Polymer, photoresist compositions including the same, and pattern formation methods
A polymer, including a first repeating unit comprising a sulfone group, wherein the sulfone group is directly bonded to a group of formula —C(R a )(R b )—; and a second repeating unit comprising an acid labile group, a base-decomposable group, a polar group, or a combination thereof, wherein R a and R b are each independently hydrogen, halogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 3-30 cycloalkenyl, substituted or unsubstituted C 3-30 heterocycloalkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 heteroarylalkyl, or substituted or unsubstituted C 3-30 alkylheteroaryl, provided that at least one of R a and R b is hydrogen.
1 . A polymer, comprising:
a first repeating unit comprising a sulfone group, wherein the sulfone group is directly bonded to a group of formula —C(R a )(R b )—; and
a second repeating unit comprising an acid labile group chosen from tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, ketal groups, tertiary carbonate groups, and tertiary carbamate groups, a base-decomposable group, a hydroxy aryl, or a combination thereof,
wherein R a and R b are each independently hydrogen, halogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 3-30 cycloalkenyl, substituted or unsubstituted C 3-30 heterocycloalkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 heteroarylalkyl, or substituted or unsubstituted C 3-30 alkylheteroaryl,
provided that at least one of R a and R b is hydrogen,
wherein the first repeating unit is derived from a first monomer represented by Formula (1):
wherein, in Formula (1),
X a is a polymerizable group comprising an ethylenically unsaturated carbon-carbon double bond;
L 1 is a single bond or a linking group;
each L 2 is independently a single bond, substituted or unsubstituted C 1-30 alkyl, or substituted or unsubstituted C 3-30 cycloalkyl; wherein at least one of L 1 or L 2 is not a single bond,
each R 1 is independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 3-30 cycloalkenyl, substituted or unsubstituted C 3-30 heterocycloalkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 heteroarylalkyl, or substituted or unsubstituted C 3-30 alkylheteroaryl;
provided that at least one L 2 or at least one R 1 comprises the group of formula —C(R a )(R b )— that is directly bonded to —S(═O) 2 —; and
n is an integer from 1 to 5.
2 . The polymer of claim 1 , wherein the at least one L 2 comprises the group of formula —C(R a )(R b )— that is directly bonded to —S(═O) 2 —.
3 . The polymer of claim 1 , wherein the at least one R 1 comprises the group of formula —C(R a )(R b )— that is directly bonded to —S(═O) 2 —.
4 . The polymer of claim 1 , wherein the first repeating unit is derived from a first monomer represented by Formulae (2) or (3):
wherein, in Formulae (2) and (3),
X b and X c are each independently a polymerizable group comprising an ethylenically unsaturated carbon-carbon double bond;
L 3 and L 4 are each independently a single bond or a divalent linking group;
R 2 , R 3 , and R 4 are each independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 3-30 cycloalkenyl, substituted or unsubstituted C 3-30 heterocycloalkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 heteroarylalkyl, or substituted or unsubstituted C 3-30 alkylheteroaryl.
5 . The polymer of claim 1 , wherein the first monomer comprises a (meth)acryloyl group or a vinyl aromatic group.
6 . The polymer of claim 1 , wherein the second repeating unit comprises the acid labile group.
7 . A photoresist composition, comprising:
a first polymer, comprising:
a first repeating unit comprising a sulfone group, wherein the sulfone group is directly bonded to a group of formula —C(R a )(R b )—;
wherein R a and R b are each independently hydrogen, halogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 3-30 cycloalkenyl, substituted or unsubstituted C 3-30 heterocycloalkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 heteroarylalkyl, or substituted or unsubstituted C 3-30 alkylheteroaryl;
provided that at least one of R a and R b is hydrogen; and
a solvent,
wherein the first repeating unit is derived from a first monomer represented by Formula (1):
wherein, in Formula (1),
X a is a polymerizable group comprising an ethylenically unsaturated carbon-carbon double bond;
L 1 is a single bond or a linking group;
each L 2 is independently a single bond, substituted or unsubstituted C 1-30 alkyl, or substituted or unsubstituted C 3-30 cycloalkyl; wherein at least one of L 1 or L 2 is not a single bond,
each R 1 is independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 3-30 cycloalkenyl, substituted or unsubstituted C 3-30 heterocycloalkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 heteroarylalkyl, or substituted or unsubstituted C 3-30 alkylheteroaryl;
provided that at least one L 2 or at least one R 1 comprises the group of formula —C(R a )(R b )— that is directly bonded to —S(═O) 2 —; and
n is an integer from 1 to 5.
8 . The photoresist composition of claim 7 , wherein the polymer further comprises a second repeating unit, and wherein the second repeating unit comprises an acid labile group, a base-decomposable group, a polar group, or a combination thereof.
9 . The photoresist composition of claim 8 , wherein the second repeating unit comprises the acid labile group.
10 . The photoresist composition of claim 7 , further comprising a photoacid generator.
11 . The photoresist composition of claim 7 , further comprising a second polymer that is structurally different than the first polymer.
12 . The photoresist composition of claim 11 , wherein one or both of the first polymer and the second polymer comprise a repeating unit comprising an acid labile group, a base-decomposable group, a polar group, or a combination thereof.
13 . A method of forming a pattern, the method comprising:
applying a layer of a photoresist composition of claim 7 on a substrate to form a photoresist composition layer;
pattern-wise exposing the photoresist composition layer with activating radiation to form an exposed photoresist composition layer; and
developing the exposed photoresist composition layer.
14 . The photoresist composition of claim 7 , wherein the at least one L 2 comprises the group of formula —C(R a )(R b )— that is directly bonded to —S(═O) 2 —.
15 . The photoresist composition of claim 7 , wherein the at least one R 1 comprises the group of formula —C(R a )(R b )— that is directly bonded to —S(═O) 2 —.
16 . The photoresist composition of claim 7 , wherein the first repeating unit is derived from a first monomer represented by Formulae (2) or (3):
wherein, in Formulae (2) and (3),
X b and X c are each independently a polymerizable group comprising an ethylenically unsaturated carbon-carbon double bond;
L 3 and L 4 are each independently a single bond or a divalent linking group;
R 2 , R 3 , and R 4 are each independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 3-30 cycloalkenyl, substituted or unsubstituted C 3-30 heterocycloalkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 heteroarylalkyl, or substituted or unsubstituted C 3-30 alkylheteroaryl.