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

Patent metadata

Field	Value
Publication number	US-11613519-B2
Application number	US-201615131135-A
Country	US
Kind code	B2
Filing date	Apr 18, 2016
Priority date	Feb 29, 2016
Publication date	Mar 28, 2023
Grant date	Mar 28, 2023

Abstract

A monomer has the structurewherein R is an organic group comprising a polymerizable carbon-carbon double bond or carbon-carbon triple bond; X and Y are independently at each occurrence hydrogen or a non-hydrogen substituent; EWG1 and EWG2 are independently at each occurrence an electron-withdrawing group; p is 0, 1, 2, 3, or 4; n is 1, 2, 3, or 4; and M+ is an organic cation. A polymer prepared from monomer is useful as a component of a photoresist composition.

First claim

The invention claimed is:

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 monovalen

Assignees

• Rohm & Haas Elect Mat

Inventors

• Aqad Emad
• Thackeray James W
• Cameron James F

Classifications

• G03F7/004

  Photosensitive materials (G03F7/12, G03F7/14 take precedence) · CPC title

• C07D317/72

  spiro-condensed with carbocyclic rings · CPC title

• C07C309/17

  containing carboxyl groups bound to the carbon skeleton · CPC title

• C07C309/12 Primary

  containing esterified hydroxy groups bound to the carbon skeleton · CPC title

• C07D409/12

  linked by a chain containing hetero atoms as chain links · CPC title