Composition for resist underlayer film and process for producing same
A composition for a resist underlayer film is provided. The composition has excellent storage stability and can form a resist underlayer film which has excellent adhesion to a resist film, can improve reproducibility of a resist pattern and is resistant to an alkaline liquid used in development and to oxygen asking during the removal of a resist. The composition comprises a hydrolyzate and/or a condensate of a silane compound of the following formula (A), R 1 b R 2 c Si(OR 3 ) 4-a (A) wherein R 1 is a monovalent organic group having at least one unsaturated bond, R 2 individually represents a hydrogen atom, a halogen atom or a monovalent organic group, R 3 individually represents a monovalent organic group, R 1 is a group other than OR 3 , a is an integer of 1 to 3, b is an integer of 1 to 3, and c is an integer of 0 to 2, provided that a=b+c.
1. A composition for a resist underlayer film comprising a hydrolyzate and/or a condensate of a mixture consisting of:
at least two kinds of silane compounds represented by the following formula (A);
at least one silane compound represented by the following formula (B); and
at least one silane compound represented by the following formula (C),
R 1 b R 2 c Si(OR 3 ) 4-a (A)
Si(OR 3 ) 4 (B)
(R 4 ) d Si(OR 3 ) 4-d (C)
wherein, in the formula (A), R 1 is a monovalent organic group having at least one unsaturated bond and R 1 in one of the at least two kinds of silane compounds contains a cyano group, R 2 individually represents a hydrogen atom, a halogen atom or a monovalent organic group, R 3 individually represents a monovalent organic group, R 1 is a group other than OR 3 , a is an integer of 1 to 3, b is an integer of 1 to 3, and c is an integer of 0 to 2, provided that a=b+c,
wherein, in the formula (B), R 3 represents a monovalent organic group, and
wherein, in the formula (C), R 3 represents a monovalent organic group, R 4 individually represents a hydrogen atom, a halogen atom or a monovalent organic group selected from the group consisting of a monovalent alkyl group, a monovalent fluoroalkyl group and a monovalent aminoalkyl group, and d is an integer of 1 to 3, wherein the monovalent organic group represented by R 4 excludes R 1 and OR 3 .
2. The composition for a resist underlayer film according to claim 1 , further containing an acid-producing compound which generates an acid by irradiation of ultraviolet radiation and/or by heating.
3. The composition for a resist underlayer film according to claim 1 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains an aromatic ring.
4. The composition for a resist underlayer film according to claim 1 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains a phenyl group, an aminophenyl group, an indenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an acenaphthyl group or an anthryl group.
5. The composition for a resist underlayer film according to claim 1 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains a phenyl group.
6. A process for producing the composition for a resist underlayer film according to claim 1 , comprising a step of hydrolyzing and/or condensing the silane compound used in the composition in an organic acid in the presence of water and a catalyst.
7. A composition for a resist underlayer film comprising:
a first component which is a hydrolyzate and/or a condensate of a first mixture consisting of at least two compounds selected from the group consisting of a silane compound represented by the following formula (A), a silane compound represented by the following formula (B), and a silane compound represented by the following formula (C); and
a second component which is other than the first component, and which is a hydrolyzate and/or a condensate of a second mixture consisting of at least one compound selected from the group consisting of the silane compound represented by the following formula (A), the silane compound represented by the following formula (B) and the silane compound represented by the following formula (C),
wherein at least two kinds of the silane compounds represented by the following formula (A) are included in the first mixture, in the second mixture, or in both thereof, and the silane compound represented by the following formula (B) is included in the first mixture, in the second mixture, or in both thereof,
R 1 b R 2 c Si(OR 3 ) 4-a (A)
wherein, in the formula (A), R 1 is a monovalent organic group having at least one unsaturated bond and R 1 in one of the at least two kinds of silane compounds contains a cyano group, R 2 individually represents a hydrogen atom, a halogen atom or a monovalent organic group, R 3 individually represents a monovalent organic group, R 1 is a group other than OR 3 , a is an integer of 1 to 3, b is an integer of 1 to 3, and c is an integer of 0 to 2, provided that a=b+c,
Si(OR 3 ) 4 (B)
wherein, in the formula (B), R 3 represents a monovalent organic group,
(R 4 ) d Si(OR 3 ) 4-d (C)
wherein, in the formula (C), R 3 represents a monovalent organic group, R 4 individually represents a hydrogen atom, a halogen atom or a monovalent organic group selected from the group consisting of a monovalent alkyl group, a monovalent fluoroalkyl group and a monovalent aminoalkyl group, and d is an integer of 1 to 3, wherein the monovalent organic group represented by R 4 excludes R 1 and OR 3 .
8. The composition for a resist underlayer film according to claim 7 , wherein the second component is a hydrolyzate and/or a condensate of the silane compound represented by the formula (B) or the silane compound represented by the formula (C).
9. The composition for a resist underlayer film according to claim 8 , further containing an acid-producing compound which generates an acid by irradiation of ultraviolet radiation and/or by heating.
10. The composition for a resist underlayer film according to claim 7 , further containing an acid-producing compound which generates an acid by irradiation of ultraviolet radiation and/or by heating.
11. The composition for a resist underlayer film according to claim 7 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains an aromatic ring.
12. The composition for a resist underlayer film according to claim 7 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains a phenyl group, an aminophenyl group, an indenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an acenaphthyl group or an anthryl group.
13. The composition for a resist underlayer film according to claim 7 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains a phenyl group.
14. A process for producing the composition for a resist underlayer film according to claim 7 , comprising a step of hydrolyzing and/or condensing the silane compound used in the composition in an organic acid in the presence of water and a catalyst.
15. A composition for a resist underlayer film comprising a mixture which consists of:
a hydrolyzate and/or a condensate of at least two kinds of silane compounds represented by the following formula (A);
a hydrolyzate and/or a condensate of at least one silane compound represented by the following formula (B); and
optionally, a hydrolyzate and/or a condensate of at least one silane compound represented by the following formula (C),
R 1 b R 2 c Si(OR 3 ) 4-a (A)
wherein, in the formula (A), R 1 is a monovalent organic group having at least one unsaturated bond and R 1 in one of the at least two kinds of silane compounds contains a cyano group, R 2 individually represents a hydrogen atom, a halogen atom or a monovalent organic group, R 3 individually represents a monovalent organic group, R 1 is a group other than OR 3 , a is an integer of 1 to 3, b is an integer of 1 to 3, and c is an integer of 0 to 2, provided that a=b+c,
Si(OR 3 ) 4 (B)
wherein, in the formula (B), R 3 represents a monovalent organic group,
(R 4 ) d Si(OR 3 ) 4-d (C)
wherein, in the formula (C), R 3 represents a monovalent organic group, R 4 individually represents a hydrogen atom, a halogen atom or a monovalent organic group selected from the group consisting of a monovalent alkyl group, a monovalent fluoroalkyl group and a monovalent aminoalkyl group, and d is an integer of 1 to 3, wherein the monovalent organic group represented by R 4 excludes R 1 and OR 3 .
16. The composition for a resist underlayer film according to claim 15 , further containing an acid-producing compound which generates an acid by irradiation of ultraviolet radiation and/or by heating.
17. The composition for a resist underlayer film according to claim 15 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains an aromatic ring.
18. The composition for a resist underlayer film according to claim 15 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains a phenyl group, an aminophenyl group, an indenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an acenaphthyl group or an anthryl group.
19. The composition for a resist underlayer film according to claim 15 , wherein R 1 in at least one silane compound other than the one of the at least two kinds of silane compounds contains a phenyl group.
20. A process for producing the composition for a resist underlayer film according to claim 15 , comprising a step of hydrolyzing and/or condensing the silane compound used in the composition in an organic acid in the presence of water and a catalyst.