Onium salt, chemically amplified resist composition and patterning process
An onium salt having formula (1) serving as an acid diffusion inhibitor and a chemically amplified resist composition comprising the acid diffusion inhibitor are provided. When processed by lithography, the resist composition forms a pattern having minimal defects and excellent lithography performance factors such as CDU, LWR and DOF.
1. A chemically amplified resist composition comprising:
(A) a base polymer comprising repeat units having the formula (a) or repeat units having the formula (b),
(B) a photoacid generator,
(C-1) an acid diffusion inhibitor comprising an onium salt having the formula (1), and
(D) an organic solvent,
wherein X is sulfur,
n is 1 when X is sulfur,
R 1 is a C 1 -C 5 straight or branched hydrocarbyl group in which at least one of hydrogen atoms of the C 1 -C 5 straight or branched hydrocarbyl group may be replaced with fluorine or in which at least one of carbons which is not terminal may be replaced with oxygen to form an ether, and R 1 is exclusive of a tertiary hydrocarbyl group,
R 2 and R 3 are each independently a C 1 -C 30 hydrocarbyl group which may contain fluorine, chlorine, bromine, iodine, cyano moiety, carbonyl moiety, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride or haloalkyl moiety, R 2 and R 3 may bond together to form a ring with X to which they are attached,
Ar is a C 6 -C 14 arylene group which may be substituted with a substituent selected from a halogen atom, hydroxy group, C 1 -C 10 hydrocarbyl group which may contain a heteroatom, C 1 -C 10 hydrocarbyloxy group which may contain a heteroatom, C 2 -C 10 hydrocarbylcarbonyl group which may contain a heteroatom, and C 2 -C 10 hydrocarbylcarbonyloxy group which may contain a heteroatom, R 2 and Ar may bond together to form a ring with X to which they are attached, wherein Ar does not include a hydroxyl group, and
Z − is a carboxylate, sulfonamide, sulfonimide or methide anion,
wherein R A is each independently hydrogen or methyl,
X A is a single bond, phenylene group, naphthylene group or (backbone)-C(═O)—O—X A1 —, X A1 is a C 1 -C 15 hydrocarbylene group which may contain a hydroxy moiety, ether bond, ester bond, or lactone ring,
X B is a single bond or ester bond,
AL 1 and AL 2 are each independently an acid labile group.
2. The chemically amplified resist composition of claim 1 , having the formula (2):
wherein R 1 , R 2 , R 3 , n, X, and Z are as defined above,
R 4 is a halogen atom, hydroxy group, C 1 -C 10 hydrocarbyl group which may contain a heteroatom, C 1 -C 10 hydrocarbyloxy group which may contain a heteroatom, C 2 -C 10 hydrocarbylcarbonyl group which may contain a heteroatom, or C 2 -C 10 hydrocarbylcarbonyloxy group which may contain a heteroatom, and
m is an integer of 0 to 4.
3. The chemically amplified resist composition of claim 1 wherein R 1 is methyl, ethyl, propyl, isopropyl, n-butyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1-trifluoromethyl-2,2,2-trifluoroethyl or 2-methoxyethyl.
4. The chemically amplified resist composition of claim 1 wherein Z − is a carboxylate anion having at least one fluorine atom or trifluoromethyl group at α- or β-position relative to the carboxy group.
5. The chemically amplified resist composition of claim 1 wherein Z − is an anion having any one of the formulae (Z-1) to (Z-5):
wherein R 11 is a C 1 -C 4 perfluoroalkyl group,
R 12 and R 13 are each independently hydrogen, fluorine, methyl or trifluoromethyl, at least one of R 12 and R 13 is fluorine or trifluoromethyl,
R 14 and R 15 are each independently hydrogen or a C 1 -C 15 hydrocarbyl group which may contain a heteroatom,
R 16 , R 17 and R 18 are each independently hydrogen or a C 1 -C 30 hydrocarbyl group which may contain a heteroatom,
L 1 and L 2 are each independently a single bond, carbonyl group or sulfonyl group.
6. A chemically amplified resist composition comprising:
(A′) a base polymer comprising repeat units having the formula (a) or repeat units having the formula (b) and repeat units adapted to generate an acid upon light exposure,
(C-1) the acid diffusion inhibitor, comprising an onium salt having the formula (1), and
(D) an organic solvent,
wherein X is sulfur,
n is 1 when X is sulfur,
R 1 is a C 1 -C 5 hydrocarbyl group which may contain fluorine or oxygen,
R 2 and R 3 are each independently a C 1 -C 30 hydrocarbyl group which may contain a heteroatom, R 2 and R 3 may bond together to form a ring with X to which they are attached,
Ar is a C 6 -C 14 arylene group which may be substituted with a substituent selected from a halogen atom, hydroxy group, C 1 -C 10 hydrocarbyl group which may contain a heteroatom, C 1 -C 10 hydrocarbyloxy group which may contain a heteroatom, C 2 -C 10 hydrocarbylcarbonyl group which may contain a heteroatom, and C 2 -C 10 hydrocarbylcarbonyloxy group which may contain a heteroatom, R 2 and Ar may bond together to form a ring with X to which they are attached, and
Z − is a carboxylate, sulfonamide, sulfonimide or methide anion,
wherein R A is each independently hydrogen or methyl,
X A is a single bond, phenylene group, naphthylene group or (backbone)-C(═O)—O—X A1 —, X A1 is a C 1 -C 15 hydrocarbylene group which may contain a hydroxy moiety, ether bond, ester bond, or lactone ring,
X B is a single bond or ester bond,
AL 1 and AL 2 are each independently an acid labile group.
7. The chemically amplified resist composition of claim 1 wherein the acid labile group has the formula (L1):
wherein R 21 is a C 1 -C 7 hydrocarbyl group in which any constituent —CH 2 — may be replaced by —O—, a is 1 or 2, and the broken line designates a valence bond.
8. The chemically amplified resist composition of claim 1 , wherein the base polymer comprises repeat units having the formula (c):
wherein R A is hydrogen or methyl,
Y A is a single bond or ester bond,
R 22 is fluorine, iodine, a carboxy group, formyl group, formyloxy group, C 1 -C 10 hydrocarbyl group which may contain a heteroatom, C 1 -C 10 hydrocarbyloxy group which may contain a heteroatom, C 2 -C 10 hydrocarbylcarbonyl group which may contain a heteroatom, C 2 -C 10 hydrocarbylcarbonyloxy group which may contain a heteroatom, or C 2 -C 10 hydrocarbyloxycarbonyloxy group which may contain a heteroatom,
b is an integer of 1 to 5, c is an integer of 0 to 4, and b+c is 1 to 5.
9. The chemically amplified resist composition of claim 6 wherein the base polymer comprises repeat units adapted to generate an acid upon light exposure, having any one of the formulae (d1) to (d4):
wherein R A is each independently hydrogen or methyl,
R f1 , R f2 and R f3 are each independently hydrogen or trifluoromethyl,
Z A and Z B are each independently a single bond or a C 1 -C 20 hydrocarbylene group which may contain a heteroatom,
Z C is a single bond, —Z C1 —, —O—Z C1 —, or —C(—O)—O—Z C1 —, Z C1 is a phenylene group which may be substituted with a substituent selected from a hydroxy group, fluorine, iodine, trifluoromethyl group, C 1 -C 10 hydrocarbyl group which may contain a heteroatom, C 1 -C 10 hydrocarbyloxy group which may contain a heteroatom, C 2 -C 10 hydrocarbylcarbonyl group which may contain a heteroatom, and C 2 -C 10 hydrocarbylcarbonyloxy group which may contain a heteroatom,
Z D is a single bond, phenylene group, —O—Z D1 —, —C(═O)—O—Z D1 — or —C(═O)—NH—Z D1 —, Z D1 is a hydrocarbylene group which may contain a heteroatom,
R 31 to R 41 are each independently a C 1 -C 30 hydrocarbyl group which may contain a heteroatom, a pair of R 31 and R 32 , R 34 and R 35 , R 37 and R 38 , or R 40 and R 41 may bond together to form a ring with the sulfur atom to which they are attached,
k 1 is 0 or 1, k 1 is 0 when Z A is a single bond, k 2 is 0 or 1, k 2 is 0 when Z B is a single bond, and
Xa − is a non-nucleophilic counter ion.
10. A pattern forming process comprising the steps of applying the chemically amplified resist composition of claim 1 to form a resist film on a substrate, exposing the resist film to KrF or ArF excimer laser radiation, and developing the exposed resist film in a developer.
11. A pattern forming process comprising the steps of applying the chemically amplified resist composition of claim 1 to form a resist film on a substrate, exposing the resist film to EB or EUV, and developing the exposed resist film in a developer.
12. The process of claim 10 wherein the developing step uses an alkaline aqueous solution as the developer to form a positive pattern in which an exposed region of the resist film is dissolved away and an unexposed region of the resist film is not dissolved.
13. The process of claim 10 wherein the developing step uses an organic solvent as the developer to form a negative pattern in which an unexposed region of the resist film is dissolved away and an exposed region of the resist film is not dissolved.
14. The onium salt of claim 1 wherein R 1 is a C 1 -C 5 straight or branched hydrocarbyl group which may contain fluorine, and R 1 is exclusive of a tertiary hydrocarbyl group.
15. The onium salt of claim 1 wherein R 1 is a C 1 -C 3 straight or branched hydrocarbyl group which may contain fluorine or oxygen.