Photoacid generator and photoresist comprising same
View Patent ↗A photoacid generator compound has the formula (I): [A-(CHR 1 ) p ] k -(L)-(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (I) wherein A is a substituted or unsubstituted, monocyclic, polycyclic, or fused polycyclic C 5 or greater cycloaliphatic group optionally comprising O, S, N, F, or a combination comprising at least one of the foregoing, R 1 is H, a single bond, or a substituted or unsubstituted C 1-30 alkyl group, wherein when R 1 is a single bond, R 1 is covalently bonded to a carbon atom of A, each R 2 is independently H, F, or C 1-4 fluoroalkyl, wherein at least one R 2 is not hydrogen, L is a linking group comprising a sulfonate group, a sulfonamide group, or a C 1-30 sulfonate or sulfonamide-containing group, Z is an organic or inorganic cation, p is an integer of 0 to 10,k is 1 or 2, m is an integer of 0 or greater, and n is an integer of 1 or greater. A precursor compound to the photoacid generator, a photoresist composition including the photoacid generator, and a substrate coated with the photoresist composition, are also disclosed.
1. A compound having the formula (I):
[A-(CHR 1 ) p ] k -(L)-(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (I)
wherein
A is a substituted or unsubstituted, polycyclic, or fused polycyclic C 5 or greater cycloaliphatic group optionally comprising O, S, N, F, or a combination comprising at least one of the foregoing,
R 1 is H, a single bond, or a substituted or unsubstituted C 1-30 alkyl group, wherein when R 1 is a single bond, R 1 is covalently bonded to a carbon atom of A,
each R 2 is independently H, F, or C 1-4 fluoroalkyl, wherein at least one R 2 is not hydrogen,
L is a linking group comprising a sulfonate group, a sulfonamide group, or a C 1-30 sulfonate or sulfonamide-containing group,
Z + is an organic or inorganic cation, and
p is an integer of 0 to 10, k is 1 or 2, m is an integer of 2-10, and n is an integer of 1 to 10.
2. The compound of claim 1 , having the formula (IIa) or (IIb):
A-(CHR 1 ) p —O—SO 2 —(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIa)
A-(CHR 1 ) p —SO 2 —O—(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIb)
wherein A, R 1 , R 2 p, m, n, and Z + are as defined for formula (I).
3. The compound of claim 1 , having the formula (IIIa) or (IIIb):
A-(CHR 1 ) p —N(R 3 )—SO 2 —(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIIa)
A-(CHR 1 ) p —SO 2 —N(R 3 )—(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIIb)
wherein A, R 1 , R 2 p, m, n, and Z + are as defined for formula (I) and R 3 is H, a C 1-20 alkyl group, or A-(CHR 1 ) p —.
4. The compound of claim 1 , having the formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), or (XII):
wherein Z + is as defined in formula (I).
5. The compound of claim 1 , wherein Z + is a cation of the formula (XIII):
wherein R 4 and R 5 are independently substituted or unsubstituted C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 6-20 heteroaralkyl, where R 4 and R 5 are separate or connected by a single bond, and Ar is a C 5-30 aromatic-containing group.
6. The compound of claim 5 , wherein the cation is of the formula (XIV), (XV), or (XVI):
wherein
R 4 and R 5 are independently substituted or unsubstituted C 1-20 alkyl, 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, or C 6-20 heteroaralkyl, where R 4 and R 5 are separate or connected by a single bond;
R 6 , R 7 , R 8 and R 9 are each independently H, a halogen, C 1-20 alkyl, C 1-20 fluoroalkyl, C 1-20 alkoxy, C 1-20 fluoroalkoxy, C 1-20 thioalkoxy, C 1-20 fluorothioalkoxy, C 1-20 alkoxycarbonyl, C 1-20 fluoroalkoxycarbonyl, C 1-20 thioalkoxycarbonyl, C 1-20 fluorothioalkoxycarbonyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 3-20 cycloalkoxy, C 3-20 fluorocycloalkoxy, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, C 6-20 fluoroaryloxy, C 5-20 heteroaryl, C 5-20 heteroaryloxy, C 5-20 heteroaryloxy, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 7-20 aralkyloxy C 7-20 fluoroaralkyloxy, or C 6-20 heteroaralkyl, or C 6-20 heteroaralkyloxy, wherein R 6 , R 7 , R 8 and R 9 are each independently unsubstituted or further substituted to include an acid-labile group, a base-labile group, or a base-soluble group, and
q is an integer of 1 to 5, r is an integer of 0 to 3, s is an integer of 0 to 4, t is an integer of 0 to 4, and a is an integer of 0 to 4.
7. The compound of claim 6 , wherein Z + is of the formula (XVII), (XVIII), (XIX), or (XX):
wherein
R 10 , R 11 , R 12 and R 14 are independently H, a halogen, C 1-10 alkyl, C 1-10 fluoroalkyl, C 1-10 alkoxy, C 1-10 fluoroalkoxy, C 3-10 cycloalkyl, C 3-10 fluorocycloalkyl, C 3-10 cycloalkoxy, or C 3-10 fluorocycloalkoxy,
R 13 is H, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl, or C 3-10 fluorocycloalkyl, and
a and b are each independently 1 or 2.
8. A photoresist composition, comprising:
an acid-sensitive polymer, and
a compound of claim 1 .
9. A coated substrate, comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a photoresist composition of claim 8 over the one or more layers to be patterned.
10. The coated substrate of claim 9 , wherein the compound of claim 1 has the formula (IIa) or (IIb):
A-(CHR 1 ) p —O—SO 2 —(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIa)
A-(CHR 1 ) p —SO 2 —O—(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIb)
wherein A, R 1 , R 2 p, m, n, and Z + are as defined for formula (I).
11. The coated substrate of claim 9 , wherein the compound of claim 1 has the formula (IIIa) or (IIIb):
A-(CHR 1 ) p —N(R 3 )—SO 2 —(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIIa)
A-(CHR 1 ) p —SO 2 —N(R 3 )—(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIIb)
wherein A, R 1 , R 2 p, m, n, and Z + are as defined for formula (I), and R 3 is H, a C 1-20 alkyl group, or A-(CHR 1 ) p —.
12. The coated substrate of claim 9 , wherein the compound of claim 1 has the formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), or (XII):
wherein Z + is as defined in formula (I).
13. The coated substrate of claim 9 , wherein, in the compound of claim 1 , Z + is a cation of the formula (XIII):
wherein R 4 and R 5 are independently substituted or unsubstituted C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 6-20 heteroaralkyl, where R 4 and R 5 are separate or connected by a single bond, and Ar is a C 5-30 aromatic-containing group.
14. The coated substrate of claim 13 , wherein the cation is of the formula (XIV), (XV), or (XVI):
wherein
R 4 and R 5 are independently substituted or unsubstituted C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, or C 6-20 heteroaralkyl, where R 4 and R 5 are separate or connected by a single bond;
R 6 , R 7 , R 8 and R 9 are each independently H, a halogen, C 1-20 alkyl, C 1-20 fluoroalkyl, C 1-20 alkoxy, C 1-20 fluoroalkoxy, C 1-20 thioalkoxy, C 1-20 fluorothioalkoxy, C 1-20 alkoxycarbonyl, C 1-20 fluoroalkoxycarbonyl, C 1-20 thioalkoxycarbonyl, C 1-20 fluorothioalkoxycarbonyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 3-20 cycloalkoxy, C 3-20 fluorocycloalkoxy, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, C 6-20 fluoroaryloxy, C 5-20 heteroaryl, C 5-20 heteroaryloxy, C 5-20 heteroaryloxy, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 7-20 aralkyloxy C 7-20 fluoroaralkyloxy, or C 6-20 heteroaralkyl, or C 6-20 heteroaralkyloxy, wherein R 6 , R 7 , R 8 and R 9 are each independently unsubstituted or further substituted to include an acid-labile group, a base-labile group, or a base-soluble group, and
q is an integer of 1 to 5, r is an integer of 0 to 3, s is an integer of 0 to 4, t is an integer of 0 to 4, and a is an integer of 0 to 4.
15. The photoresist of claim 8 , wherein the compound of claim 1 has the formula (IIa) or (IIb):
A-(CHR 1 ) p —O—SO 2 —(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIa)
A-(CHR 1 ) p —SO 2 —O—(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIb)
wherein A, R 1 , R 2 p, m, n, and Z + are as defined for formula (I).
16. The photoresist of claim 8 , wherein the compound of claim 1 has the formula (IIIa) or (IIIb):
A-(CHR 1 ) p —N(R 3 )—SO 2 —(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIIa)
A-(CHR 1 ) p —SO 2 —N(R 3 )—(CH 2 ) m —(C(R 2 ) 2 ) n —SO 3 − Z + (IIIb)
wherein A, R 1 , R 2 p, m, n, and Z + are as defined for formula (I), and R 3 is H, a C 1-20 alkyl group, or A-(CHR 1 ) p —.
17. The photoresist of claim 8 , wherein the compound of claim 1 has the formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), or (XII):
wherein Z + is as defined in formula (I).
18. The photoresist of claim 8 , wherein, in the compound of claim 1 , Z + is a cation of the formula (XIII):
wherein R 4 and R 5 are independently substituted or unsubstituted C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 6-20 heteroaralkyl, where R 4 and R 5 are separate or connected by a single bond, and Ar is a C 5-30 aromatic-containing group.
19. The photoresist of claim 18 , wherein the cation is of the formula (XIV), (XV), or (XVI):
wherein
R 4 and R 5 are independently substituted or unsubstituted C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, or C 6-20 heteroaralkyl, where R 4 and R 5 are separate or connected by a single bond;
R 6 , R 7 , R 8 and R 9 are each independently H, a halogen, C 1-20 alkyl, C 1-20 fluoroalkyl, C 1-20 alkoxy, C 1-20 fluoroalkoxy, C 1-20 thioalkoxy, C 1-20 fluorothioalkoxy, C 1-20 alkoxycarbonyl, C 1-20 fluoroalkoxycarbonyl, C 1-20 thioalkoxycarbonyl, C 1-20 fluorothioalkoxycarbonyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 3-20 cycloalkoxy, C 3-20 fluorocycloalkoxy, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, C 6-20 fluoroaryloxy, C 5-20 heteroaryl, C 5-20 heteroaryloxy, C 5-20 heteroaryloxy, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 7-20 aralkyloxy C 7-20 fluoroaralkyloxy, or C 6-20 heteroaralkyl, or C 6-20 heteroaralkyloxy, wherein R 6 , R 7 , R 8 and R 9 are each independently unsubstituted or further substituted to include an acid-labile group, a base-labile group, or a base-soluble group, and
q is an integer of 1 to 5, r is an integer of 0 to 3, s is an integer of 0 to 4, t is an integer of 0 to 4, and a is an integer of 0 to 4.
20. The photoresist of claim 19 , wherein Z + is of the formula (XVII), (XVIII), (XIX), or (XX):
wherein
R 10 , R 11 , R 12 and R 14 are independently H, a halogen, C 1-10 alkyl, C 1-10 fluoroalkyl, C 1-10 alkoxy, C 1-10 fluoroalkoxy, C 3-10 cycloalkyl, C 3-10 fluorocycloalkyl, C 3-10 cycloalkoxy, or C 3-10 fluorocycloalkoxy,
R 13 is H, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl, or C 3-10 fluorocycloalkyl, and
a and b are each independently 1 or 2.
21. A compound having the formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), or (XII):
wherein Z′ is as defined in formula (I).
22. A photoresist composition comprising:
an acid-sensitive polymer, and
a compound having the formula (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), or (XII):
wherein Z′ is as defined in formula (I).