Chemically amplified resist composition and patterning process
A chemically amplified resist composition comprising a quencher containing a quaternary ammonium iodide, dibromoiodide, bromodiiodide or triiodide, and an acid generator exhibits a sensitizing effect and an acid diffusion suppressing effect and forms a pattern having improved resolution, LWR and CDU.
1. A chemically amplified resist composition comprising a quencher containing a quaternary ammonium salt selected from the group consisting of a quaternary ammonium iodide, quaternary ammonium dibromoiodide, quaternary ammonium bromodiiodide, and quaternary ammonium triiodide, and an acid generator,
wherein the acid generator is a polymer comprising recurring units of at least one selected from recurring units having the formulae (f1) to (f3) wherein the polymer is a base polymer:
wherein R A is each independently hydrogen or methyl,
Z 1 is a single bond, phenylene, —O—Z 11 —, or —C(═O)—Z 12 —Z 11 —, Z 11 is a C 1 -C 6 straight, branched or cyclic alkylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 11 is a C 2 -C 6 straight, branched or cyclic alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 11 is a phenylene group, Z 12 is —O— or —NH—,
R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , and R 58 are each independently a C 1 -C 12 straight, branched or cyclic alkyl group which may contain a carbonyl, ester or ether moiety, or R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , and R 58 are each independently a C 6 -C 12 aryl, C 7 -C 20 aralkyl, or mercaptophenyl group,
Z 2 is a single bond, —Z 21 —C(═O)—O—, —Z 21 —O—, or —Z 21 —O—C(═O)—, Z 21 is a C 1 -C 12 straight, branched or cyclic alkylene group which may contain a carbonyl, ester or ether moiety,
Z 3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z 31 —, or —C(═O)—Z 32 —Z 31 —, Z 31 is a C 1 -C 6 straight, branched or cyclic alkylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 31 is a C 2 -C 6 straight, branched or cyclic alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 31 is a phenylene, fluorinated phenylene or trifluoromethyl-substituted phenylene group, Z 32 is —O— or —NH—,
A 1 is hydrogen or trifluoromethyl, and M − is a non-nucleophilic counter ion.
2. The resist composition of claim 1 wherein the quaternary ammonium salt has the formula (1) or (2):
wherein R 1 to R 4 and R 5 to R 10 are each independently a C 1 -C 24 straight, branched or cyclic alkyl group, C 2 -C 24 straight, branched or cyclic alkenyl group, C 2 -C 24 straight, branched or cyclic alkynyl group, or C 6 -C 24 aryl group, R 1 to R 4 and R 5 to R 10 may contain a halogen, hydroxyl, carboxyl, ether, ester, thiol, thioester, thionoester, dithioester, amino, nitro, sulfone or ferrocenyl moiety, a pair of R 1 and R 2 , R 1 and R 4 , R 2 and R 3 , and/or R 3 and R 4 may bond together to form a ring, or a pair of R 1 and R 2 , R 1 and R 4 , R 2 and R 3 , or R 3 and R 4 , taken together, may form a double bond, R 11 is a C 2 -C 12 straight, branched or cyclic alkylene group which may contain an ether and/or ester moiety, X − is an anion selected from the group consisting of I − , Br 2 I − , BrI 2 − and I 3 − .
3. The resist composition of claim 1 wherein the base polymer is an acid labile group-free polymer.
4. The resist composition of claim 1 , further comprising an organic solvent.
5. The resist composition of claim 1 , further comprising a surfactant.
6. A pattern forming process comprising the steps of coating the resist composition of claim 1 onto a substrate, baking, exposing the resulting resist film to high-energy radiation, and developing the resist film with a developer.
7. The process of claim 6 wherein the high-energy radiation is ArF excimer laser of wavelength 193 nm or KrF excimer laser of wavelength 248 nm.
8. The process of claim 6 wherein the high-energy radiation is EB or EUV of wavelength 3 to 15 nm.
9. A chemically amplified resist composition comprising
a quencher containing a quaternary ammonium salt selected from the group consisting of a quaternary ammonium iodide, quaternary ammonium dibromoiodide, quaternary ammonium bromodiiodide, and quaternary ammonium triiodide,
an acid generator, and
a base polymer,
wherein the acid generator is capable of generating sulfonic acid, imidic acid or methide acid, and the base polymer consists of
recurring units having the formula (a1) or recurring units having the formula (a2), and at least one selected from the group consisting of
recurring units (b) having a phenolic hydroxyl group as an adhesive group,
recurring units (c) having another adhesive group selected from the group consisting of hydroxyl (other than the foregoing phenolic hydroxyl), lactone ring, ether, ester, carbonyl and cyano groups,
recurring units (d) selected from the group of units consisting of indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene, and derivatives thereof,
recurring units (e) derived from compounds selected from the group consisting of styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindene, vinyl-pyridine, and vinylcarbazole, and
recurring units of at least one selected from recurring units having the formulae (f1) to (f3):
wherein R A is each independently hydrogen or methyl, R 21 and R 22 are each independently an acid labile group, X 1 is a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing ester moiety or lactone ring, and X 2 is a single bond or ester group,
wherein R A is each independently hydrogen or methyl,
Z 1 is a single bond, phenylene, —O—Z 11 , —C(═O)—Z 12 —Z 11 —, is a C 1 -C 6 straight, branched or cyclic alkylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 11 is a C 2 -C 6 straight, branched or cyclic alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 11 is a phenylene group, Z 12 is —O— or —NH—,
R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , and R 58 are each independently a C 1 -C 12 straight, branched or cyclic alkyl group which may contain a carbonyl, ester or ether moiety, or R 51 R 52 , R 53 , R 54 R 55 , R 56 , R 57 , and R 58 are each independently a C 6 -C 12 aryl, C 7 -C 20 aralkyl, or mercaptophenyl group,
Z 2 is a single bond, —Z 21 —C(═O)—O—, —Z 21 —O—, or —Z 21 —O—C(═O)—, Z 21 is a C 1 -C 12 straight, branched or cyclic alkylene group which may contain a carbonyl, ester or ether moiety,
Z 3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z 31 —, or —C(═O)—Z 32 —Z 31 —, Z 31 is a C 1 -C 6 straight, branched or cyclic alkylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 31 is a C 2 -C 6 straight, branched or cyclic alkenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, or Z 31 is a phenylene, fluorinated phenylene or trifluoromethyl-substituted phenylene group, Z 32 is —O— or —NH—,
A 1 is hydrogen or trifluoromethyl, and M − is a non-nucleophilic counter ion.
10. The resist composition of claim 9 which is a chemically amplified positive resist composition.
11. The resist composition of claim 9 wherein the quaternary ammonium salt has the formula (1) or (2):
wherein R 1 to R 4 and R 5 to R 10 are each independently a C 1 -C 24 straight, branched or cyclic alkyl group, C 2 -C 24 straight, branched or cyclic alkenyl group, C 2 -C 24 straight, branched or cyclic alkynyl group, or C 6 -C 24 aryl group, R 1 to R 4 and R 5 to R 10 may contain a halogen, hydroxyl, carboxyl, ether, ester, thiol, thioester, thionoester, dithioester, amino, nitro, sulfone or ferrocenyl moiety, a pair of R 1 and R 2 , R 1 and R 4 , R 2 and R 3 , and/or R 3 and R 4 may bond together to form a ring, or a pair of R 1 and R 2 , R 1 and R 4 , R 2 and R 3 , or R 3 and R 4 , taken together, may form a double bond, R 11 is a C 2 -C 12 straight, branched or cyclic alkylene group which may contain an ether and/or ester moiety, X − is an anion selected from the group consisting of I − , Br 2 I − , BrI 2 − and I 3 − .
12. A pattern forming process comprising the steps of coating the resist composition of claim 9 onto a substrate, baking, exposing the resulting resist film to high-energy radiation, and developing the resist film with a developer.
13. A chemically amplified negative resist composition comprising
a quencher containing a quaternary ammonium salt selected from the group consisting of a quaternary ammonium iodide, quaternary ammonium dibromoiodide, quaternary ammonium bromodiiodide, and quaternary ammonium triiodide,
an acid generator, and
a base polymer,
wherein the base polymer is an acid labile group free polymer.
14. The resist composition of claim 13 wherein the quaternary ammonium salt has the formula (1) or (2):
wherein R 1 to R 4 and R 5 to R 10 are each independently a C 1 -C 24 straight, branched or cyclic alkyl group, C 2 -C 24 straight, branched or cyclic alkenyl group, C 2 -C 24 straight, branched or cyclic alkynyl group, or C 6 -C 24 aryl group, R 1 to R 4 and R 5 to R 10 may contain a halogen, hydroxyl, carboxyl, ether, ester, thiol, thioester, thionoester, dithioester, amino, nitro, sulfone or ferrocenyl moiety, a pair of R 1 and R 2 , R 1 and R 4 , R 2 and R 3 , and/or R 3 and R 4 may bond together to form a ring, or a pair of R 1 and R 2 , R 1 and R 4 , R 2 and R 3 , or R 3 and R 4 , taken together, may form a double bond, R 11 is a C 2 -C 12 straight, branched or cyclic alkylene group which may contain an ether and/or ester moiety, X − is an anion selected from the group consisting of I − , Br 2 I − , BrI 2 − and I 3 − .
15. A pattern forming process comprising the steps of coating the resist composition of claim 13 onto a substrate, baking, exposing the resulting resist film to high-energy radiation, and developing the resist film with a developer.