Crosslinkable compound-containing photocurable stepped substrate-coating composition
A stepped substrate-coating composition for forming a coating film having filling property of a pattern and flattening property including a compound (E) having a partial structure (I) and a partial structure (II) having a hydroxy group formed by a reaction of an epoxy group with a proton-generating compound, a solvent (F), and a crosslinkable compound (H), wherein the partial structure (I) is from Formulae (1-1) to (1-5) or including a partial structure of Formula (1-6) combined with a partial structure of Formula (1-7) or (1-8), and the partial structure (II) is of the following Formula (2-1) or (2-2), wherein the compound (E) contains the epoxy and hydroxy group at a molar ratio (epoxy group)/(hydroxy group) of 0 or more and 0.5 or less, and contains the partial structure (II) so the molar ratio (partial structure (II))/(partial structure (I)+partial structure (II)) is 0.01 or more and 0.8 or less.
1. A photocurable stepped substrate-coating composition comprising:
a compound (E) containing a partial structure (I) and a partial structure (II) that contains a hydroxy group formed by a reaction of an epoxy group with a proton-generating compound;
a solvent (F); and
a crosslinkable compound (H), wherein
the partial structure (I) is at least one partial structure selected from the group consisting of partial structures of Formulae (1-1) to (1-5) described below, or a partial structure including a partial structure of Formula (1-6) in a combination with a partial structure of Formula (1-7) or (1-8), and
the partial structure (II) is a partial structure of Formula (2-1) or (2-2) described below
wherein R 1 , R 1a , R 3 , and R 5 are each independently a saturated C 1-10 hydrocarbon group, an aromatic C 6-40 hydrocarbon group, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group selected from combinations thereof, R 5a and R 6a are each independently a divalent group selected from a C 1-10 alkylene group, a C 6-40 arylene group, an oxygen atom, a carbonyl group, a sulfur atom, or combinations thereof, R 2 , R 2a , R 4 , and R 6 are each independently a hydrogen atom, a saturated C 1-10 hydrocarbon group, an unsaturated C 2-10 hydrocarbon group, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group selected from combinations thereof, and are a monovalent group, R 1 , R 1a , and R 3 are a divalent group, R 5 is a trivalent group, R 7 , R 8 , R 9 , R 10 , and R 11 are each independently a hydrogen atom or a saturated C 1-10 hydrocarbon group, n is the number of repeating units and is 1 to 10, and a dotted line is a chemical bond between adjacent atoms,
wherein the compound (E) is selected from the group consisting of
and
wherein the photocurable stepped substrate-coating composition is a resist underlayer film-forming composition used in a lithography process in manufacturing of a semiconductor device.
2. The photocurable stepped substrate-coating composition according to claim 1 , further comprising an acid catalyst.
3. The photocurable stepped substrate-coating composition according to claim 1 , wherein the compound (E) contains the epoxy group and the hydroxy group at a molar ratio (epoxy group)/(hydroxy group) of 0 or more and 0.5 or less, and contains the partial structure (II) so that a molar ratio (partial structure (II))/(partial structure (I)+partial structure (II)) is 0.01 or more and 0.8 or less.
4. The photocurable stepped substrate-coating composition according to claim 1 , wherein the compound (E) has the partial structure (I) and the partial structure (II) in a proportion of each of the partial structures (I) and (II) of 1 to 1,000 structures.
5. The photocurable stepped substrate-coating composition according to claim 1 , wherein the resist underlayer film-forming composition has a property of both a photocrosslinking function and a thermal crosslinking function.
6. A method for manufacturing a coated substrate comprising steps of (i) applying the photocurable stepped substrate-coating composition according to claim 1 to a stepped substrate, and (ii) exposing the composition.
7. The method for manufacturing a coated substrate according to claim 6 , further comprising a step (ia) of heating the photocurable stepped substrate-coating composition at a temperature of 70 to 400° C. for 10 seconds to 5 minutes after the composition is applied in the step (i).
8. The method for manufacturing a coated substrate according to claim 6 , wherein a wavelength of exposure light in the step (ii) is 150 nm to 248 nm.
9. The method for manufacturing a coated substrate according to claim 6 , wherein an exposure dose in the step (ii) is 10 mJ/cm 2 to 3,000 mJ/cm 2 .
10. The method for manufacturing a coated substrate according to claim 6 , wherein the substrate has an open area (unpatterned area) and a pattern area including dense (DENCE) and crude (ISO) pattern areas, and an aspect ratio of pattern at the pattern area is 0.1 to 10.
11. The method for manufacturing a coated film according to claim 6 , wherein a difference in level of coating (Bias) between the open area and the pattern area is 1 to 50 nm.
12. A method for manufacturing a semiconductor device comprising steps of:
forming an underlayer film from the photocurable stepped substrate-coating composition according to claim 1 on a stepped substrate;
forming a resist film on the underlayer film;
forming a resist pattern by irradiation of the resist film with light or an electron beam and development;
etching the underlayer film using the resist pattern formed to form a patterned underlayer film; and
processing a semiconductor substrate by using the patterned underlayer film.
13. The method for manufacturing a semiconductor device according to claim 12 , wherein the stepped substrate has an open area (unpatterned area) and a pattern area including dense (DENCE) and crude (ISO) pattern areas, and an aspect ratio of patterns at the pattern area is 0.1 to 10.
14. The method for manufacturing a semiconductor device according to claim 12 , wherein the step of forming an underlayer film from the photocurable stepped substrate-coating composition includes steps of (i) applying the photocurable stepped substrate-coating composition to the stepped substrate and (ii) exposing the composition.
15. The method for manufacturing a semiconductor device according to claim 14 , further comprising a step (ia) of heating the photocurable stepped substrate-coating composition at a temperature of 70 to 400° C. for 10 seconds to 5 minutes after the composition is applied in the step (i).
16. The method for manufacturing a semiconductor device according to claim 14 , wherein a wavelength of exposure light in the step (ii) is 150 nm to 248 nm.
17. The method for manufacturing a semiconductor device according to claim 14 , wherein an exposure dose in the step (ii) is 10 mJ/cm 2 to 3,000 mJ/cm 2 .
18. The method for manufacturing a semiconductor device according to claim 12 , wherein the underlayer film formed from the photocurable stepped substrate-coating composition has a difference in level of coating of 1 to 50 nm.
19. A method for manufacturing a semiconductor device comprising steps of:
forming an underlayer film from the photocurable stepped substrate-coating composition according to claim 1 on a stepped substrate;
forming a hard mask on the underlayer film;
forming a resist film on the hard mask;
forming a resist pattern by irradiation of the resist film with light or an electron beam and development;
etching the hard mask using the resist pattern formed to form a patterned hard mask;
etching the underlayer film using the patterned hard mask to form a patterned underlayer film; and
processing a semiconductor substrate by using the patterned underlayer film.
20. The method for manufacturing a semiconductor device according to claim 19 , wherein the stepped substrate has an open area (unpatterned area) and a pattern area including dense (DENCE) and crude (ISO) pattern areas, and an aspect ratio of patterns at the pattern area is 0.1 to 10.
21. The method for manufacturing a semiconductor device according to claim 19 , wherein the step of forming an underlayer film from the photocurable stepped substrate-coating composition includes steps of (i) applying the photocurable stepped substrate-coating composition to the stepped substrate and (ii) exposing the composition.
22. The method for manufacturing a semiconductor device according to claim 21 , further comprising a step (ia) of heating the photocurable stepped substrate-coating composition at a temperature of 70 to 400° C. for 10 seconds to 5 minutes after the composition is applied in the step (i).
23. The method for manufacturing a semiconductor device according to claim 21 , wherein a wavelength of exposure light in the step (ii) is 150 nm to 248 nm.
24. The method for manufacturing a semiconductor device according to claim 21 , wherein an exposure dose in the step (ii) is 10 mJ/cm 2 to 3,000 mJ/cm 2 .
25. The method for manufacturing a semiconductor device according to claim 19 , wherein the underlayer film formed from the photocurable stepped substrate-coating composition has a difference in level of coating of 1 to 50 nm.