Photoresist compositions and pattern formation methods
A photoresist composition comprising a polymer, a photoacid generator, an additive comprising a tertiary carbon atom as a ring-forming atom of a lactone ring, and a solvent.
1. A photoresist composition, comprising:
a polymer;
a photoacid generator;
an additive of Formula (1a); and
a solvent:
wherein, in Formula (1a),
R 1 and R 2 are each independently substituted or unsubstituted C 1-4 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl;
each of R 1 and R 2 optionally further comprises as part of their structure one or more groups selected from —O—, —C(O)—, —S—, —S(O) 2 —, and —N(R 1a )—, wherein R 1a is hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl;
R 3a and R 3b are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl; wherein the substituted C 1-20 alkyl is substituted with nitro, cyano, hydroxyl, carboxylic acid or an alkali metal or ammonium salt thereof, halogen, thiol, C 1-6 alkylthio, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 haloalkyl, C 1-9 alkoxy, C 1-6 haloalkoxy, C 3-12 cycloalkyl, C 5-18 cycloalkenyl, C 2-18 heterocycloalkenyl, C 6-12 aryl, C 7-19 arylalkyl, C 7-12 alkylaryl, C 3-12 heterocycloalkyl, C 3-12 heteroaryl, or a combination thereof; and wherein the C 1-20 heteroalkyl and the C 3-12 heterocycloalkyl each independently has a heteroatom selected from O, S, Si, P, or a combination thereof;
each R 4 is independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl;
each R 4 optionally further comprises as part of their structure one or more groups selected from —O—, —C(O)—, —S—, —S(O) 2 —, and —N(R 2a )—, wherein R 2a is hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl;
R 1 and R 2 together optionally form a ring via a single bond or a divalent linking group;
any two of R 3a , R 3b , or R 4 together optionally form a ring via a single bond or a divalent linking group;
when n is 2 or greater, any two R 4 groups together optionally form a ring via a single bond or a divalent linking group;
m is an integer from 1 to 5; and
n is an integer from 0 to 2m.
2. The photoresist composition of claim 1 , wherein the additive has a boiling point of greater than or equal to 200° C.
3. The photoresist composition of claim 1 , wherein the polymer comprises an acid-labile repeating unit derived from a monomer represented by one or more of Formulae (2), (3), (4), (5), or (6):
wherein, in Formulae (2) to (6),
R a to R c are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 alkyl;
L 1 is a divalent linking group;
R 6 to R 11 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 3-20 heteroaryl, wherein each of R 6 to R 11 optionally further comprises a divalent linking group as part of their structure;
provided that no more than one of R 6 to R 8 is hydrogen, and provided that when one of R 6 to R 8 is hydrogen, at least one of the others from R 6 to R 8 is substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl; and provided that no more than one of R 9 to R 11 is hydrogen, and provided that when one of R 9 to R 11 is hydrogen, at least one of the others from R 9 to R 11 is substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl;
any two of R 6 to R 8 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
any two of R 9 to R 11 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
R 12 , R 13 , R 18 , and R 19 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 3-20 heteroaryl, wherein each of R 12 , R 13 , R 18 , and R 19 optionally further comprises a divalent linking group as part of their structure;
R 14 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl, wherein R 14 optionally further comprises a divalent linking group as part of its structure;
any two of R 12 to R 14 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
R 15 to R 17 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 3-20 heteroaryl, wherein each of R 15 to R 1 optionally further comprises a divalent linking group as part of their structure;
provided that no more than one of R 15 to R 17 is hydrogen, and provided that when one of R 15 to R 17 is hydrogen, at least one of the others from R 15 to R 17 is substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl;
any two of R 15 to R 17 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted,
R 20 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl, wherein R 20 optionally further comprises a divalent linking group as part of its structure;
any two of R 18 to R 20 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
X a and X b are each independently a polymerizable group selected from norbornyl or vinyl;
n1 and n2 are each independently 0 or 1; and
L 2 and L 3 are each independently a single bond or a divalent linking group, provided that L 2 is not a single bond when X a is vinyl, and provided that L 3 is not a single bond when X b is vinyl.
4. The photoresist composition of claim 1 , wherein the polymer comprises a repeating unit derived from one or more monomers of Formulae (7) or (8)
wherein,
R d and R f are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 alkyl;
L 4 and L 6 are each independently a single bond or a divalent linking group;
L 5 is a divalent linking group;
q is 0 or 1;
R 22 is a substituted or unsubstituted organic group comprising one or more heteroatoms; and
R 23 is a substituted or unsubstituted C 4-20 lactone-containing group or a substituted or unsubstituted C 4-20 sultone-containing group.
5. The photoresist composition of claim 1 , wherein
the polymer comprises a repeating unit comprising a photoacid generator,
the photoacid generator is a non-polymeric compound, or
the polymer comprises a repeating unit comprising a first photoacid generator and a second photoacid generator that is a non-polymeric compound.
6. The photoresist composition of claim 1 , further comprising a photo-decomposable quencher or a basic quencher.
7. A method for forming a pattern, the method comprising:
applying a layer of a photoresist composition of claim 1 on a substrate to provide a photoresist composition layer;
pattern-wise exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer; and
developing the exposed photoresist composition layer to provide the pattern.
8. The method of claim 7 , wherein the activating radiation has a wavelength of 248 nm.
9. The method of claim 7 , wherein the photoresist composition layer has a thickness of greater than 5 micrometers.
10. The method of claim 7 , wherein the additive has a boiling point of greater than or equal to 200° C.
11. The method of claim 7 , wherein the polymer comprises an acid-labile repeating unit derived from a monomer represented by one or more of Formulae (2), (3), (4), (5), or (6):
wherein, in Formulae (2) to (6),
R a to R c are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 alkyl;
L 1 is a divalent linking group;
R 6 to R 11 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 3-20 heteroaryl, wherein each of R 6 to R 11 optionally further comprises a divalent linking group as part of their structure;
provided that no more than one of R 6 to R 8 is hydrogen, and provided that when one of R 6 to R 8 is hydrogen, at least one of the others from R 6 to R 8 is substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl; and provided that no more than one of R 9 to R 11 is hydrogen, and provided that when one of R 9 to R 11 is hydrogen, at least one of the others from R 9 to R 11 is substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl;
any two of R 6 to R 8 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
any two of R 9 to R 11 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
R 12 , R 13 , R 18 , and R 19 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 3-20 heteroaryl, wherein each of R 12 , R 13 , R 18 , and R 19 optionally further comprises a divalent linking group as part of their structure;
R 14 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl, wherein R 14 optionally further comprises a divalent linking group as part of its structure;
any two of R 12 to R 14 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
R 15 to R 17 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 3-20 heteroaryl, wherein each of R 15 to R 17 optionally further comprises a divalent linking group as part of their structure;
provided that no more than one of R 15 to R 17 is hydrogen, and provided that when one of R 15 to R 17 is hydrogen, at least one of the others from R 15 to R 17 is substituted or unsubstituted C 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl;
any two of R 15 to R 17 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted,
R 20 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 heterocycloalkyl, wherein R 20 optionally further comprises a divalent linking group as part of its structure;
any two of R 18 to R 20 together optionally form a ring, wherein the ring optionally further comprises a divalent linking group as part of its structure, and wherein the ring is substituted or unsubstituted;
X a and X b are each independently a polymerizable group selected from norbornyl or vinyl;
n1 and n2 are each independently 0 or 1; and
L 2 and L 3 are each independently a single bond or a divalent linking group, provided that L 2 is not a single bond when X a is vinyl, and provided that L 3 is not a single bond when X b is vinyl.
12. The method of claim 7 , wherein the polymer comprises a repeating unit derived from one or more monomers of Formulae (7) or (8)
wherein,
R d and R f are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 alkyl;
L 4 and L 6 are each independently a single bond or a divalent linking group;
L 5 is a divalent linking group;
q is 0 or 1;
R 22 is a substituted or unsubstituted organic group comprising one or more heteroatoms; and
R 23 is a substituted or unsubstituted C 4-20 lactone-containing group or a substituted or unsubstituted C 4-20 sultone-containing group.
13. The method of claim 7 , wherein
the polymer comprises a repeating unit comprising a photoacid generator,
the photoacid generator is a non-polymeric compound, or
the polymer comprises a repeating unit comprising a first photoacid generator and a second photoacid generator that is a non-polymeric compound.
14. The method of claim 7 , further comprising a photo-decomposable quencher or a basic quencher.
15. The photoresist composition of claim 1 , wherein the additive is selected from one or more of:
wherein,
R 1a and R 2b are each independently hydrogen, substituted or unsubstituted C 1-3 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl; and
R 1b , R 2b , R 4c , R 4d , and R n are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl.
16. The method of claim 7 , wherein the additive is selected from one or more of:
wherein,
R 1a and R 2a are each independently hydrogen, substituted or unsubstituted C 1-3 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl; and
R 1b , R 2b , R 4c , R 4d , and R n are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl.
17. The photoresist composition of claim 1 , wherein the additive is selected from one or more of:
wherein,
R 1a and R 2b are each independently hydrogen, substituted or unsubstituted C 1-3 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl; and
R 1b , R 2b , R 4c , and R 4d are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl.
18. The method of claim 7 , wherein the additive is selected from one or more of:
wherein,
R 1a and R 2a are each independently hydrogen, substituted or unsubstituted C 1-3 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl; and
R 1b , R 2b , R 4c , and R 4d are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, 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 3-20 heteroaryl.