Composition for forming a resist underlayer film, and pattern-forming method
A composition for forming a resist underlayer film is provided, which contains: a calixarene-based compound obtained from a calixarene by substituting at least a part of hydrogen atoms each on phenolic hydroxyl groups comprised in the calixarene, with a monovalent organic group having 1 to 30 carbon atoms; and an organic solvent. The monovalent organic group preferably includes a crosslinkable group. A part of hydrogen atoms each on phenolic hydroxyl groups of the calixarene-based compound is preferably substituted. The ratio of the number of substituted phenolic hydroxyl groups to the number of unsubstituted phenolic hydroxyl groups in the calixarene-based compound is preferably no less than 30/70 and no greater than 99/1.
1. A composition comprising:
a calixarene-based compound represented by formula (3); and
an organic solvent,
wherein in the formula (3), R represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and at least one R is the monovalent organic group; m is an integer of 4 to 12; Y represents a hydrocarbon group having 1 to 10 carbon atoms; q is an integer of 0 to 7; p is an integer of 1 to 3, wherein a sum of p and q is no less than 1 and no greater than 8; and k is 0 or 1; X represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom, wherein a plurality of Rs are identical or different, a plurality of Xs are identical or different, a plurality of “k”s are identical or different, a plurality of “p”s are identical or different, and a plurality of “q”s are identical or different, and wherein in a case where Y is present in a plurality of number, a plurality of Ys are identical or different,
wherein, in a case where p is 2,
X is a phenyl group substituted with —OR; or
the monovalent organic group represented by R is at least one group selected from the group consisting of a benzyl group, a cyclopentyl group, a group comprising a polymerizable carbon-carbon triple bond, a group comprising an epoxy group, a group comprising an alkoxymethyl group, a group comprising a formyl group, a group comprising an acetyl group, a group comprising a dialkylaminomethyl group, a group comprising a dimethylolaminomethyl group, a group represented by formula (a), a group represented by formula (b), and group represented by formula (c):
wherein R a and R a′ each independently represent a single bond or an alkanediyl group having 1 to 10 carbon atoms; R a″ represents a single bond, an alkanediyl group, a hydroxyalkanediyloxy group or (R″O) i ; R″ represents an alkanediyl group; “i” is an integer of 1 to 10; R b″ represents a hydrogen atom; and R b , R b′ , R c , R c′ , R c″ , R d , R d′ and R d″ each independently represent a hydrogen atom or a monovalent hydrocarbon group,
wherein at least one monovalent organic group represented by R is the group represented by the formula (b).
2. The composition according to claim 1 , wherein a part of hydrogen atoms on phenolic hydroxyl groups of the calixarene-based compound is substituted.
3. The composition according to claim 2 , wherein a ratio of the number of substituted phenolic hydroxyl groups to the number of unsubstituted phenolic hydroxyl groups in the calixarene-based compound is no less than 30/70 and no greater than 99/1.
4. The composition according to claim 1 , wherein the calixarene-based compound is derived from a compound obtained by subjecting a compound represented by formula (1) and a compound represented by formula (2) to a condensation reaction,
wherein in the formula (1), Y, k, p and q are as defined in the formula (3), and
wherein in the formula (2), X is as defined in the formula (3); and j is 1 or 2.
5. The composition according to claim 1 , wherein a molecular weight of the calixarene-based compound is no less than 500 and no greater than 3,000.
6. The composition according to claim 1 , wherein the organic solvent comprises a polyhydric alcohol partial ether acetate solvent, a ketone solvent, a carboxylic acid ester solvent, or a mixed solvent thereof.
7. The composition according to claim 1 , further comprising a resin other than a resin corresponding to the calixarene-based compound.
8. The composition according to claim 7 , wherein the resin other than the resin corresponding to the calixarene-based compound comprises a crosslinkable group.
9. The composition according to claim 7 , wherein the resin other than the resin corresponding to the calixarene-based compound comprises a novolak resin, a resol resin, a styrene resin, an acenaphthylene resin, a polyarylene resin or a mixture thereof.
10. The composition according to claim 7 , wherein a weight average molecular weight of the resin other than the resin corresponding to the calixarene-based compound is no less than 2,000 and no greater than 8,000.
11. The composition according to claim 7 , wherein a content of the resin other than the resin corresponding to the calixarene-based compound with respect to 100 parts by mass of the calixarene-based compound is no less than 5 parts by mass and no greater than 1,000 parts by mass.
12. The composition according to claim 1 , wherein the monovalent organic group represented by R is the group represented by the formula (b).
13. The composition according to claim 1 , wherein the organic solvent comprises a polyhydric alcohol partial ether acetate solvent, a ketone solvent, a carboxylic acid ester solvent, or a mixed solvent thereof.
14. A pattern-forming method comprising:
applying the composition according to claim 1 directly or indirectly on a substrate to provide a resist underlayer film;
forming a resist pattern directly or indirectly on the resist underlayer film;
forming a pattern on the substrate through dry etching of the resist underlayer film, the substrate, or both the resist underlayer film and the substrate using the resist pattern as a mask; and
removing the resist underlayer film remaining on the substrate using a basic solution,
wherein the method further comprises subjecting the resist underlayer film to heating or an acid treatment before removing the resist underlayer film.
15. The pattern-forming method according to claim 14 , further comprising after providing the resist underlayer film and before forming the resist pattern:
providing an intermediate layer directly or indirectly on the resist underlayer film,
wherein the intermediate layer is further dry etched in forming the pattern.
16. The pattern-forming method according to claim 14 , wherein a part of hydrogen atoms on phenolic hydroxyl groups of the calixarene-based compound is substituted.
17. The pattern-forming method according to claim 16 , wherein a ratio of the number of substituted phenolic hydroxyl groups to the number of unsubstituted phenolic hydroxyl groups in the calixarene-based compound is no less than 30/70 and no greater than 99/1.
18. The pattern-forming method according to claim 14 , wherein the calixarene-based compound is derived from a compound obtained by subjecting a compound represented by formula (1) and a compound represented by formula (2) to a condensation reaction,
wherein in the formula (1), Y, k, p and q are as defined in the formula (3), and
wherein in the formula (2), X is as defined in the formula (3); and j is 1 or 2.
19. The pattern-forming method according to claim 14 , wherein a molecular weight of the calixarene-based compound is no less than 500 and no greater than 3,000.