ORGANOSILANE POLYMERS, HARDMASK COMPOSITIONS INCLUDING THE SAME AND METHODS OF PRODUCING SEMICONDUCTOR DEVICES USING ORGANOSILANE HARDMASK COMPOSITIONS

Abstract

Provided herein, according to some embodiments of the invention, are organosilane polymers prepared by reacting organosilane compounds including (a) at least one compound of Formula I

Description

Claims

1. An organosilane polymer prepared by reacting organosilane compounds comprising (c) at least one compound of Formula I Si(OR1)(OR2)(OR3)R4   (I)

2. The organosilane polymer of claim 1, wherein R1, R2, R3 and R9 are each independently a methyl or an ethyl group; R6, R7 and R8 are each independently a C1-C4 alkyl group or a phenyl group; and n is an integer in a range of 0 to 5.

3. The organosilane polymer of claim 1, wherein the organosilane compounds comprise the at least one compound of Formula I, the at least one compound of Formula II and at least one compound of Formula III Si(OR10)(OR11)(OR12)H   (III)

4. The organosilane polymer of claim 3, wherein R10, R11 and R12 are each independently a methyl or ethyl group.

5. The organosilane polymer of claim 1, wherein reacting the organosilane compounds occurs in the presence of an acid catalyst.

6. The organosilane polymer of claim 5, wherein the acid catalyst comprises at least one acid selected from the group consisting of nitric acid, sulfuric acid, p-toluenesulfonic acid monohydrate, diethyl sulfate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.

7. The organosilane polymer of claim 1, wherein the at least one compound of Formula I is present in an amount in a range of about 5 to about 90 parts by weight and the at least one compound of Formula II is present in an amount in a range of about 5 to about 90 parts by weight.

8. The organosilane polymer of claim 3, wherein the at least one compound of Formula I and the at least one compound of Formula II are together present in an amount in a range of about 100 parts by weight and the at least one compound of Formula III is present in an amount in a range of about 5 to about 90 parts by weight.

9. The organosilane polymer of claim 1 comprising the structure of Formula IV

10. The organosilane polymer of claim 9, wherein R′, R″, R′″ and R″″ are each independently selected from the group consisting of methyl, ethyl, phenyl and —(CH2)nPh, wherein n is an integer in a range of 0 to 5.

11. The organosilane polymer of claim 3, wherein the organosilane polymer comprises the structure of Formula IV

12. The organosilane polymer of claim 11, wherein R′, R″, R′″ and R″″ are each independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl and —(CH2)nPh, wherein n is an integer in a range of 0 to 5.

13. An antireflective hardmask composition comprising the organosilane polymer of claim 1; and a solvent.

14. An antireflective hardmask composition comprising the organosilane polymer of claim 9; and a solvent.

15. An antireflective hardmask composition comprising the organosilane polymer of claim 11; and a solvent.

16. The antireflective hardmask composition of claim 13, wherein the solvent comprises at least one solvent selected from the group consisting of propylene glycol monomethyl ether, ethyl lactate, cyclohexanone and 1-methoxypropan-2-ol.

17. The antireflective hardmask composition of claim 13, further comprising at least one of a crosslinking agent, a radical stabilizer and a surfactant.

18. The hardmask composition of claim 13, further comprising at least one compound selected from the group consisting of pyridine p-toluenesulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.

19. An organosilane polymer prepared by the reaction of (a) at least one compound of Formula I Si(OR1)(OR2)(OR3)R4   (I)

20. The organosilane polymer of claim 19, wherein R1, R2, R3, R9, R10, R11, R12, R13, R14 and R15 are each independently a methyl or an ethyl group, R6, R7 and R8 are each independently a C1-C4 alkyl group or a phenyl group, R16 is selected from the group consisting of —(CH2)mC(═O)CH3, —(CH2)mOC(═O)C(CH3)═CH2 and CH2CH═CH2, n is an integer in a range of 0 to 5 and m is an integer in a range of 1 to 5.

21. The organosilane polymer of claim 19, wherein reacting the organosilane compounds occurs in the presence of an acid catalyst.

22. The organosilane polymer of claim 21, wherein the acid catalyst comprises at least one acid selected from the group consisting of nitric acid, sulfuric acid, p-toluenesulfonic acid monohydrate, diethyl sulfate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.

23. The organsilane polymer of claim 19, wherein the at least one compound of Formula I is present in an amount in a range of about 5 to about 90 parts by weight; the at least one compound of Formula II is present in an amount in a range of about 5 to about 90 parts by weight, the at least one compound of Formula III is present in an amount in a range of about 5 to about 90 parts by weight; and the at least one compound of Formula V is present in an amount in a range of about 5 to about 90 parts by weight.

24. The organosilane polymer of claim 19 comprising the structure of Formula IV

25. The organosilane polymer of claim 24, wherein R′, R″, R′″ and R″″ are each independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl and —(CH2)nPh, —(CH2)mC(═O)CH3, —(CH2)mOC(═O)C(CH3)═CH2 and —CH2CH═CH2, wherein n is an integer in a range of 0 to 5 and m is an integer in a range of 1 to 5.

26. A hardmask composition comprising the organosilane polymer of claim 19; and a solvent.

27. A hardmask composition comprising the organosilane polymer of claim 24; and a solvent.

28. The hardmask composition of claim 19, further comprising at least one of a crosslinking agent, a radical stabilizer and a surfactant.

29. The hardmask composition of claim 19, further comprising at least one compound selected from the group consisting of pyridine p-toluenesulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.

30. A method of forming a semiconductor device comprising forming a material layer on a substrate;forming an organic hardmask layer on the material layer;forming an antireflective hardmask layer from an antireflective hardmask composition on the organic hardmask layer;forming a photosensitive imaging layer on the antireflective hardmask layer; patternwise exposing the imaging layer to radiation to form a pattern of radiation-exposed regions in the imaging layer;selectively removing portions of the imaging layer, the antireflective hardmask and the organic hardmask layer to expose portions of the material layer; andetching the exposed portions of the material layer to form a patterned material layer;wherein the antireflective hardmask composition comprises an organosilane polymer, or a hydrolysis product thereof, prepared by reacting organosilane compounds comprising(d) at least one compound of Formula I Si(OR1)(OR2)(OR3)R4   (I)

31. The method according to claim 30, wherein selectively removing portions of the imaging layer, the antireflective hardmask layer and the organic hardmask layer comprises selectively removing portions of the imaging layer to expose portions of the antireflective hardmask layer,selectively removing portions of the antireflective hardmask layer to expose portions of the organic hardmask layer, andselectively removing portions of the organic hardmask layer to expose portions of the material layer.

32. The method of claim 30, wherein the hydrolysis product comprises at least one of the compounds selected from the group consisting of Ph(CH2)nSi(OH)3; SiH(OH)3; Si(CH3)(OH)3; and SiR1(OH)3; wherein n is an integer in a range of 0 to 5 and R1 is methyl or ethyl.

33. A semiconductor integrated circuit device produced by the method according to claim 30.

34. A method of forming a semiconductor device comprising forming a material layer on a substrate;forming an organic hardmask layer on the material layer;forming an antireflective hardmask layer from an antireflective hardmask composition on the organic hardmask layer;forming a photosensitive imaging layer on the antireflective hardmask layer; patternwise exposing the imaging layer to radiation to form a pattern of radiation-exposed regions in the imaging layer;selectively removing portions of the imaging layer, the antireflective hardmask and the organic hardmask layer to expose portions of the material layer; andetching the exposed portions of the material layer to form a patterned material layer;wherein the antireflective hardmask composition comprises an organosilane polymer, or a hydrolysis product thereof, prepared by the reaction of(a) at least one compound of Formula I Si(OR1)(OR2)(OR3)R4   (I)

35. The method according to claim 34, wherein selectively removing portions of the imaging layer, the antireflective hardmask layer and the organic hardmask layer comprises selectively removing portions of the imaging layer to expose portions of the antireflective hardmask layer,selectively removing portions of the antireflective hardmask layer to expose portions of the organic hardmask layer, andselectively removing portions of the organic hardmask layer to expose portions of the material layer.

36. The method of claim 34, wherein the hydrolysis product comprises at least one of the compounds selected from the group consisting of Ph(CH2)nSi(OH)3; SiH(OH)3; Si(CH3)(OH)3 and (OH)3Si(CH2)m(C═O)OCH3, wherein n is an integer in a range of 0 to 5 and m is an integer in a range of 1 to 5.

37. The method of claim 34, wherein the hydrolysis product comprises at least one of the compounds selected from the group consisting of Ph(CH2)nSi(OH)3; SiH(OH)3; Si(CH3)(OH)3 and (OH)3Si(CH2)mO(C═O)C(CH3)═CH2, wherein n is an integer in a range of 0 to 5 and m is an integer in a range of 1 to 5.

38. A semiconductor integrated circuit device produced by the method according to claim 34.