Hardmask compositions for resist underlayer film and method for producing semiconductor integrated circuit device using the same

1. A hardmask composition for a resist underlayer film, comprising:

(a) a first polymer prepared by the reaction of a compound of Formula 1

wherein n is a number of 3 to 20, with a compound of Formula 2

(R) m —Si—(OCH 3 ) 4-m   (2)

wherein R is a monovalent organic group and m is 0, 1 or 2;

(b) a second polymer comprising a structure represented by Formula 3

wherein R 1 is aryl; R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, alkyl, aryl and allyl; and a, b and c are each independently a positive integer;

(c) an acid or base catalyst; and

(d) an organic solvent.

2. The hardmask composition of claim 1 , wherein R 1 is selected from the group consisting of phenyl, naphthyl and anthracenyl; and R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, C 1-10 alkyl, C 6-10 aryl and allyl; and a, b and c are each independently an integer from 1 to 60.

3. The hardmask composition according to claim 1 , wherein the base catalyst comprises one or more ammonium hydroxides of the formula NH 4 OH or N(R′) 4 OH, wherein R′ is a monovalent organic group.

4. The hardmask composition according to claim 1 , wherein the acid catalyst is selected from the group consisting of p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

5. The hardmask composition according to claim 1 , wherein the first polymer is present in an amount in a range of about 1 to about 50 parts by weight, based on the total weight of the composition.

6. The hardmask composition according to claim 1 , wherein the second polymer is present in an amount in a range of about 1 to about 30 parts by weight, based on the total weight of the composition.

7. The hardmask composition according to claim 1 , wherein the first polymer comprises at least one structure selected from the structures represented by Formulae 10-14:

wherein R is a monovalent organic radical; and w, x, y and z are each independently positive integers.

8. The hardmask composition according to claim 1 , further comprising one or more of a crosslinking agent and a surfactant.

9. A hardmask composition for a resist underlayer film, comprising:

(a) a first polymer prepared by the reaction of a compound of Formula 1

wherein n is a number of 3 to 20, with a compound of Formula 2

(R) m —Si—(OCH 3 ) 4-m   (2)

wherein R is a monovalent organic group and m is 0, 1 or 2;

(b) a second polymer comprising a structure represented by Formula 4

wherein R 5 is an arylene; R 6 is selected from the group consisting of hydroxyaryl, epoxy-substituted aryl, arylalkyl and an arylcarbonyl; and d is a positive integer;

(c) an acid or base catalyst; and

(d) an organic solvent.

10. The hardmask composition of claim 9 , wherein R 5 is selected from one of the following two arylene groups

R 6 is selected from the group consisting of R 5 OH,

CH 2 R 7 and C(═O)R 7 , wherein R 7 is selected from the group consisting of anthracenyl, naphthyl and phenyl; and d is an integer from 3 to 20.

11. The hardmask composition according to claim 9 , wherein the base catalyst comprises one or more ammonium hydroxides of the formula NH 4 OH or N(R′) 4 OH, wherein R′ is a monovalent organic group.

12. The hardmask composition according to claim 9 , wherein the acid catalyst is selected from the group consisting of p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

13. The hardmask composition according to claim 9 , wherein the first polymer is present in an amount in a range of about 1 to about 50 parts by weight, based on the total weight of the composition.

14. The hardmask composition according to claim 9 , wherein the second polymer is present in an amount in a range of about 1 to about 30 parts by weight, based on the total weight of the composition.

15. The hardmask composition according to claim 9 , wherein the first polymer comprises at least one structure selected from the structures represented by Formulae 10-14:

wherein R is a monovalent organic radical; and w, x, y and z are each independently positive integers.

16. The hardmask composition according to claim 9 , further comprising one or more of a crosslinking agent and a surfactant.

17. A hardmask composition for a resist underlayer film, comprising:

(a) a first polymer prepared by the reaction of a compound of Formula 1

wherein n is a number of 3 to 20, with a compound of Formula 2

(R) m —Si—(OCH 3 ) 4-m   (2)

wherein R is a monovalent organic group and m is 0, 1 or 2;

(b) a second polymer comprising a structure represented by Formula 5 below:

R 8 is selected from the group consisting of hydrogen, alkyl, aryl and allyl; R 9 is hydroxyarylene and e is a positive integer;

(c) an acid or base catalyst; and

(d) an organic solvent.

18. The hardmask composition according to claim 17 , wherein R 8 is selected from the group consisting of hydrogen, C 1-10 alkyl, C 6-10 aryl and allyl, R 9 is selected from the group consisting of hydroxynapthylidene, hydroxyphenylene and a compound having the structure of

wherein R 10 and R 11 are each independently selected from the group consisting of hydrogen, hydroxyl, C 1-10 alkyl, C 6-10 aryl, allyl and halogen, and R 12 and R 13 are each independently selected from the group consisting of hydrogen, a crosslinking functionality and a chromophore; and e is an integer from 1 to 190.

19. The hardmask composition according to claim 17 , wherein the base catalyst comprises one or more ammonium hydroxides of the formula NH 4 OH or N(R′) 4 OH, wherein R′ is a monovalent organic group.

20. The hardmask composition according to claim 17 , wherein the acid catalyst is selected from the group consisting of p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

21. The hardmask composition according to claim 17 , wherein the first polymer is present in an amount in a range of about 1 to about 50 parts by weight, based on the total weight of the composition.

22. The hardmask composition according to claim 17 , wherein the second polymer is present in an amount in a range of about 1 to about 30 parts by weight, based on the total weight of the composition.

23. The hardmask composition according to claim 17 , wherein the first polymer comprises at least one structure selected from the structures represented by Formulae 10-14:

wherein R is a monovalent organic radical; and w, x, y and z are each independently positive integers.

24. The hardmask composition according to claim 17 , further comprising one or more of a crosslinking agent and a surfactant.

25. A hardmask composition for a resist underlayer film, comprising:

(a) a first polymer prepared by the reaction of a compound of Formula 1

wherein n is a number of 3 to 20, with a compound of Formula 2

(R) m —Si—(OCH 3 ) 4-m   (2)

wherein R is a monovalent organic group and m is 0, 1 or 2;

(b) a second polymer comprising a structure represented by Formula 6 below:

wherein R 14 is aryl; R 15 and R 16 are each independently selected from the group consisting of hydrogen, alkyl, aryl and allyl; and f and g are each independently a positive integer;

(c) an acid or base catalyst; and

(d) an organic solvent.

26. The hardmask composition according to claim 25 , wherein R 14 is selected from the group consisting of phenyl, naphthyl and anthracenyl; R 15 and R 16 are each independently selected from the group consisting of hydrogen, C 1-10 alkyl, C 6-10 aryl and allyl; and f and g are each independently an integer from 1 to 60.

27. The hardmask composition according to claim 25 , wherein the base catalyst comprises one or more ammonium hydroxides of the formula NH 4 OH or N(R′) 4 OH, wherein R′ is a monovalent organic group.

28. The hardmask composition according to claim 25 , wherein the acid catalyst is selected from the group consisting of p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

29. The hardmask composition according to claim 25 , wherein the first polymer is present in an amount in a range of about 1 to about 50 parts by weight, based on the total weight of the composition.

30. The hardmask composition according to claim 25 , wherein the second polymer is present in an amount in a range of about 1 to about 30 parts by weight, based on the total weight of the composition.

31. The hardmask composition according to claim 25 , wherein the first polymer comprises at least one structure selected from the structures represented by Formulae 10-14:

wherein R is a monovalent organic radical; and w, x, y and z are each independently positive integers.

32. The hardmask composition according to claim 25 , further comprising one or more of a crosslinking agent and a surfactant.

33. A hardmask composition for a resist underlayer film, comprising:

(a) a first polymer comprising about 10 to about 99 mol %, based on the total moles of silicon-containing monomeric units, of the monomeric unit of Formula 7 below:

and about 1 to about 90 mol %, based on the total moles of silicon-containing monomeric units, of at least one monomeric unit selected from the monomeric units of Formulae 8 and 9 below:

wherein R, R′ and R″ are each independently a monovalent organic group;

(b) a second polymer comprising at least one structure selected from the structures represented by Formulae 3 to 6

wherein R 1 is aryl; R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, alkyl, aryl and allyl; and a, b and c are each independently a positive integer;

wherein R 5 is an arylene; R 6 is selected from the group consisting of hydroxyaryl, epoxy-substituted aryl, arylalkyl and an arylcarbonyl; and d is a positive integer;

R 8 is selected from the group consisting of hydrogen, alkyl, aryl and allyl; R 9 is hydroxyarylene and e is a positive integer;

wherein R 14 is aryl; R 15 and R 16 are each independently selected from the group consisting of hydrogen, alkyl, aryl and allyl; and f and g are each independently a positive integer;

(c) an acid or base catalyst; and

(d) an organic solvent.

34. The hardmask composition of claim 33 , wherein

R 1 is selected from the group consisting of phenyl, naphthyl and anthracenyl;

R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, C 1-10 alkyl, C 6-10 aryl and allyl;

R 5 is selected from one of the following two arylene groups

R 6 is selected from the group consisting of R 5 OH,

CH 2 R 7 and C(═O)R 7 , wherein R 7 is selected from the group consisting of anthracenyl, naphthyl and phenyl;

R 8 is selected from the group consisting of hydrogen, C 1-10 alkyl, C 6-10 aryl and allyl;

R 9 is selected from the group consisting of hydroxynapthylidene, hydroxyphenylene and a compound having the structure of

wherein R 10 and R 11 are each independently selected from the group consisting of hydrogen, hydroxyl, C 1-10 alkyl, C 6-10 aryl, allyl and halogen, and R 12 and R 13 are each independently selected from the group consisting of hydrogen, a crosslinking functionality and a chromophore;

R 14 is selected from the group consisting of phenyl, naphthyl and anthracenyl;

R 15 and R 16 are each independently selected from the group consisting of hydrogen, C 1-10 alkyl, C 6-10 aryl and allyl; and

a, b and c are each independently an integer from 1 to 60, d is an integer from 3 to 20, e is an integer from 1 to 190, and f and g are each independently an integer from 1 to 60.

35. The hardmask composition according to claim 33 , wherein the base catalyst comprises one or more ammonium hydroxides of the formula NH 4 OH or N(R′) 4 OH, wherein R′ is a monovalent organic group.

36. The hardmask composition according to claim 33 , wherein the acid catalyst is selected from the group consisting of p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.

37. The hardmask composition according to claim 33 , wherein the first polymer is present in an amount in a range of about 1 to about 50 parts by weight, based on the total weight of the composition.

38. The hardmask composition according to claim 33 , wherein the second polymer is present in an amount in a range of about 1 to about 30 parts by weight, based on the total weight of the composition.

39. The hardmask composition according to claim 33 , further comprising one or more of a crosslinking agent and a surfactant.

40. A method for producing a semiconductor integrated circuit device, comprising the steps of:

(a) providing a material layer on a substrate;

(b) forming a hardmask layer on the material layer wherein the hardmask layer is composed of an organic material;

(c) forming an antireflective hardmask layer using the hardmask composition according to claim 1 for a resist underlayer film on the material layer;

(d) forming a radiation-sensitive imaging layer on the antireflective hardmask layer;

(e) patternwise exposing the imaging layer to radiation to form a pattern of radiation-exposed regions in the imaging layer;

(f) selectively removing portions of the radiation-sensitive imaging layer and the antireflective hardmask layer to expose portions of the hardmask material layer containing an organic material;

(g) selectively removing portions of the patterned antireflective hardmask layer and the hardmask material layer containing an organic material to expose portions of the material layer; and

(h) etching the exposed portions of the material layer to form a patterned material layer.

41. A semiconductor integrated circuit device produced by the method according to claim 40 .

42. A method for producing a semiconductor integrated circuit device, comprising the steps of:

(a) providing a material layer on a substrate;

(b) forming a hardmask layer on the material layer wherein the hardmask layer is composed of an organic material;

(c) forming an antireflective hardmask layer using the hardmask composition according to claim 9 for a resist underlayer film on the material layer;

(d) forming a radiation-sensitive imaging layer on the antireflective hardmask layer;

(e) patternwise exposing the imaging layer to radiation to form a pattern of radiation-exposed regions in the imaging layer;

(f) selectively removing portions of the radiation-sensitive imaging layer and the antireflective hardmask layer to expose portions of the hardmask material layer containing an organic material;

(g) selectively removing portions of the patterned antireflective hardmask layer and the hardmask material layer containing an organic material to expose portions of the material layer; and

(h) etching the exposed portions of the material layer to form a patterned material layer.

43. A semiconductor integrated circuit device produced by the method according to claim 42 .

44. A method for producing a semiconductor integrated circuit device, comprising the steps of:

(a) providing a material layer on a substrate;

(b) forming a hardmask layer on the material layer wherein the hardmask layer is composed of an organic material;

(c) forming an antireflective hardmask layer using the hardmask composition according to claim 17 for a resist underlayer film on the material layer;

(d) forming a radiation-sensitive imaging layer on the antireflective hardmask layer;

(e) patternwise exposing the imaging layer to radiation to form a pattern of radiation-exposed regions in the imaging layer;

(f) selectively removing portions of the radiation-sensitive imaging layer and the antireflective hardmask layer to expose portions of the hardmask material layer containing an organic material;

(g) selectively removing portions of the patterned antireflective hardmask layer and the hardmask material layer containing an organic material to expose portions of the material layer; and

(h) etching the exposed portions of the material layer to form a patterned material layer.

45. A semiconductor integrated circuit device produced by the method according to claim 44 .

46. A method for producing a semiconductor integrated circuit device, comprising the steps of:

(a) providing a material layer on a substrate;

(b) forming a hardmask layer on the material layer wherein the hardmask layer is composed of an organic material;

(c) forming an antireflective hardmask layer using the hardmask composition according to claim 25 for a resist underlayer film on the material layer,

(d) forming a radiation-sensitive imaging layer on the antireflective hardmask layer;

(e) patternwise exposing the imaging layer to radiation to form a pattern of radiation-exposed regions in the imaging layer;

(f) selectively removing portions of the radiation-sensitive imaging layer and the antireflective hardmask layer to expose portions of the hardmask material layer containing an organic material;

(g) selectively removing portions of the patterned antireflective hardmask layer and the hardmask material layer containing an organic material to expose portions of the material layer; and

(h) etching the exposed portions of the material layer to form a patterned material layer.

47. A semiconductor integrated circuit device produced by the method according to claim 46 .

48. A method for producing a semiconductor integrated circuit device, comprising the steps of:

(a) providing a material layer on a substrate;

(b) forming a hardmask layer on the material layer wherein the hardmask layer is composed of an organic material;

(c) forming an antireflective hardmask layer using the hardmask composition according to claim 33 for a resist underlayer film on the material layer;

(d) forming a radiation-sensitive imaging layer on the antireflective hardmask layer;

(e) patternwise exposing the imaging layer to radiation to form a pattern of radiation-exposed regions in the imaging layer;

(f) selectively removing portions of the radiation-sensitive imaging layer and the antireflective hardmask layer to expose portions of the hardmask material layer containing an organic material;

(g) selectively removing portions of the patterned antireflective hardmask layer and the hardmask material layer containing an organic material to expose portions of the material layer; and

(h) etching the exposed portions of the material layer to form a patterned material layer.

49. A semiconductor integrated circuit device produced by the method according to claim 48 .