Coating composition for photoresist underlayer
A photoresist underlayer composition, comprising a polymer comprising a repeating unit of formula (1): wherein Ar is a monocyclic or polycyclic C 5-60 aromatic group, wherein the aromatic group comprises one or more aromatic ring heteroatoms, a substituent group comprising a heteroatom, or a combination thereof; R 1 is hydrogen, 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 2-30 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; and R 2 is 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 2-30 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, wherein R 1 and R 2 can be optionally taken together to form a ring.
1. A photoresist underlayer composition, comprising:
a polymer comprising a repeating unit of formula (1); and
a crosslinking agent:
wherein
Ar is a monocyclic or polycyclic C 5-60 aromatic group, wherein the C 5-60 aromatic group comprises one or more aromatic ring heteroatoms, a substituent group comprising a heteroatom, or a combination thereof;
R 1 is hydrogen, 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 2-30 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; and
R 2 is 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 2-30 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,
wherein R 1 and R 2 can be optionally taken together to form a ring,
wherein the photoresist underlayer composition is free of a photoacid generator.
2. The photoresist underlayer composition of claim 1 , wherein Ar is a monocyclic or polycyclic C 5-60 heteroarylene group or a monocyclic or polycyclic C 6-60 arylene group, optionally substituted with at least one of substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 haloalkyl, 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, substituted or unsubstituted C 4-30 heteroarylalkyl, halogen, —OR 11 , —SR 12 , or —NR 13 R 14 , wherein R 11 to R 14 are each independently hydrogen, 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,
provided that the monocyclic or polycyclic C 6-60 arylene group is substituted with at least one substituent group comprising a heteroatom.
3. The photoresist underlayer composition of claim 1 , wherein Ar comprises a group of formula (2):
wherein,
A1, A2, and A3 each may be present or absent, and each independently represents 1 to 3 fused aromatic rings;
R 3 and R 4 are each independently 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 2-30 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, halogen, —OR 21 , —SR 22 , or —NR 23 R 24 ; and
provided that at least one of R 3 or R 4 is —OR 21 , —SR 22 , or —NR 23 R 24 ;
R 21 to R 24 are each independently hydrogen, 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;
m is an integer 0 to 4;
n is an integer 0 to 4; and
provided that the sum of m and n is an integer greater than 0.
4. The photoresist underlayer composition of claim 1 , wherein Ar comprises a group of formulae (3a), (3b), or (3c):
wherein,
A4 may be present or absent, and represents 1 to 3 fused aromatic rings;
Z 1 and Z 2 are each independently C or N;
each R 5 is independently 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 2-30 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; and
p is an integer of 0 to 4,
wherein A4 comprises at least one heteroaryl ring, at least one of Z 1 and Z 2 is N, or a combination thereof.
5. The photoresist underlayer composition of claim 1 , wherein Ar comprises a group of formula (4):
wherein,
L 1 is a single bond, —O—, —S—, —S(O)—, —SO 2 —, —C(O)—, —CR 41 R 42 —, —NR 43 —, or —PR 44 —;
L 2 is absent, a single bond, —O—, —S—, —S(O)—, —SO 2 —, —C(O)—, substituted or unsubstituted C 1-2 alkylene, substituted or unsubstituted C 6-30 arylene, or substituted or unsubstituted C 5-30 heteroarylene;
R 8 and R 9 are each independently 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 2-30 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, halogen, —OR 45 , —SR 46 , or —NR 47 R 48 ;
R 41 to R 48 are each independently hydrogen, 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 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;
a is an integer of 0 to 4; and
b is an integer of 0 to 4.
6. The photoresist underlayer composition of claim 1 , wherein the monocyclic or polycyclic C 5-60 aromatic group is a monocyclic or polycyclic C 6-60 arylene group substituted with hydroxyl.
7. The photoresist underlayer composition of claim 1 , wherein the polymer comprises a repeating unit of formula (6):
wherein R 1 and R 2 are as defined in any one of claims 1 to 6 .
8. The photoresist underlayer composition of claim 1 , further comprising one or more of a curing agent, and a surfactant.
9. A method of forming a pattern, the method comprising: (a) applying a layer of the photoresist underlayer composition of claim 1 on a substrate; (b) curing the applied photoresist underlayer composition to form a photoresist underlayer; and (c) forming a photoresist layer over the photoresist underlayer.
10. The method of claim 9 , further comprising forming a silicon-containing layer, an organic antireflective coating layer, or a combination thereof, above the photoresist underlayer prior to forming the photoresist layer.
11. The method of claim 9 , further comprising patterning the photoresist layer and transferring a pattern from the patterned photoresist layer to the photoresist underlayer and to a layer below the photoresist underlayer.
12. The method of claim 9 , wherein in the polymer comprising the repeating unit of formula (1),
Ar is a monocyclic or polycyclic C 5-60 heteroarylene group or a monocyclic or polycyclic C 6-60 arylene group, optionally substituted with at least one of substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 haloalkyl, 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, substituted or unsubstituted C 4-30 heteroarylalkyl, halogen, —OR 11 , —SR 12 , or —NR 13 R 14 , wherein R 11 to R 14 are each independently hydrogen, 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,
provided that the monocyclic or polycyclic C 6-60 arylene group is substituted with at least one substituent group comprising a heteroatom.
13. The method of claim 9 , wherein in the polymer comprising the repeating unit of formula (1), Ar comprises a group of formula (2):
wherein,
A1, A2, and A3 each may be present or absent, and each independently represents 1 to 3 fused aromatic rings;
R 3 and R 4 are each independently 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 2-30 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, halogen, —OR 21 , —SR 22 , or —NR 23 R 24 ; and
provided that at least one of R 3 or R 4 is —OR 21 , —SR 22 , or —NR 23 R 24 ;
R 21 to R 24 are each independently hydrogen, 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;
m is an integer 0 to 4;
n is an integer 0 to 4; and
provided that the sum of m and n is an integer greater than 0.
14. The method of claim 9 , wherein in the polymer comprising the repeating unit of formula (1), wherein Ar comprises a group of formulae (3a), (3b), or (3c):
wherein,
A4 may be present or absent, and represents 1 to 3 fused aromatic rings;
Z 1 and Z 2 are each independently C or N;
each R 5 is independently 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 2-30 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; and
p is an integer of 0 to 4,
wherein A4 comprises at least one heteroaryl ring, at least one of Z 1 and Z 2 is N, or a combination thereof.
15. The method of claim 9 , wherein in the polymer comprising the repeating unit of formula (1), Ar comprises a group of formula (4):
wherein,
L 1 is a single bond, —O—, —S—, —S(O)—, —SO 2 —, —C(O)—, —CR 41 R 42 —, —NR 43 —, or —PR 44 —;
L 2 is absent, a single bond, —O—, —S—, —S(O)—, —SO 2 —, —C(O)—, substituted or unsubstituted C 1-2 alkylene, substituted or unsubstituted C 6-30 arylene, or substituted or unsubstituted C 5-30 heteroarylene;
R 8 and R 9 are each independently 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 2-30 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, halogen, —OR 45 , —SR 46 , or —NR 47 R 48 ;
R 41 to R 48 are each independently hydrogen, 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 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;
a is an integer of 0 to 4; and
b is an integer of 0 to 4.
16. The method of claim 9 , wherein in the polymer comprising the repeating unit of formula (1), the monocyclic or polycyclic C 5-60 aromatic group is a monocyclic or polycyclic C 6-60 arylene group substituted with hydroxyl.
17. The method of claim 9 , wherein the polymer comprises a repeating unit of formula (6):
wherein R 1 and R 2 are as defined in any one of claims 1 to 6 .
18. The method of claim 9 , wherein the photoresist underlayer composition further comprises one or more of a curing agent, and a surfactant.