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-11947258-B2
Application number	US-202318174316-A
Country	US
Kind code	B2
Filing date	Feb 24, 2023
Priority date	Feb 29, 2016
Publication date	Apr 2, 2024
Grant date	Apr 2, 2024

Abstract

A monomer has the structure

wherein 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 polymer comprising repeat units derived from a monomer having a 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 polymer 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.

3. The polymer 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.

4. The polymer of claim 1 , wherein the monomer is selected from the group consisting of

wherein M ± is defined as in claim 1 .

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

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

6. The polymer of claim 1 , wherein the (B) one or more divalent groups is substituted with iodine.

7. The polymer of claim 1 , wherein M + is
an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl groups and aryl groups, wherein each of the alkyl group and the aryl group is independently substituted or unsubstituted; or
a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl groups and aryl groups, wherein each of the alkyl group and the aryl group is independently substituted or unsubstituted.

8. The polymer of claim 1 , wherein M + has a structure:

wherein,
R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a halogen, —CN, —OH, a C 1-10 alkyl group, a C 1-10 fluoroalkyl group, a C 1-10 alkoxy group, a C 1-10 fluoroalkoxy group, a C 3-10 cycloalkyl group, a C 3-10 fluorocycloalkyl group, a C 3-10 cycloalkoxy group, or a C 3-10 fluorocycloalkoxy group, each of which except a halogen, —CN, and —OH is substituted or unsubstituted;
J is a single bond or a connecting group selected from S, O, and C═O;
each occurrence of p is independently an integer of 0, 1, 2, 3, or 4;
r is 0, 1, 2, 3, 4, or 5; and
s and t are each independently 0, 1, 2, 3, or 4,
wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently optionally comprises an acid cleavable group.

9. A photoresist composition, comprising the polymer of claim 1 .

10. The photoresist composition of claim 9 , 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.

11. The photoresist composition of claim 9 , 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.

12. The photoresist composition of claim 9 , wherein the monomer is selected from the group consisting of:

wherein M + is defined as in claim 1 .

13. The photoresist composition of claim 9 , wherein the monomer is selected from the group consisting of:

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

14. The photoresist composition of claim 9 , wherein the (B) one or more divalent groups is substituted with iodine.

15. The photoresist composition of claim 9 , wherein M + is
an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl groups and aryl groups, wherein each of the alkyl group and the aryl group is independently substituted or unsubstituted; or
a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl groups and aryl groups, wherein each of the alkyl group and the aryl group is independently substituted or unsubstituted.

16. The photoresist composition of claim 9 , wherein M + has a structure:

wherein,
R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a halogen, —CN, —OH, a C 1-10 alkyl group, a C 1-10 fluoroalkyl group, a C 1-10 alkoxy group, a C 1-10 fluoroalkoxy group, a C 3-10 cycloalkyl group, a C 3-10 fluorocycloalkyl group, a C 3-10 cycloalkoxy group, or a C 3-10 fluorocycloalkoxy group, each of which except a halogen, —CN, and —OH is substituted or unsubstituted;
J is a single bond or a connecting group selected from S, O, and C═O;
each occurrence of p is independently an integer of 0, 1, 2, 3, or 4;
r is 0, 1, 2, 3, 4, or 5; and
s and t are each independently 0, 1, 2, 3, or 4, wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently optionally comprises an acid cleavable group.

17. A method of forming a photoresist relief image, the method comprising:
(a) applying a layer of a 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.

18. The method of claim 17 , wherein in the polymer, 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

Assignees

• Rohm & Haas Elect Mat
• Rohm And Hass Electronic Mat Llc

Inventors

• Aqad Emad
• Thackeray James W
• Cameron James F

Classifications

• G03F7/0045 Primary

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• C07C303/32

  of salts of sulfonic acids · CPC title

• C07C309/06

  containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton · CPC title

• C07C309/07

  containing oxygen atoms bound to the carbon skeleton · CPC title

• C07C309/12 Primary

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