Photoacid-generating compound, polymer derived therefrom, photoresist composition including the photoacid-generating compound or polymer, and method of forming a photoresist relief image
View Patent ↗A photoacid-generating compound has the structure where R 1 , R 2 , R 3 , R 4 , Q, and X are defined herein. The photoacid-generating compound can be used as a component of a photoresist composition, or as a monomer incorporated into a polymer useful in a photoresist composition. The photoacid-generating compound provides a desired balance of solubility and line width roughness.
1. A photoacid-generating compound having the structure
wherein
R 1 is a C 6-20 polycyclic hydrocarbyl group comprising a hydroxyl group, a lactone group, or a combination thereof;
R 2 is a C 6-20 polycyclic hydrocarbyl group comprising a hydroxyl group, a lactone group, or a combination thereof, or
—[(CH 2 ) n —Y—SO 3 − Z + ],
wherein n is 0, 1, or 2; Y is a C 1-4 alkylene group comprising at least one fluorine atom, provided that when n is 0, Y is a C 2-4 alkylene group comprising at least one fluorine atom; and Z + is an organic cation;
R 3 and R 4 are each independently hydrogen, cyano, C 1-6 alkyl, C 1-6 fluoroalkyl, optionally substituted C 6-12 aryl, or —C(O)O—R 11 wherein R 11 is a C 1-20 alkyl group optionally comprising one or more heteroatoms; and
Q is
wherein
R 5 and R 6 are each independently hydrogen, fluorine, cyano, trifluoromethyl, C 1-6 alkyl, C 6-20 hydrocarbyl comprising a lactone group, or —OR 12 wherein R 12 is C 1-20 alkyl, or C 6-20 hydrocarbyl comprising a lactone group; and
R 7 , R 8 , R 9 , and R 10 are each independently hydrogen; hydroxyl: —OR 13 wherein R 13 is a C 1-20 hydrocarbyl group optionally comprising one or more heteroatoms; —SR 13 wherein R 13 is defined above; —OC(O)R 13 wherein R 13 is defined above; —N(R 14 )C(O)R 13 wherein R 13 is defined above and R 14 is hydrogen or a C 1-20 hydrocarbyl group optionally comprising one or more heteroatoms; —[OC(O)—C(R a )═CH 2 ] wherein R a is hydrogen or fluoro or cyano or C 1-10 alkyl or C 1-10 fluoroalkyl; —[S—(CH 2 ) n —Y—SO 3 − Z + ] wherein n, Y, and Z + are defined above, —[S—(CH 2 ) n —Y—SO 3 − Z + ] wherein n, Y, and Z + are defined above, or —[O—C(O)—(CH 2 ) n —Y—SO 3 − Z + ] wherein n, Y, and Z + are defined above; and
X is —CH 2 —, —O—, —C(O)—, —S(O)—, or —S(O) 2 —;
provided that the photoacid-generating compound comprises
exactly one occurrence of —[(CH 2 ) n —Y—SO 3 − Z + ],
1 or 2 occurrences of the C 6-20 polycyclic hydrocarbyl group comprising a hydroxyl group, a lactone group, or a combination thereof, and
1, 2, or 3 total occurrences of hydroxyl groups and lactone groups; and
provided that when Q is
and R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are hydrogen, and R 2 is —[(CH 2 ) n —Y—SO 3 − Z + ], then
R 1 excludes —C(O)O— groups and —S(O) 2 — groups.
2. The photoacid-generating compound of claim 1 , wherein Q is
wherein R 5 and R 6 are hydrogen; and R 2 is
—[(CH 2 ) n —Y—SO 3 − Z + ],
wherein n is 0, 1, or 2; Y is a C 1-4 alkylene group comprising at least one fluorine atom, provided that when n is 0, Y is a C 2-4 alkylene group comprising at least one fluorine atom; and Z + is an organic cation.
3. The photoacid-generating compound of claim 1 , wherein Q is
wherein one of R 7 and R 8 is hydroxyl and the other of R 7 and R 8 is hydrogen; wherein one of R 9 and R 10 is [O—(CH 2 ) n —Y—SO 3 − Z + ], —[OC(O)—(CH 2 ) n —Y—SO 3 − Z + ], or —[S—(CH 2 ) n —Y—SO 3 − Z + ], and the other of R 9 and R 10 is hydrogen; and R 2 is a C 8-12 polycyclic hydrocarbyl group comprising a hydroxyl group, a lactone group, or a combination thereof.
4. The photoacid-generating compound of claim 1 , wherein Q is
wherein R 7 and R 9 are hydrogen; wherein one of R 8 and R 10 is [O—(CH 2 ) n —Y—SO 3 − Z + ] or —[S—(CH 2 ) n —Y—SO 3 − Z + ] or —[O—C(O)—(CH 2 ) n —Y—SO 3 − Z + ] wherein n is 0, 1, or 2, Y is a C 1-4 alkylene group comprising at least one fluorine atom, and Z + is an organic cation, and the other of R 8 and R 10 is hydrogen; and R 2 is a C 8-12 polycyclic hydrocarbyl group comprising a hydroxyl group, a lactone group, or a combination thereof.
5. The photoacid-generating compound of claim 1 , wherein Q is
and
R 2 is
—[(CH 2 ) n —Y—SO 3 − Z + ],
wherein n is 0, 1, or 2; Y is a C 1-4 alkylene group comprising at least one fluorine atom, provided that when n is 0, Y is a C 2-4 alkylene group comprising at least one fluorine atom; and Z + is an organic cation.
6. The photoacid-generating compound of claim 1 , selected from the group consisting of
wherein Z + is an organic cation.
7. The photoacid-generating compound of claim 1 , wherein Q is
wherein one of R 7 and R 9 is hydrogen or hydroxyl and the other of R 7 and R 9 is hydrogen; wherein one of R 8 and R 10 is —[OC(O)C(R a )═CH 2 ] wherein R a is hydrogen, fluoro, cyano, C 1-10 alkyl, or C 1-10 fluoroalkyl, and the other of R 8 and R 10 is hydrogen; and wherein R 2 is
—[(CH 2 ) n —Y—SO 3 − Z + ],
wherein n is 0, 1, or 2; Y is a C 1-4 alkylene group comprising at least one fluorine atom, provided that when n is 0, Y is a C 2-4 alkylene group comprising at least one fluorine atom; and Z + is an organic cation.
8. A polymer comprising repeat units derived from the photoacid-generating compound of claim 7 .
9. A photoresist composition comprising the photoacid-generating compound of claim 1 .
10. A method of forming a photoresist relief image, comprising:
(a) applying a layer of the photoresist composition of claim 9 on a substrate to form a photoresist layer;
(b) pattern-wise exposing the photoresist layer to activating radiation to form an exposed photoresist layer; and
(c) developing the exposed photoresist layer to provide a photoresist relief image.
11. A photoresist composition comprising the polymer of claim 8 .