Resist composition and patterning process
A resist composition comprises a polymer comprising recurring units having formula (1) wherein R 1 , R 4 , R 7 , and R 14 are H or methyl, R 2 , R 3 , R 15 , and R 16 are H, alkyl or fluoroalkyl, R is F or H, R 5 is alkylene, R 6 is fluorinated alkyl, R 8 is a single bond or alkylene, R 10 and R 11 are H, F, methyl or trifluoromethyl, R 12 and R 13 are a single bond, —O— or —CR 18 R 19 —, R 9 , R 18 , and R 19 are H, F, methyl or trifluoromethyl, R 17 is alkylene, X 1 , X 2 and X 3 are —C(═O)—O—, —O—, or —C(═O)—R 20 —C(═O)—O— wherein R 20 is alkylene, 0≦(a-1)<1, 0≦(a-2)<1, 0≦(a-3)<1, 0<(a-1)+(a-2)+(a-3)<1, 0<b<1, and 0<(a-1)+(a-2)+(a-3)+b≦1.
1. A resist composition which is a chemically amplified positive resist composition, comprising
100 parts by weight of a base resin comprising at least recurring units having acid labile groups and recurring units having hydroxyl groups and/or adhesive groups of lactone ring, and
0.1 to 50 parts by weight the polymer comprising recurring units of formula (1):
wherein R 1 , R 4 , R 7 , and R 14 are each independently hydrogen or methyl,
R 2 , R 3 , R 15 , and R 16 are each independently hydrogen or a straight, branched or cyclic C 1 -C 20 alkyl or fluoroalkyl group, or R 2 and R 3 , and R 15 and R 16 may bond together to form a ring with the carbon atom to which they are attached, and in this case, R 2 and R 3 , and R 15 and R 16 , taken together, stand for a straight, branched or cyclic C 2 -C 20 alkylene or fluoroalkylene group,
R is fluorine or hydrogen, or may bond with R 5 to form a ring of 3 to 10 carbon atoms in total with the carbon atom to which they are attached,
R 5 is a straight, branched or cyclic C 1 -C 6 alkylene group in which at least one hydrogen atom may be substituted by a fluorine atom,
R 6 is a straight or branched C 1 -C 10 alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, R 5 and R 6 may bond together to form a ring with the carbon atoms to which they are attached, and in this case, R 5 and R 6 , taken together, stand for a trivalent organic group of 2 to 12 carbon atoms in total in which at least one hydrogen atom is substituted by a fluorine atom,
R 8 is a single bond or a C 1 -C 4 alkylene group,
R 10 and R 11 are each independently hydrogen, fluorine, methyl or trifluoromethyl,
R 12 and R 13 are each independently a single bond, —O— or —CR 18 R 19 —,
R 9 , R 18 , and R 19 are hydrogen, fluorine, methyl or trifluoromethyl,
R 17 is a straight or branched C 1 -C 4 alkylene group or may bond with R 15 or R 16 to form a C 3 -C 10 aliphatic ring with the carbon atom to which they are attached,
X 1 , X 2 and X 3 are each independently —C(═O)—O—, —O—, or —C(═O)—R 20 —C(═O)—O— wherein R 20 is a straight, branched or cyclic C 1 -C 10 alkylene group,
the subscripts are numbers in the range: 0≦(a-1)<1, 0≦(a-2)<1, 0≦(a-3)<1, 0<(a-1)+(a-2)+(a-3)<1, 0<b<1, and 0<(a-1)+(a-2)+(a-3)+b≦1.
2. The resist composition of claim 1 , further comprising at least one member selected from the group consisting of an organic solvent, a basic compound, a dissolution regulator, a crosslinker, and a surfactant.
3. A pattern forming process comprising the steps of:
applying the resist composition of claim 1 onto a substrate to form a coating,
heat treating the coating and exposing it to high-energy radiation, and
developing the exposed coating with a developer.
4. The process of claim 3 , wherein the high-energy radiation has a wavelength of 180 to 250 nm.
5. The process of claim 3 , wherein the exposing step is by immersion lithography involving exposing the coating to high-energy radiation through a liquid.
6. The process of claim 5 , wherein the immersion lithography involves using high-energy radiation having a wavelength of 180 to 250 nm, introducing a liquid between the resist-coated substrate and a projection lens, and exposing the substrate to the high-energy radiation through the liquid.
7. The process of claim 5 , wherein the liquid is water.
8. The process of claim 3 , wherein the high-energy radiation is an electron beam.
9. A pattern forming process comprising the steps of:
applying the resist composition of claim 1 onto a mask blank substrate to form a coating,
heat treating the coating and exposing it to high-energy radiation, and
developing the coating with a developer.
10. The resist composition of claim 1 , wherein the recurring units (a-1) in formula (1) are selected from the group consisting of the following formulae:
wherein R 1 is each independently hydrogen or methyl,
the recurring units (a-2) in formula (I) are selected from the group consisting of the following formulae:
wherein R 4 is each independently hydrogen or methyl,
the recurring units (a-3) in formula (I) are selected from the group consisting of the following formulae:
wherein R 7 is each independently hydrogen or methyl, and
the recurring units (b) in formula (I) are selected from the group consisting of the following formulae:
wherein R 14 is each independently hydrogen or methyl.
11. A pattern forming process comprising the steps of:
applying a resist composition of claim 1 onto a substrate to form a coating,
heat treating the coating and exposing it to an electron beam, and
developing the exposed coating with a developer,
said resist composition comprising a polymer comprising recurring units having the general formula (1):
wherein R 1 , R 4 , R 7 , and R 14 are each independently hydrogen or methyl,
R 2 , R 3 , R 15 , and R 16 are each independently hydrogen or a straight, branched or cyclic C 1 -C 20 alkyl or fluoroalkyl group, or R 2 and R 3 , and R 15 and R 16 may bond together to form a ring with the carbon atom to which they are attached, and in this case, R 2 and R 3 , and R 15 and R 16 , taken together, stand for a straight, branched or cyclic C 2 -C 20 alkylene or fluoroalkylene group,
R is fluorine or hydrogen, or may bond with R 5 to form a ring of 3 to 10 carbon atoms in total with the carbon atom to which they are attached,
R 5 is a straight, branched or cyclic C 1 -C 6 alkylene group in which at least one hydrogen atom may be substituted by a fluorine atom,
R 6 is a straight or branched C 1 -C 10 alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, R 5 and R 6 may bond together to form a ring with the carbon atoms to which they are attached, and in this case, R 5 and R 6 , taken together, stand for a trivalent organic group of 2 to 12 carbon atoms in total in which at least one hydrogen atom is substituted by a fluorine atom,
R 8 is a single bond or a C 1 -C 4 alkylene group,
R 10 and R 11 are each independently hydrogen, fluorine, methyl or trifluoromethyl,
R 12 and R 13 are each independently a single bond, —O— or —CR 18 R 19 —,
R 9 , R 18 , and R 19 are hydrogen, fluorine, methyl or trifluoromethyl,
R 17 is a straight or branched C 1 -C 4 alkylene group or may bond with R 15 or R 16 to form a C 3 -C 10 aliphatic ring with the carbon atom to which they are attached,
X 1 , X 2 and X 3 are each independently —C(═O)—O—, —O—, or —C(═O)—R 20 —C(═O)—O— wherein R 20 is a straight, branched or cyclic C 1 -C 10 alkylene group,
the subscripts are numbers in the range: 0≦(a-1)<1, 0≦(a-2)<1, 0≦(a-3)<1, 0<(a-1)+(a-2)+(a-3)<1, 0<b<1, and 0<(a-1)+(a-2)+(a-3)+b≦1.
12. A resist composition which is a chemically amplified negative resist composition,
comprising a polymer comprising recurring units having the general formula (1):
wherein R 1 , R 4 , R 7 , and R 14 are each independently hydrogen or methyl,
R 2 , R 3 , R 15 , and R 16 are each independently hydrogen or a straight, branched or cyclic C 1 -C 20 alkyl or fluoroalkyl group, or R 2 and R 3 , and R 15 and R 16 may bond together to form a ring with the carbon atom to which they are attached, and in this case, R 2 and R 3 , and R 15 and R 16 , taken together, stand for a straight, branched or cyclic C 2 -C 20 alkylene or fluoroalkylene group,
R is fluorine or hydrogen, or may bond with R 5 to form a ring of 3 to 10 carbon atoms in total with the carbon atom to which they are attached,
R 5 is a straight, branched or cyclic C 1 -C 6 alkylene group in which at least one hydrogen atom may be substituted by a fluorine atom,
R 6 is a straight or branched C 1 -C 10 alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, R 5 and R 6 may bond together to form a ring with the carbon atoms to which they are attached, and in this case, R 5 and R 6 , taken together, stand for a trivalent organic group of 2 to 12 carbon atoms in total in which at least one hydrogen atom is substituted by a fluorine atom,
R 8 is a single bond or a C 1 -C 4 alkylene group,
R 10 and R 11 are each independently hydrogen, fluorine, methyl or trifluoromethyl,
R 12 and R 13 are each independently a single bond, —O— or —CR 18 R 19 —,
R 9 , R 18 , and R 19 are hydrogen, fluorine, methyl or trifluoromethyl,
R 17 is a straight or branched C 1 -C 4 alkylene group or may bond with R 15 or R 16 to form a C 3 -C 10 aliphatic ring with the carbon atom to which they are attached,
X 1 , X 2 and X 3 are each independently —C(═O)—O—, —O—, or —C(═O)—R 20 —C(═O)—O— wherein R 20 is a straight, branched or cyclic C 1 -C 10 alkylene group,
the subscripts are numbers in the range: 0≦(a-1)<1, 0≦(a-2)<1, 0≦(a-3)<1, 0<(a-1)+(a-2)+(a-3)<1, 0<b<1, and 0<(a-1)+(a-2)+(a-3)+b≦1.
13. The resist composition of claim 12 , further comprising at least one member selected from the group consisting of an organic solvent, a basic compound, a crosslinker, and a surfactant.
14. A pattern forming process comprising the steps of:
applying the resist composition of claim 12 onto a substrate to form a coating,
heat treating the coating and exposing it to high-energy radiation, and
developing the exposed coating with a developer.
15. The process of claim 14 , wherein the exposing step is by immersion lithography involving exposing the coating to high-energy radiation through a liquid, wherein the immersion lithography involves using high-energy radiation having a wavelength of 180 to 250 nm, introducing a liquid between the resist-coated substrate and a projection lens, and exposing the substrate to the high-energy radiation through the liquid.
16. The process of claim 15 , wherein the liquid is water.
17. The process of claim 14 , wherein the high-energy radiation is an electron beam.
18. A pattern forming process comprising the steps of:
applying the resist composition of claim 12 onto a mask blank substrate to form a coating,
heat treating the coating and exposing it to high-energy radiation, and
developing the coating with a developer.