PHOTORESIST COMPOSITIONS AND PATTERN FORMATION METHODS
A photoresist composition comprises a first polymer comprising a first repeating unit comprising a hydroxy-aryl group and a second repeating unit comprising an acid-labile group, wherein the first polymer does not comprise a lactone group; a second polymer comprising a first repeating unit comprising a hydroxy-aryl group, a second repeating unit comprising an acid-labile group, and a third repeating unit comprising a lactone group; a photoacid generator; and a solvent.
1 . A photoresist composition comprising:
a first polymer comprising a first repeating unit comprising a hydroxy-aryl group and a second repeating unit comprising an acid-labile group, wherein the first polymer does not comprise a lactone group;
a second polymer comprising a first repeating unit comprising a hydroxy-aryl group, a second repeating unit comprising an acid-labile group, and a third repeating unit comprising a lactone group;
a photoacid generator; and
a solvent.
2 . The photoresist composition of claim 1 , wherein the first repeating unit of the first polymer is derived from one or more monomers of formula (1):
wherein,
R a is hydrogen, halogen, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
R b is hydrogen, —C(O)— forming a ring with L 1 , or a single bond forming a ring with Ar 1 ;
L 1 is a single bond or a divalent linking group optionally comprising —N(R 2a )—, wherein R 2a is hydrogen, C 1-6 alkyl, or a single bond forming the ring with R b ;
provided that R b is —C(O)— forming the ring with L 1 when R 2 is the single bond forming the ring with R b ;
Ar 1 is a hydroxy-substituted C 6-60 aryl group, a hydroxy-substituted C 4-60 heteroaryl group, or a combination thereof, each optionally further substituted with one or more of substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 alkynyl, 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 4-60 heteroaryl, substituted or unsubstituted C 5-60 heteroarylalkyl, substituted or unsubstituted C 5-60 alkylheteroaryl, —OR 21 , or —NR 22 R 23 , wherein R 21 to R 23 are each independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, 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 4-30 heteroaryl, substituted or unsubstituted C 5-30 heteroarylalkyl, or substituted or unsubstituted C 5-30 alkylheteroaryl.
3 . The photoresist composition of claim 1 , wherein the second repeating unit of the first polymer and the second repeating unit of the second polymer are each independently derived from one or more monomers of formula (2a), (2b), (2c), (2d), or (2e):
wherein,
R c , R d , and R e are each independently hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
R 1 to R 6 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 cycloalkenyl, substituted or unsubstituted C 3-20 heterocycloalkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl; provided that only one of R 1 to R 3 can be hydrogen and only one of R 4 to R 6 can be hydrogen, and provided that when one of R 1 to R 3 is hydrogen, one or both of the others of R 1 to R 3 are substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 4-20 heteroaryl, and when one of R 4 to R 6 is hydrogen, one or both of the others of R 4 to R 6 are substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 4-20 heteroaryl;
any two of R 1 to R 3 together optionally form a ring, and each of R 1 to R 3 optionally comprises as part of their structure one or more groups chosen from —O—, —C(O)—, —N(R 42 )—, —S—, or —S(O) 2 —, wherein R 42 may be hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 1-20 heterocycloalkyl;
any two of R 4 to R 6 together optionally form a ring, and each of R 4 to R 6 optionally comprises as part of their structure one or more groups chosen from —O—, —C(O)—, —N(R 43 )—, —S—, or —S(O) 2 —, wherein R 43 is hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 1-20 heterocycloalkyl;
L 2 is a divalent linking group;
R 7 to R 8 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl;
R 7 to R 8 may be each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl;
R 9 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 1-30 heterocycloalkyl;
optionally, one of R 7 or R 8 together with R 9 forms a heterocyclic ring;
R 10 to R 12 may be each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl, any two of R 10 to R 12 together optionally form a ring, and each of R 10 to R 12 optionally comprise as part of their structure one or more groups chosen from —O—, —C(O)—, —N(R 44 )—, —S—, or —S(O) 2 —, wherein R 44 may be hydrogen, a straight chain or branched C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or monocyclic or polycyclic C 1-20 heterocycloalkyl; provided that only one of R 10 to R 12 can be hydrogen when the acid-labile group is not an acetal group, provided that when one of R 10 to R 12 is hydrogen, one or both of the others of R 10 to R 12 are substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 4-20 heteroaryl;
X a is a polymerizable group selected from norbornyl or vinyl;
n is 0 or 1; and
L 3 is a single bond or a divalent linking group, provided that L 3 is not a single bond when X a is vinyl.
4 . The photoresist composition of claim 1 , wherein the third repeating unit of the second polymer is derived from one or more monomers of formula (4):
wherein,
R f is hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
L 4 is a single bond or a divalent linking group;
R 14 is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group or a monocyclic, polycyclic, or fused polycyclic C 4-20 sultone-containing group.
5 . The photoresist composition of any one of claim 1 , wherein the photoacid generator is non-polymeric.
6 . The photoresist composition of claim 1 , wherein the photoacid generator comprises a sulfonate group on the anion, and
the photoresist composition further comprises a second photoacid generator that is non-polymeric, wherein the second photoacid generator comprises an anion that is free of sulfonate groups.
7 . The photoresist composition of claim 1 , further comprising a photo-decomposable quencher.
8 . The photoresist composition of claim 1 , further comprising a base-labile material comprising one or more base-labile groups, wherein the base-labile material is different from the first polymer and the second polymer.
9 . The photoresist composition of claim 1 , wherein a weight ratio of the first polymer to the second polymer is from 1:4 to 4:1.
10 . A pattern formation method, comprising:
(a) applying a layer of a photoresist composition on a substrate;
(b) pattern-wise exposing the photoresist composition layer to activating radiation; and
(c) developing the exposed photoresist composition layer to provide a resist relief image,
wherein the photoresist composition comprises:
a first polymer comprising a first repeating unit comprising a hydroxy-aryl group and a second repeating unit comprising an acid-labile group, wherein the first polymer does not comprise a lactone group;
a second polymer comprising a first repeating unit comprising a hydroxy-aryl group, a second repeating unit comprising an acid-labile group, and a third repeating unit comprising a lactone group;
a photoacid generator; and
a solvent.
11 . The method of claim 10 , wherein the first repeating unit of the first polymer is derived from one or more monomers of formula (1):
wherein,
R a is hydrogen, halogen, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
R b is hydrogen, —C(O)— forming a ring with L 1 , or a single bond forming a ring with Ar 1 ;
L 1 is a single bond or a divalent linking group optionally comprising —N(R 2a )—, wherein R 2a is hydrogen, C 1-6 alkyl, or a single bond forming the ring with R b ;
provided that R b is —C(O)— forming the ring with L 1 when R 2 is the single bond forming the ring with R b ;
Ar 1 is a hydroxy-substituted C 6-60 aryl group, a hydroxy-substituted C 4-60 heteroaryl group, or a combination thereof, each optionally further substituted with one or more of substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 heterocycloalkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 alkynyl, 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 4-60 heteroaryl, substituted or unsubstituted C 5-60 heteroarylalkyl, substituted or unsubstituted C 5-60 alkylheteroaryl, —OR 21 , or —NR 22 R 23 , wherein R 21 to R 23 are each independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, 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 4-30 heteroaryl, substituted or unsubstituted C 5-30 heteroarylalkyl, or substituted or unsubstituted C 5-30 alkylheteroaryl.
12 . The method of claim 10 , wherein the second repeating unit of the first polymer and the second repeating unit of the second polymer are each independently derived from one or more monomers of formula (2a), (2b), (2c), (2d), or (2e):
wherein,
R c , R d , and R e are each independently hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
R 1 to R 6 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 cycloalkenyl, substituted or unsubstituted C 3-20 heterocycloalkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl; provided that only one of R 1 to R 3 can be hydrogen and only one of R 4 to R 6 can be hydrogen, and provided that when one of R 1 to R 3 is hydrogen, one or both of the others of R 1 to R 3 are substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 4-20 heteroaryl, and when one of R 4 to R 6 is hydrogen, one or both of the others of R 4 to R 6 are substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 4-20 heteroaryl;
any two of R 1 to R 3 together optionally form a ring, and each of R 1 to R 3 optionally comprises as part of their structure one or more groups chosen from —O—, —C(O)—, —N(R 42 )—, —S—, or —S(O) 2 —, wherein R 42 may be hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 1-20 heterocycloalkyl;
any two of R 4 to R 6 together optionally form a ring, and each of R 4 to R 6 optionally comprises as part of their structure one or more groups chosen from —O—, —C(O)—, —N(R 43 )—, —S—, or —S(O) 2 —, wherein R 43 is hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 1-20 heterocycloalkyl;
L 2 is a divalent linking group;
R 7 to R 8 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl;
R 7 to R 8 may be each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl;
R 9 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 1-30 heterocycloalkyl;
optionally, one of R 7 or R 8 together with R 9 forms a heterocyclic ring;
R 10 to R 12 may be each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl, any two of R 10 to R 12 together optionally form a ring, and each of R 10 to R 12 optionally comprise as part of their structure one or more groups chosen from —O—, —C(O)—, —N(R 44 )—, —S—, or —S(O) 2 —, wherein R 44 may be hydrogen, a straight chain or branched C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or monocyclic or polycyclic C 1-20 heterocycloalkyl; provided that only one of R 10 to R 12 can be hydrogen when the acid-labile group is not an acetal group, provided that when one of R 10 to R 12 is hydrogen, one or both of the others of R 10 to R 12 are substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 4-20 heteroaryl;
X a is a polymerizable group selected from norbornyl or vinyl;
n is 0 or 1; and
L 3 is a single bond or a divalent linking group, provided that L 3 is not a single bond when X a is vinyl.
13 . The method of claim 10 , wherein the third repeating unit of the second polymer is derived from one or more monomers of formula (4):
wherein,
R f is hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
L 4 is a single bond or a divalent linking group;
R 14 is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group or a monocyclic, polycyclic, or fused polycyclic C 4-20 sultone-containing group.
14 . The method of claim 10 , wherein the photoacid generator is non-polymeric.
15 . The method of claim 10 , wherein the photoacid generator comprises a sulfonate group on the anion, and
the photoresist composition further comprises a second photoacid generator that is non-polymeric, wherein the second photoacid generator comprises an anion that is free of sulfonate groups.
16 . The method of claim 10 , wherein the photoresist composition further comprises a photo-decomposable quencher.
17 . The method of claim 10 , further comprising a base-labile material comprising one or more base-labile groups, wherein the base-labile material is different from the first polymer and the second polymer.
18 . The method of claim 10 , wherein a weight ratio of the first polymer to the second polymer is from 1:4 to 4:1.