Underlayer compositions and patterning methods
An 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; X is C or O; R 1 , R 2 ; R a and R b are as provided herein; optionally, R 1 and R 2 can be taken together form a 5- to 7-membered ring; optionally, one of R 11 to R 13 can be taken together with R 1 to form a 5- to 7-membered ring; wherein R a and R b optionally may be taken together to form a 5- to 7-membered ring; wherein one of R a or R b optionally may be taken together with R 2 to form a 5- to 7-membered ring; and when X is O, R a and R b are absent.
1. An 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;
X is C or O;
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;
R 2 is substituted or unsubstituted C 4-30 alkyl, 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, substituted or unsubstituted C 4-30 heteroarylalkyl, or —NR 11 R 12 , wherein R 11 to R 12 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;
optionally, R 1 and R 2 can be taken together form a 5- to 7-membered carbocyclic ring;
optionally, one of R 11 to R 12 can be taken together with R 1 to form a 5- to 7-membered ring;
when X is C, Ra and Rb 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 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 a and R b optionally may be taken together to form a 5- to 7-membered ring;
wherein one of R a or R b optionally may be taken together with R 2 to form a 5- to 7-membered ring which is not an aromatic ring; and
when X is O, R a and R b are absent,
provided that Ar comprises a group of formula (2), formula (3a), formula (3b), or formula (3c) when the repeating unit of formula (1) is represented by formulae (11) or (12),
wherein, in formula (2),
A1, A2, and A3 are each 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 31 , —SR 32 , or —NR 33 R 34 ;
provided that at least one of R 3 or R 4 is —OR 31 , —SR 32 , or —NR 33 R 34 ;
R 31 to R 34 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, and wherein, in formulae (3a), (3b), and (3c),
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.
2. The 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 21 , —SR 22 , or —NR 23 R 24 , wherein 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,
provided that the monocyclic or polycyclic C 6-60 arylene group is substituted with at least one substituent group comprising a heteroatom.
3. The 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 31 , —SR 32 , or —NR 33 R 34 ;
provided that at least one of R 3 or R 4 is —OR 31 , —SR 32 , or —NR 33 R 34 ;
R 31 to R 34 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 underlayer composition of claim 1 , wherein Ar comprises a group of formula (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 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 51 R 52 —, —NR 53 —, or —PR 54 —;
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 55 , —SR 56 , or —NR 57 R 58 ;
R 51 to R 58 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 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 underlayer composition of claim 1 , wherein X is C.
8. The underlayer composition of claim 1 , wherein the polymer comprises a repeating unit of any one or more of formulae (6), (7), or (9) to (12):
wherein Ar is as defined in any one of claim 1 .
9. The underlayer composition of claim 1 , further comprising one or more of a curing agent, a crosslinking agent, or a surfactant.
10. A method of forming a pattern, the method comprising: (a) applying a layer of the underlayer composition of claim 1 on a substrate; (b) curing the applied underlayer composition to form an underlayer; and (c) forming a photoresist layer over the underlayer.
11. The method of claim 10 , further comprising forming a silicon-containing layer, an organic antireflective coating layer, or a combination thereof, above the underlayer prior to forming the photoresist layer.
12. The method of claim 10 , further comprising patterning the photoresist layer and transferring a pattern from the patterned photoresist layer to the underlayer to a layer below the underlayer.
13. The method of claim 10 , 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 21 , —SR 22 , or —NR 23 R 24 , wherein 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,
provided that the monocyclic or polycyclic C 6-60 arylene group is substituted with at least one substituent group comprising a heteroatom.
14. The method of claim 10 , 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 31 , —SR 32 , or —NR 33 R 34 ;
provided that at least one of R 3 or R 4 is —OR 31 , —SR 32 , or —NR 33 R 34 ;
R 31 to R 34 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.
15. The method of claim 10 , wherein Ar comprises a group of formula (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.
16. The method of claim 10 , wherein Ar comprises a group of formula (4):
wherein,
L 1 is a single bond, —O—, —S—, —S(O)—, —SO 2 —, —C(O)—, —CR 51 R 52 —, —NR 53 —, or —PR 54 —;
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 55 , —SR 56 , or —NR 57 R 58 ;
R 51 to R 58 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.
17. The method of claim 10 , wherein the monocyclic or polycyclic C 5-60 aromatic group is a monocyclic or polycyclic C 6-60 arylene group substituted with hydroxyl.
18. The method of claim 10 , wherein the polymer comprises a repeating unit of any one or more of formulae (6), (7), or (9) to (12):
wherein Ar is as defined in claim 1 .
19. The method of claim 10 , wherein X is C.
20. The method of claim 10 , wherein the underlayer composition further comprises one or more of a curing agent, a crosslinking agent, or a surfactant.