group consisting of O, OH, S, and Se, and n3 is an integer from 10 to 200, and multiple X3 may be identical or different from each other, and R1 is an organic group having 1 to 20 carbon atoms, and r1 is an integer from 1 to 10, and if r1 is 2 or more, multiple R1s may be the same or different from each other, and q3 is an integer from 2 to 40 and: <Chemical Formula a-4> Among the above chemical formula a-4, M 4-1 is one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo, and W, and m4-1 is an integer from 4 to 60, and multiple M4-1s may be identical or different from each other, and M 4-2 is one or more atoms selected from the group consisting of P, As, Si, Ge, Sn, B, Al, Ga, In, Fe, Zn, Co, Te, Cu, Ag, and Mn, and m4-2 is an integer from 1 to 10, and if m4-2 is 2 or more, multiple M4-2s may be identical or different from each other, and X 4 is one or more selected from the group consisting of O, OH, S, and Se, and n4 is an integer from 10 to 200, and multiple X 4 may be identical or different from each other, and R2 is an organic group having 1 to 20 carbon atoms, and r2 is an integer from 1 to 10, and if r2 is 2 or more, multiple R2 may be the same or different from each other, and q4 is an integer from 2 to 40 and: <Chemical Formula a-5> Among the above chemical formula a-5, M 5-1 is one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo, and W, and m5-1 is an integer from 4 to 60, and multiple M5-1s may be identical or different from each other, and M 5-2 is one or more atoms selected from the group consisting of P, As, Si, Ge, Sn, B, Al, Ga, In, Fe, Zn, Co, Te, Cu, Ag, and Mn, and m5-2 is an integer from 1 to 10, and if m5-2 is 2 or more, multiple M5-2s may be identical or different from each other, and X 5 is one or more selected from the group consisting of O, OH, S, and Se, and n5 is an integer from 10 to 200, and multiple X 5 may be identical or different from each other, and h is an integer from 1 to 10, and R3 is an organic group having 1 to 20 carbon atoms, and r3 is an integer from 1 to 10, and if r3 is 2 or more, multiple R3s may be identical or different from each other, and q5 is an integer from 2 to 40 and: <Chemical Formula a-6> Among the above chemical formula a-6, M6 is one or more metal atoms selected from the group consisting of V, Nb, Ta, Mo, and W, and m6 is an integer from 4 to 60, and multiple M6s may be identical or different from each other, and X 6 is one or more selected from the group consisting of O, OH, S, and Se, and n6 is an integer from 10 to 200, and multiple X 6 may be identical or different from each other, and Z is an inorganic functional group comprising one or more atoms selected from the group consisting of nitrogen atoms, phosphorus atoms, and sulfur atoms, and an oxygen atom, and p is an integer from 1 to 10, and if p is 2 or greater, multiple Zs may be identical or different from each other, and q6 is an integer from 2 to 40.
  8. In Paragraph 7, A radiation-sensitive resist composition in which q1 in the above formula a-1, q2 in the above formula a-2, q3 in the above formula a-3, q4 in the above formula a-4, q5 in the above formula a-5, and q6 in the above formula a-6 are each independently integers from 3 to 15.
  9. In paragraph 1, The anion (a) is [Nb 6 O 19 ] 8- , [Nb 7 O 22 ] 9- , [Nb 10 O 28 ] 6- , [Ta 6 O 19 ] 8- , [Ta 10 O 28 ] 6- , [Mo 6 O 19 ] 2- , [W 6 O 19 ] 2- , [W 7 O 24 ] 6- , [W 10 O 32 ] 4- , [W 10 O 34 ] 8- , [Mo 7 O 24 ] 6- , [Mo 8 O 26 ] 4- , [Mo 10 O 34 ] 8- , [W 12 O 40 (OH) 2 ] 10- , [W 12 O 38 (OH) 2 ] 6- , [V 4 O 12 ] 4- , [V 10 O 28 ] 6- , [V 12 O 32 ] 4- , [V 13 O 34 ] 4- , [V 18 O 42 ] 12- , [NbW 5 O 19 ] 3- , [Nb 4 W 2 O 19 ] 6- , [V 2 W 4 O 19 ] 4- , [NbVW 4 O 19 ] 4- , [V 5 Mo 8 O 40 ] 7- , [W 6 O 18 S] 2- , [W 3 OS 8 ] 2- , [W 4 S 12 ] 2- ; [TeMo 6 O 24 ] 6- , [CoW 6 As 6 O 30 ] 4- , [SW 12 O 40 ] 2- , [PW 12 O 40 ] 3- , [AsW 12 O 40 ] 3- , [SiW 12 O 40 ] 4- , [GeW 12 O 40 ] 4- , [BW 12 O 40 ] 5- , [AlW 12 O 40 ] 5- , [GaW 12 O 40 ] 5- , [FeW 12 O 40 ] 5- , [ZnW 12 O 40 ] 6- , [CoW 12 O 40 ] 6- , [SMo 12 O 40 ] 2- , [PMo 12 O 40 ] 3- , [AsMo 12 O 40 ] 3- , [SiMo 12 O 40 ] 4- , [GeMo 12 O 40 ] 4- , [SiMo 2 W 10 O 40 ] 4- , [SiVW 11 O 40 ] 5- , [SiMo 2 VW 9 O 40 ] 5- , [SiW 11 O 39 ] 8- , [PW 11 O 39 ] 8- , [B 3 W 39 O 132 ] 21- , [AsW 9 O 33 ] 9- , [P 2 W 18 O 62 ] 6- , [As 2 W 18 O 62 ] 6- , [S 2 W 18 O 62 ] 4- , [P 2 Mo 18 O 62 ] 6- , [As 2 Mo 18 O 62 ] 6- , [S 2 Mo 18 O 62 ] 4- , [AgP 5 W 30 O 110 ] 14- , [Sn 8 W 18 O 66 ] 8- , [Sn 3 W 18 Si 2 O 68 ] 14- , [Sn 3 W 18 P 2 O 68 ] 12- , [SnW 12 O 42 ] 10- , [Te 10 W 28 O 118 ] 28- , [Te 2 W 18 Cu 3 O 69 ] 16- , [Te 4 W 20 O 80 ] 24- , [Te 9 W 28 O 112 ] 24- , [Te 2 W 58 O 198 ] 36- , [TeW 18 O 63 ] 8- , [TeW 18 O 62 ] 10- , [TeW 6 O 24 ] 6- , [Te 2 W 17 O 61 ] 12- , [TeW 15 O 54 ] 14- , [InW 11 PO 40 ] 8- , [InW 11 SiO 40 ] 9- ; [Mo 6 O 17 (NC 6 H 5 ) 2 ] 2- , [Mo 8 O 24 {CH 3 C(CH 2 O) 3 } 2 ] 6- ; [InW 3 O 4 (C 2 H 4 COO) 8 ] 22- , [MnMo 6 O 18 {CH 3 C(CH 2 O) 3 } 2 ] 3- , [ZnMo 6 O 18 {CH 3 C(CH 2 O) 3 } 2 ] 4- , [PW 9 O 30 (C 2 H 5 PO 3 ) 2 ] 6- ; {ZnW 12 O 40 [Cu(phen)(H 2 O)] 2 } 2- ; and A radioactive resist composition comprising one or more selected from [Mo 6 O 18 (NO)] 3-, [Mo 5 O 15 (PO 4 ) 2 ] 6- , [ W 5 O 15 ( PO 4 ) 2 ] 6-, [Mo 5 O 15 (HPO 4 ) 2 ] 4- , and [Mo 5 O 15 (SO 3 ) 2 ] 4- .
  10. In paragraph 1, A radiation-reducing resist composition in which the above organic cation (b) is one or more selected from the group consisting of a secondary ammonium cation having 2 to 30 carbon atoms, a tertiary ammonium cation having 2 to 30 carbon atoms, a phosphonium cation having 1 to 30 carbon atoms, a sulfonium cation having 1 to 30 carbon atoms, an iodium cation having 1 to 30 carbon atoms, a pyridinium cation having 5 to 30 carbon atoms, an imidazolium cation having 3 to 30 carbon atoms, a diazonium cation having 1 to 30 carbon atoms, a guanidinium cation having 1 to 30 carbon atoms, and a hydrazinium cation having 1 to 30 carbon atoms.
  11. In paragraph 1, A radiation-reducing resist composition in which the above organic cation (b) is one or more selected from the group consisting of a secondary ammonium cation having 2 to 30 carbon atoms, a tertiary ammonium cation having 2 to 30 carbon atoms, a phosphonium cation having 1 to 30 carbon atoms, a pyridinium cation having 5 to 30 carbon atoms, an imidazolium cation having 3 to 30 carbon atoms, a guanidinium cation having 1 to 30 carbon atoms, and a hydrazinium cation having 1 to 30 carbon atoms.
  12. In paragraph 1, A radiation-sensitive resist composition in which the molecular weight of the organic cation (b) is 50 to 5000.
  13. In paragraph 1, A radiation-sensitive resist composition having a total molecular weight of ionic salt (A) of 650 to 30,000.
  14. In paragraph 1, A radiation-reducing resist composition in which the ratio of the molecular weight of the anion (a) to the total molecular weight of the organic cation (b) [molecular weight of (a) / total molecular weight of (b)] is 0.3 to 30.
  15. In paragraph 1, The above solvent (B) is selected from alcohol-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and any combination thereof, in a radiation-reducing resist composition.
  16. In paragraph 1, The above solvent (B) is a radioactive resist composition that substantially does not contain water.
  17. In paragraph 1, The above-mentioned radioactive resist composition is a positive type radioactive resist composition.
  18. A step of forming a resist film by applying a radioactive resist composition of any one of claims 1 to 17 onto a substrate; A step of exposing at least a portion of the resist film to radiation; and A pattern forming method comprising the step of developing an exposed resist film using a developer.
  19. In Paragraph 18, A pattern forming method in which the exposure step is performed by irradiating one or more types selected from visible light, ultraviolet light, far ultraviolet light (DUV), extreme ultraviolet light (EUV), X-rays, gamma rays, electron beams (EB), and alpha rays.
  20. In Paragraph 18, The above-mentioned exposed resist film includes an exposed portion and a non-exposed portion, and A pattern forming method in which the exposure portion is removed during the above-mentioned developing step.

Description

Radiation-sensitive resist composition including the same and method of forming pattern using the same The present invention relates to a radiation-sensitive resist composition and a method for forming a pattern using the same. There is a continuous demand for the miniaturization of semiconductor processing to achieve higher speeds and lower power consumption in semiconductor chips, and research and development of lithography technology, which is at the center of this, is underway. Recently, as the light source for lithography has shifted to extreme ultraviolet (EUV), it has become possible to obtain resist patterns with line widths of 20 nm or less. The chemically amplified resists used to obtain these resist patterns are known to have superior sensitivity and resolution compared to the materials used for excimer lasers. However, in order to obtain resist patterns with linewidths of 10 nm or less required in the future, both the sensitivity and resolution of chemical amplification resists must be improved. Specifically, the problem of the low EUV absorption rate of organic materials included in chemical amplification resists must be solved so that the energy of photons emitted by EUV can be efficiently converted into chemical reactions. Figure 1 is a diagram showing the FT-IR spectrum of compound 1 obtained in Synthesis Example 1. Figure 2 is a diagram showing the FT-IR spectrum of compound 2 obtained in Synthesis Example 2. Figure 3 is a diagram showing the FT-IR spectrum of compound 3 obtained in Synthesis Example 3. Figure 4 is a diagram showing the FT-IR spectrum of compound 4 obtained in Synthesis Example 4. Figure 5 is a diagram showing the FT-IR spectrum of compound 5 obtained in Synthesis Example 5. Figure 6 is a diagram showing the FT-IR spectrum of compound 6 obtained in Synthesis Example 6. Figure 7 is a diagram showing the FT-IR spectrum of compound 7 obtained in Synthesis Example 7. Figure 8 is a diagram showing the FT-IR spectrum of compound 8 obtained in Synthesis Example 8. Figure 9 is a diagram showing the FT-IR spectrum of compound 9 obtained in Synthesis Example 9. Figure 10 is a figure showing the FT-IR spectrum of compound 10 obtained in Synthesis Example 10. Figure 11 is a diagram showing the FT-IR spectrum of compound 11 obtained in Synthesis Example 11. Figure 12 is a diagram showing the FT-IR spectrum of compound 12 obtained in Synthesis Example 12. Figure 13 is a figure showing the FT-IR spectrum of compound 13 obtained in Synthesis Example 13. Figure 14 is a diagram showing the FT-IR spectrum of compound 14 obtained in Synthesis Example 14. Figure 15 is a figure showing the FT-IR spectrum of compound 15 obtained in Synthesis Example 15. Figure 16 is a diagram showing the FT-IR spectrum of compound 16 obtained in Synthesis Example 16. Figure 17 is a diagram showing the FT-IR spectrum of compound 17 obtained in Synthesis Example 17. Figure 18 is a diagram showing the FT-IR spectrum of compound 18 obtained in Synthesis Example 18. Figure 19 is a diagram showing the FT-IR spectrum of compound 19 obtained in Synthesis Example 19. Figure 20 is a figure showing the FT-IR spectrum of compound 20 obtained in Synthesis Example 20. Figure 21 is a diagram showing the FT-IR spectrum of compound 21 obtained in Synthesis Example 21. Figure 22 is a diagram showing the FT-IR spectrum of compound 22 obtained in Synthesis Example 22. Figure 23 is a diagram showing the FT-IR spectrum of compound 23 obtained in Synthesis Example 23. Figure 24 is a diagram showing the FT-IR spectrum of compound 24 obtained in Synthesis Example 24. Figure 25 is a figure showing the FT-IR spectrum of compound 25 obtained in Synthesis Example 25. Figure 26 is a diagram showing the FT-IR spectrum of compound 26 obtained in Synthesis Example 26. Figure 27 is a diagram showing the FT-IR spectrum of compound 27 obtained in Synthesis Example 27. Figure 28 is a diagram showing the FT-IR spectrum of compound 28 obtained in Synthesis Example 28. Figure 29 is a diagram showing the FT-IR spectrum of compound 29 obtained in Synthesis Example 29. Figure 30 is a figure showing the FT-IR spectrum of compound 30 obtained in Synthesis Example 30. Figure 31 is a diagram showing the FT-IR spectrum of compound 31 obtained in Synthesis Example 31. Figure 32 is a diagram showing the FT-IR spectrum of compound 32 obtained in Synthesis Example 32. Figure 33 is a diagram showing the FT-IR spectrum of compound 33 obtained in Synthesis Example 33. Figure 34 is a diagram showing the FT-IR spectrum of compound 34 obtained in Synthesis Example 34. Figure 35 is a figure showing the FT-IR spectrum of compound 35 obtained in Synthesis Example 35. Figure 36 is a diagram showing the FT-IR spectrum of compound 36 obtained in Synthesis Example 36. Figure 37 is a figure showing the FT-IR spectrum of compound 37 obtained in Synthesis Example 37. Figure 38 is a diagram showing the FT-IR spectrum of compound 38 obtained in Synthesis Example 38. Figure 39 is a