Polymerizable photoacid generators
View Patent ↗A compound has formula (I): Q-O-(A)-Z − G + (I) wherein Q is a halogenated or non-halogenated, C 2-30 olefin-containing group, A is a fluorine-substituted C 1-30 alkylene group, a fluorine-substituted C 3-30 cycloalkylene group, a fluorine-substituted C 6-30 arylene group, or a fluorine-substituted C 7-30 alkylene-arylene group, Z is an anionic group comprising sulfonate, sulfonamide, or sulfonimide, and G + has formula (II): wherein X is S or I, each R 0 is halogenated or non-halogenated and is independently C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; a polycyclic or monocyclic C 4-30 aryl group; or a combination of these, wherein when X is S, one of the R 0 groups is optionally attached to one adjacent R 0 group by a single bond, and a is 2 or 3, wherein when X is I, a is 2, or when X is S, a is 3. A copolymer, a photoresist, a coated substrate and method of patterning are disclosed.
1. A copolymer comprising:
a first polymerized unit formed from a compound having the formula
or a combination comprising at least one of the foregoing, where each R 1 is independently H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl, and G + has formula (VI):
wherein R 6 , R 7 , and R 8 are each independently hydroxy, nitrile, halogen, C 1-10 alkyl, C 1-10 fluoroalkyl, C 1-10 alkoxy, C 1-10 fluoroalkoxy, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, or C 6-20 fluoroaryloxy, r is an integer from 0 to 5, and s and t are each independently an integer from 0 to 4;
a second polymerized unit comprising an acid sensitive functional group; and
a third polymerized unit comprising a polar group, wherein the third polymerized unit is formed from a polar monomer chosen from
or a combination comprising at least one of the foregoing, wherein R 10 is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl.
2. The copolymer of claim 1 , wherein the second polymerized unit is formed from an acid sensitive monomer comprising:
or a combination comprising at least one of the foregoing, wherein R 9 is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl.
3. A photoresist composition comprising the copolymer of claim 1 .
4. A coated substrate, comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a photoresist composition of claim 3 over the one or more layers to be patterned.
5. A method of forming an electronic device, comprising: (a) applying a layer of a photoresist composition of claim 3 on a substrate; (b) patternwise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image.
6. The method of claim 5 , wherein the radiation is extreme-ultraviolet or e-beam radiation.
7. The copolymer of claim 1 , wherein the second polymerized unit is formed from an acid sensitive monomer comprising
wherein R 9 is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl.
8. A copolymer comprising
a first polymerized unit formed from a compound having the formula
or a combination comprising at least one of the foregoing, where each R 1 is independently H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl, and G + has formula (VI)
wherein R 6 , R 7 , and R 8 are each independently hydroxy, nitrile, halogen, C 1-10 alkyl, C 1-10 fluoroalkyl, C 1-10 alkoxy, C 1-10 fluoroalkoxy, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, or C 6-20 fluoroaryloxy, r is an integer from 0 to 5, and s and t are each independently an integer from 0 to 4;
a second polymerized unit comprising an acid sensitive functional group; wherein the second polymerized unit is formed from an acid sensitive monomer comprising
or a combination comprising at least one of the foregoing, wherein R 9 is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl; and
a third polymerized unit comprising a polar group, wherein the third polymerized unit is formed from the following monomer:
wherein R 10 is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl.
9. A photoresist composition comprising the copolymer of claim 8 .
10. A method of forming an electronic device, comprising: (a) applying a layer of a photoresist composition of claim 9 on a substrate; (b) patternwise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image.