Photoresist compositions and pattern formation methods
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; a second polymer comprising a first repeating unit comprising an acid-labile group, a second repeating unit comprising a lactone group, and a third repeating unit comprising a base-soluble group, wherein the base-soluble group has a pKa of less than or equal to 12, and wherein the base-soluble group does not comprise a hydroxy-substituted aryl group; a photoacid generator; and a solvent, wherein the first polymer and the second polymer are different from each other.
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 repeating unit is present in the first polymer in an amount from 30 to 50 mol %, based on total repeating units in the first polymer;
a second polymer comprising a first repeating unit comprising an acid-labile group, a second repeating unit comprising a lactone group, and a third repeating unit comprising a base-soluble group, wherein the base-soluble group has a pKa of less than or equal to 12, and wherein the base-soluble group does not comprise a hydroxy-aryl group;
a photoacid generator; and
a solvent,
wherein the first polymer and the second polymer are different from each other,
wherein the first polymer and the second polymer are present in a weight ratio from 1:2 to 1:4, and
wherein the second repeating unit of the first polymer is derived from a monomer of formula (2a′), (2b′), (2c′), (2d′), or (2e′):
wherein, in formulae (2a′), (2b′), (2c′), (2d′), or (2e′),
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 3-20 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 4-20 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;
any two of R 1 to R 3 together optionally form a ring, and each of R 1 to R 3 optionally may include as part of their structure one or more groups selected from —O—, —C(O)—, —N(R 42 )—, —S—, or —S(O) 2 —, wherein R 42 is hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
any two of R 4 to R 6 together optionally form a ring, and each of R 4 to R 6 optionally may include as part of their structure one or more groups selected 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 3-20 heterocycloalkyl;
L 2 is a divalent linking;
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 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 4-20 heteroaryl,
R 9 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl, wherein one of R 7 or R 8 optionally forms a heterocyclic ring together with R 9 ;
R 10 to R 12 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 4-20 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 selected from —O—, —C(O)—, —N(R 44 )—, —S—, or —S(O) 2 —, wherein R 44 is hydrogen, straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
X a is a polymerizable group selected from norbornyl or vinyl;
n is 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.
2. The photoresist composition of claim 1 , wherein the first repeating unit of the first polymer is of formula (1a):
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 comprising one or more of substituted or unsubstituted C 1-30 alkylene, substituted or unsubstituted C 3-30 cycloalkylene, substituted or unsubstituted C 1-30 heterocycloalkylene, substituted or unsubstituted C 6-30 arylene, substituted or unsubstituted divalent C 7-30 arylalkyl, substituted or unsubstituted C 1-30 heteroarylene, or substituted or unsubstituted divalent C 3-30 heteroarylalkyl, —O—, —C(O)—, —C(O)—O—, —C(O)—N (R 2a )—, —S—, —S(O) 2 —, —N(R 2a )—S(O) 2 —, —C 1-12 hydrocarbylene-, —O—(C 1-12 hydrocarbylene)—, —C(O)—O—(C 1-12 hydrocarbylene)-, or —C(O)—O—(C 1-12 hydrocarbylene)—O—, 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 2a is the single bond forming the ring with R b ;
Ar 1 comprises a hydroxy-substituted C 6-60 aryl group, a hydroxy-substituted C 5-60 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 3-30 heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl, —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 2-30 heterocycloalkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl.
3. The photoresist composition of claim 1 , wherein the first repeating unit of the second polymer is derived from a monomer 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 3-20 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 4-20 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;
any two of R 1 to R 3 together optionally form a ring, and each of R 1 to R 3 optionally may include as part of their structure one or more groups selected from —O—, —C(O)—, —N(R 42 )—, —S—, or —S(O) 2 —, wherein R 42 is hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
any two of R 4 to R e together optionally form a ring, and each of R 4 to R 6 optionally may include as part of their structure one or more groups selected 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 3-20 heterocycloalkyl;
L 2 is a divalent linking;
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 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 4-20 heteroaryl,
R 9 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl, wherein one of R 7 or R 8 optionally forms a heterocyclic ring together with R 9 ;
R 10 to R 12 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 4-20 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 selected from —O—, —C(O)—, —N(R 44 )—, —S—, or —S(O) 2 —, wherein R 44 is hydrogen, straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
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 second repeating unit of the second polymer is derived from a monomer of formula (4), and
the third repeating unit of the second polymer is derived from a monomer of formula (5):
wherein, in Formulae (4) and (5),
R f and R g are each independently 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 44 is hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
R 14 is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group;
Q 1 is one or more of substituted or unsubstituted C 1-30 alkylene, substituted or unsubstituted C 3-30 cycloalkylene, substituted or unsubstituted C 1-30 heterocycloalkylene, substituted or unsubstituted C 6-30 arylene, substituted or unsubstituted divalent C 7-30 arylalkyl, substituted or unsubstituted C 1-30 heteroarylene, or substituted or unsubstituted divalent C 3-30 heteroarylalkyl, or —C(O)—O—;
W is the base-soluble group comprising —C(O)—OH; —C(CF 3 ) 2 OH; an amide; an imide; or —NH—S(O) 2 —Y 1 wherein Y 1 is F or C 1-4 perfluoroalkyl; and
a is an integer of 1 to 3.
5. The photoresist composition of claim 4 , wherein the third repeating unit of the second polymer is derived from a monomer chosen from the following:
wherein,
R g is hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl; and
Y 1 is F or C 1-4 perfluoroalkyl.
6. The photoresist composition of claim 4 , wherein the third repeating unit of the second polymer is derived from a monomer chosen from the following:
wherein,
R g is hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl; and
Y 1 is F or C 1-4 perfluoroalkyl.
7. The photoresist composition of claim 1 , wherein the first polymer or the second polymer comprises a repeating unit comprising the photoacid generator.
8. The photoresist composition of claim 7 , further comprising a non-polymeric photoacid generator.
9. The photoresist composition of claim 1 , further comprising a photo-decomposable quencher.
10. 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.
11. A pattern formation method, comprising:
(a) applying a layer of a photoresist composition of claim 1 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.
12. The method of claim 11 , wherein the first repeating unit of the first polymer is of formula (1a):
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 comprising one or more of substituted or unsubstituted C 1-30 alkylene, substituted or unsubstituted C 3-30 cycloalkylene, substituted or unsubstituted C 1-30 heterocycloalkylene, substituted or unsubstituted C 6-30 arylene, substituted or unsubstituted divalent C 7-30 arylalkyl, substituted or unsubstituted C 1-30 heteroarylene, or substituted or unsubstituted divalent C 3-30 heteroarylalkyl, —O—, —C(O)—, —C(O)—O—, —C(O)—N(R 2a )—, —S—, —S(O) 2 —, —N(R 2a )—S(O) 2 —, —C 1-12 hydrocarbylene-, —O—(C 1-12 hydrocarbylene)-, —C(O)—O—(C 1-12 hydrocarbylene)-, or —C(O)—O—(C 1-12 hydrocarbylene)—O—, 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 2a is the single bond forming the ring with R b ;
Ar 1 comprises a hydroxy-substituted C 6-60 aryl group, a hydroxy-substituted C 5-60 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 3-30 heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl, —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 2-30 heterocycloalkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl.
13. The method of claim 11 , wherein the first repeating unit of the second polymer are each independently derived from a monomer 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 3-20 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 4-20 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;
any two of R 1 to R 3 together optionally form a ring, and each of R 1 to R 3 optionally may include as part of their structure one or more groups selected from —O—, —C(O)—, —N(R 42 )—, —S—, or —S(O) 2 —, wherein R 42 is hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
any two of R 4 to R 6 together optionally form a ring, and each of R 4 to R 6 optionally may include as part of their structure one or more groups selected 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 3-20 heterocycloalkyl;
L 2 is a divalent linking;
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 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 4-20 heteroaryl,
R 9 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl, wherein one of R 7 or R 8 optionally forms a heterocyclic ring together with R 9 ;
R 10 to R 12 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 4-20 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 selected from —O—, —C(O)—, —N(R 44 )—, —S—, or —S(O) 2 —, wherein R 44 is hydrogen, straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
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.
14. The method of claim 11 , wherein
the second repeating unit of the second polymer is derived from a monomer of formula (4), and
the third repeating unit of the second polymer is derived from a monomer of formula (5):
wherein, in Formulae (4) and (5),
R f and R g are each independently 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 44 is hydrogen, a straight chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C 3-20 heterocycloalkyl;
R 14 is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group;
Q 1 is one or more of substituted or unsubstituted C 1-30 alkylene, substituted or unsubstituted C 3-30 cycloalkylene, substituted or unsubstituted C 1-30 heterocycloalkylene, substituted or unsubstituted C 6-30 arylene, substituted or unsubstituted divalent C 7-30 arylalkyl, substituted or unsubstituted C 1-30 heteroarylene, or substituted or unsubstituted divalent C 3-30 heteroarylalkyl, or —C(O)—O—;
W is the base-soluble group comprising —C(O)—OH; —C(CF 3 ) 2 OH; an amide; an imide; or —NH—S(O) 2 —Y 1 wherein Y 1 is F or C 1-4 perfluoroalkyl; and
a is an integer of 1 to 3.
15. The method of claim 11 , wherein the first polymer or the second polymer comprises a repeating unit comprising the photoacid generator.
16. The method of claim 15 , further comprising a non-polymeric photoacid generator.
17. The method of claim 11 , further comprising a photo-decomposable quencher.
18. The method of claim 11 , 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.