Photoacid-generating monomer, polymer derived therefrom, photoresist composition including the polymer, and method of forming a photoresist relief image using the photoresist composition

1. A monomer having the structure

wherein

R is an organic group consisting of (A) a polymerizable carbon-carbon double bond or carbon-carbon triple bond group selected from the group consisting of C 2-12 alkenyl, C 2-12 alkynyl, acryloyl, 2-(C 1-12 -alkyl)acryloyl, 2-(C 1-12 -fluoroalkyl)acryloyl, 2-cyanoacryloyl, and 2-fluoroacryloyl, and (B) one or more divalent groups selected from a straight chain or branched non-fluorinated C 1-20 alkylene group, a monocyclic or polycyclic non-fluorinated C 3-20 cycloalkylene group, a monocyclic or polycyclic C 3-20 heterocycloalkylene group, a monocyclic or polycyclic C 6-20 arylene group, a monocyclic or polycyclic C 1-20 heteroarylene group, and a combination thereof;

wherein the C 1-20 alkylene group, C 3-20 cycloalkylene group, the monocyclic or polycyclic C 3-20 heterocycloalkylene group, the monocyclic or polycyclic C 6-20 arylene group, and the monocyclic or polycyclic C 1-20 heteroarylene group are optionally substituted with at least one monovalent substituent selected from chlorine, bromine, iodine, hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, nitro, C 1-18 alkyl, C 1-18 alkoxyl, C 6-18 aryl, C 6-18 aryloxyl, C 7-18 alkylaryl, or C 7-18 alkylaryloxyl;

X and Y are independently at each occurrence hydrogen or a non-fluorinated non-hydrogen substituent;

EWG1 and EWG2 are independently at each occurrence an electron-withdrawing group;

p is 1, 2, 3, or 4;

n is 2, 3, or 4; and

M + is an organic cation.

2. The monomer of claim 1 , wherein EWG1 and EWG2 are independently at each occurrence F, partially fluorinated alkyl or perfluorinated alkyl.

3. The monomer of claim 2 , wherein EWG1 and EWG2 are at each occurrence F.

4. The monomer of claim 1 , wherein EWG1 and EWG2 are independently at each occurrence F, CF 3 , —CN, —NO 2 , —C(═O)R 11 , —C(═O)OR 11 , and —SO 2 R 11 , wherein R 11 is a C 1-30 aliphatic organic group, a C 6-30 aromatic organic group, or a C 1-30 heteroaromatic organic group.

5. The monomer of claim 1 , wherein R is selected from the group consisting of

wherein R 1 is hydrogen, fluoro, cyano, C 1-10 alkyl, or C 1-10 fluoroalkyl.

6. A monomer having the structure

wherein

R is an organic group consisting of (A) a polymerizable carbon-carbon double bond or carbon-carbon triple bond group selected from the group consisting of C 2-12 alkenyl, C 2-12 alkynyl, acryloyl, 2-(C 1-12 -alkyl)acryloyl, 2-(C 1-12 -fluoroalkyl)acryloyl, 2-cyanoacryloyl, and 2-fluoroacryloyl, and (B) one or more divalent groups selected from a straight chain or branched non-fluorinated C 1-20 alkylene group, a monocyclic or polycyclic non-fluorinated C 3-20 cycloalkylene group, a monocyclic or polycyclic C 3-20 heterocycloalkylene group, a monocyclic or polycyclic C 6-20 arylene group, a monocyclic or polycyclic C 1-20 heteroarylene group, and a combination thereof;

wherein the C 1-20 alkylene group, the C 3-20 cycloalkylene group, the monocyclic or polycyclic C 3-20 heterocycloalkylene group, the monocyclic or polycyclic C 6-20 arylene group, and the monocyclic or polycyclic C 1-20 heteroarylene group are optionally substituted with at least one monovalent substituent selected from chlorine, bromine, iodine, hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, nitro, C 1-18 alkyl, C 1-18 alkoxyl, C 6-18 aryl, C 6-18 aryloxyl, C 7-18 alkylaryl, or C 7-18 alkylaryloxyl;

X and Y are independently at each occurrence hydrogen or a non-fluorinated non-hydrogen substituent;

EWG1 and EWG2 are independently at each occurrence an electron-withdrawing group;

p is 1, 2, 3, or 4;

n is 1, 2, 3, or 4,

provided that the sum of n and p is at least 3; and

M + is an organic cation.

7. A monomer having the structure

wherein

R is an organic group consisting of (A) a polymerizable carbon-carbon double bond or carbon-carbon triple bond group selected from the group consisting of C 2-12 alkenyl, C 2-12 alkynyl, acryloyl, 2-(C 1-12 -alkyl)acryloyl, 2-(C 1-12 -fluoroalkyl)acryloyl, 2-cyanoacryloyl, and 2-fluoroacryloyl, and (B) one or more divalent groups selected from a straight chain or branched non-fluorinated C 1-20 alkylene group, a monocyclic or polycyclic non-fluorinated C 3-20 cycloalkylene group, a monocyclic or polycyclic C 3-20 heterocycloalkylene group, a monocyclic or polycyclic C 6-20 arylene group, a monocyclic or polycyclic C 1-20 heteroarylene group, and any combination thereof;

wherein the C 1-20 alkylene group, the C 3-20 cycloalkylene group, the monocyclic or polycyclic C 3-20 heterocycloalkylene group, the monocyclic or polycyclic C 6-20 arylene group, and the monocyclic or polycyclic C 1-20 heteroarylene group are optionally substituted with at least one monovalent substituent selected from chlorine, bromine, iodine, hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, nitro, C 1-18 alkyl, C 1-18 alkoxyl, C 6-18 aryl, C 6-18 aryloxyl, C 7-18 alkylaryl, or C 7-18 alkylaryloxyl;

EWG1 and EWG2 are independently at each occurrence an electron-withdrawing group;

n is 1, 2, 3, or 4;

p is 1, 2, 3, or 4;

X and Y are hydrogen; and

M + is an organic cation.

8. The monomer of claim 1 , selected from the group consisting of

wherein M + is defined as in claim 1 .

9. The monomer of claim 1 , selected from the group consisting of

wherein M + is defined as in claim 1 .

10. The monomer of claim 1 , selected from the group consisting of:

wherein R, X, Y, M, n, and p are as defined in claim 1 .

11. The monomer of claim 6 , selected from the group consisting of:

wherein R, X, Y, M, n, and p are as defined in claim 6 .

12. The monomer of claim 7 , selected from the group consisting of:

wherein R, X, Y, M, n, and p are as defined in claim 7 .

13. The monomer of claim 1 , wherein the C 1-20 alkylene group, C 3-20 cycloalkylene group, the monocyclic or polycyclic C 3-20 heterocycloalkylene group, the monocyclic or polycyclic C 6-20 arylene group, and the monocyclic or polycyclic C 1-20 heteroarylene group are optionally substituted with at least one monovalent substituent selected from hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, nitro, C 1-18 alkyl, C 1-18 alkoxyl, C 6-18 aryl, C 6-18 aryloxyl, C 7-18 alkylaryl, or C 7-18 alkylaryloxyl.

14. The monomer of claim 6 , wherein the C 1-20 alkylene group, C 3-20 cycloalkylene group, the monocyclic or polycyclic C 3-20 heterocycloalkylene group, the monocyclic or polycyclic C 6-20 arylene group, and the monocyclic or polycyclic C 1-20 heteroarylene group are optionally substituted with at least one monovalent substituent selected from hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, nitro, C 1-18 alkyl, C 1-18 alkoxyl, C 6-18 aryl, C 6-18 aryloxyl, C 7-18 alkylaryl, or C 7-18 alkylaryloxyl.

15. The monomer of claim 7 , wherein the C 1-20 alkylene group, C 3-20 cycloalkylene group, the monocyclic or polycyclic C 3-20 heterocycloalkylene group, the monocyclic or polycyclic C 6-20 arylene group, and the monocyclic or polycyclic C 1-20 heteroarylene group are optionally substituted with at least one monovalent substituent selected from hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, nitro, C 1-18 alkyl, C 1-18 alkoxyl, C 6-18 aryl, C 6-18 aryloxyl, C 7-18 alkylaryl, or C 7-18 alkylaryloxyl.