Resist composition and patterning process
A resist composition comprising a base polymer and a sulfonium or iodonium salt of a fluorinated sulfonic acid having a phenylene group which is substituted with an iodized phenyl-containing group and a nitro group is provided. The resist composition has a high sensitivity and forms a pattern with improved LWR or CDU, independent of whether it is of positive or negative tone.
1. A resist composition comprising a base polymer and a sulfonium salt having the formula (A-1) or an iodonium salt having the formula (A-2):
wherein k is an integer of 0 to 2, p is an integer of 1 to 5, q is an integer of 0 to 4, p+q is from 1 to 5, r is 1 or 2, s is an integer of 0 to 3, r+s is from 1 to 4,
L 1 is a single bond, ether bond, ester bond, amide bond, or a C 1 -C 6 saturated hydrocarbylene group in which some constituent —CH 2 — may be replaced by an ether bond, ester bond or amide bond,
L 2 is a single bond or a C 1 -C 20 divalent linking group which may contain oxygen, sulfur or nitrogen,
Rf 1 to Rf 4 are each independently hydrogen, fluorine or trifluoromethyl, at least one of Rf 1 to Rf 4 being fluorine or trifluoromethyl,
R 1 is a hydroxy, carboxy, fluorine, chlorine, bromine, amino group, or a C 1 -C 20 hydrocarbyl group, C 1 -C 20 hydrocarbyloxy group, C 2 -C 20 hydrocarbyloxycarbonyl group, C 2 -C 20 hydrocarbylcarbonyloxy group, or C 1 -C 20 hydrocarbylsulfonyloxy group, which may contain fluorine, chlorine, bromine, hydroxy, amino or ether bond, or —N(R 1A ) (R 1B ), —N(R 1C )—C(═O)—R 1D , or —N(R 1C )—C(═O)—O—R 1D , wherein R 1A and R 1B are each independently hydrogen or a C 1 -C 6 saturated hydrocarbyl group, R 1C is hydrogen or a C 1 -C 6 saturated hydrocarbyl group which may contain halogen, hydroxy moiety, a C 1 -C 6 saturated hydrocarbyloxy moiety, C 2 -C 6 saturated hydrocarbylcarbonyl moiety, or C 2 -C 6 saturated hydrocarbylcarbonyloxy moiety, R 1D is a C 1 -C 16 aliphatic hydrocarbyl group or C 6 -C 12 aryl group, which may contain halogen, hydroxy moiety, a C 1 -C 6 saturated hydrocarbyloxy moiety, C 2 -C 6 saturated hydrocarbylcarbonyl moiety, or C 2 -C 6 saturated hydrocarbylcarbonyloxy moiety,
R 2 is a C 1 -C 4 alkyl group, C 1 -C 4 alkyloxy group, C 2 -C 5 alkylcarbonyloxy group, or halogen fluorine, or chlorine,
R 3 , R 4 , R 5 , R 6 and R 7 are each independently halogen or a C 1 -C 20 hydrocarbyl group which may contain a heteroatom, R 3 and R 4 may bond together to form a ring with the sulfur atom to which they are attached.
2. The resist composition of claim 1 wherein the base polymer comprises repeat units having the formula (a1) or repeat units having the formula (a2):
wherein R A is each independently hydrogen or methyl,
X 1 is a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing an ester bond, ether bond or lactone ring,
X 2 is a single bond or ester bond,
X 3 is a single bond, ether bond or ester bond,
R 11 and R 12 are each independently an acid labile group,
R 13 is fluorine, trifluoromethyl group, cyano group, a C 1 -C 6 saturated hydrocarbyl group, C 1 -C 6 saturated hydrocarbyloxy group, C 2 -C 7 saturated hydrocarbylcarbonyl group, C 2 -C 7 saturated hydrocarbylcarbonyloxy group, or C 2 -C 7 saturated hydrocarbyloxycarbonyl group,
R 14 is a single bond or a C 1 -C 6 alkanediyl group in which some constituent —CH 2 — may be replaced by an ether bond or ester bond,
a is 1 or 2, and b is an integer of 0 to 4.
3. The resist composition of claim 2 which is a chemically amplified positive resist composition.
4. The resist composition of claim 1 wherein the base polymer is free of an acid labile group.
5. The resist composition of claim 4 which is a chemically amplified negative resist composition.
6. The resist composition of claim 1 wherein the base polymer comprises repeat units of at least one type selected from repeat units having the formulae (f1) to (f3):
wherein R A is each independently hydrogen or methyl,
Z 1 is a single bond, a C 1 -C 6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C 7 -C 18 group obtained by combining the foregoing, or —O—Z 11 —, —C(═O)—O—Z 11 — or —C(═O)—NH—Z 11 —, Z 11 is a C 1 -C 6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C 7 -C 18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety,
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 saturated hydrocarbylene group which may contain a carbonyl moiety, ester bond or ether bond,
Z 3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene group, —O—Z 31 —, —C(═O)—O—Z 31 —, or —C(═O)—NH—Z 31 —, Z 31 is a C 1 -C 6 aliphatic hydrocarbylene group, phenylene group, fluorinated phenylene group, or trifluoromethyl-substituted phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety,
R 21 to R 28 are each independently halogen or a C 1 -C 20 hydrocarbyl group which may contain a heteroatom, a pair of R 23 and R 24 or R 26 and R 27 may bond together to form a ring with the sulfur atom to which they are attached,
R HF is hydrogen or trifluoromethyl, and
M − is a non-nucleophilic counter ion.
7. The resist composition of claim 1 , further comprising an organic solvent.
8. The resist composition of claim 1 , further comprising a quencher.
9. The resist composition of claim 1 , further comprising a surfactant.
10. A pattern forming process comprising the steps of applying the resist composition of claim 1 onto a substrate to form a resist film thereon, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.
11. The process of claim 10 wherein the high-energy radiation is ArF excimer laser of wavelength 193 nm or KrF excimer laser of wavelength 248 nm.
12. The process of claim 10 wherein the high-energy radiation is EB or EUV of wavelength 3 to 15 nm.
13. The resist composition of claim 1 , wherein L 2 is a single bond, an amide bond, or a C 1 -C 20 hydrocarbylene group in which some constituent —CH 2 — may be replaced by an ester bond, ether bond, amide bond or sulfonic ester bond, and the constituent —CH 2 — may be located at the end of the group.
14. The resist composition of claim 8 , wherein the quencher is a sulfonium salt of iodized benzene ring-containing carboxylic acid having the following formula (D)
wherein R 201 is hydroxy, fluorine, chlorine, bromine, amino, nitro, cyano, or a C 1 -C 6 saturated hydrocarbyl, C 1 -C 6 saturated hydrocarbyloxy, C 2 -C 6 saturated hydrocarbylcarbonyloxy or C 1 -C 4 saturated hydrocarbylsulfonyloxy group, in which some or all hydrogen may be substituted by halogen, or —N(R 201A ) (R 201B ), —N(R 201C )—C(═O)—R 201D , or —N(R 201C )—C(═O)—O—R 201D , R 201A and R 201B are each independently hydrogen or a C 1 -C 6 saturated hydrocarbyl group, R 201C is hydrogen or a C 1 -C 6 saturated hydrocarbyl group, R 201D is a C 1 -C 6 saturated hydrocarbyl or C 2 -C 8 unsaturated aliphatic hydrocarbyl group, groups R 201 may be the same or different when y and/or z is 2 or 3,
x is an integer of 1 to 5, y is an integer of 0 to 3, and z is an integer of 1 to 3,
L 11 is a single bond, or a C 1 -C 20 (z+1)-valent linking group which may contain at least one moiety selected from ether bond, carbonyl moiety, ester bond, amide bond, sultone ring, lactam ring, carbonate bond, halogen, hydroxy moiety, and carboxy moiety,
R 202 , R 203 and R 204 are each independently halogen, or a C 1 -C 20 hydrocarbyl group which may contain a heteroatom, R 202 and R 203 may bond together to form a ring with the sulfur atom to which they are attached.