Composition for photoresist underlayer
A photoresist underlayer composition, comprising: a first polymer comprising a crosslinkable group; a second polymer comprising: a first repeating unit comprising a repeating unit comprising a photoacid generator, and a second repeating unit comprising a hydroxy-substituted C 1-30 alkyl group, a hydroxy-substituted C 3-30 cycloalkyl group, or a hydroxy-substituted C 6-30 aryl group; an acid catalyst; and a solvent.
1. A coated substrate, comprising:
a cured layer of a photoresist underlayer composition disposed on a substrate; and
a photoresist layer disposed on the cured layer of the photoresist underlayer composition,
wherein the photoresist underlayer composition is different from the photoresist layer,
wherein the photoresist underlayer composition comprises:
a first polymer comprising an isocyanurate repeating unit and a crosslinkable group;
a second polymer comprising:
a first repeating unit comprising a repeating unit comprising a photoacid generator, and
a second repeating unit comprising a hydroxy-substituted C 1-30 alkyl group, a hydroxy-substituted C 3-30 cycloalkyl group, or a hydroxy-substituted C 6-30 aryl group;
an acid catalyst, wherein the acid catalyst is different from the photoacid generator of the second polymer; and
a solvent.
2. The coated substrate of claim 1 , wherein the isocyanurate repeating unit is derived from a monomer of formula (1):
wherein, in formula (1),
K, L, and M are each independently a linear or branched C 1-10 hydrocarbon group, a C 1-10 alkoxycarbonyl group, a C 1-10 alkanoyloxy group, each of which is optionally substituted with a carboxylic acid group, or a linear or branched C 1-10 hydroxyalkyl group optionally substituted with a C 1-5 alkoxycarbonyl group or a C 1-5 substituted alkoxy group, and
wherein at least one hydrogen atom of the first polymer is substituted with a functional group independently chosen from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amido, vinyl, and a combination thereof.
3. The coated substrate of claim 1 , wherein the first repeating unit of the second polymer comprises a repeating unit derived from a monomer of formula (2):
wherein, in formula (2),
R a is hydrogen, fluorine, cyano, a substituted or unsubstituted C 1-10 alkyl, or a substituted or unsubstituted C 1-10 fluoroalkyl,
L 1 is a single bond or a divalent linking group,
A is a divalent linking group;
Z − is an anionic moiety comprising sulfonate, an anion of a sulfonamide, an anion of a sulfonimide, or a methide anion; and
G + is an organic cation.
4. The coated substrate of claim 3 , wherein -L 1 -A-Z − is represented by one of formulae (3) to (5b):
wherein, in formulae (3) to (5b),
Q 1 and Q 2 are each independently a fluorine-substituted divalent linking group;
Q 3 is a divalent linking group;
Q 4 is a single bond or a divalent linking group; and
R f is a fluorine-substituted C 1-30 alkyl, a fluorine-substituted C 3-30 cycloalkyl, or a single bond forming a ring with Q 3 .
5. The coated substrate of claim 3 , wherein G + is a cation represented by one of formulae (6), (7), or (8):
wherein, in formulae (6), (7), and (8):
X is I or S;
R h , R i , R j , and R k are each independently hydroxy, nitrile, halogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 fluoroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 fluorocycloalkyl, substituted or unsubstituted C 1-30 alkoxy, substituted or unsubstituted C 3-30 alkoxycarbonylalkyl, substituted or unsubstituted C 3-30 alkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 cycloalkoxy, substituted or unsubstituted C 5-30 cycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 cycloalkoxycarbonylalkoxy, substituted or unsubstituted C 1-30 fluoroalkoxy, substituted or unsubstituted C 3-30 fluoroalkoxycarbonylalkyl, substituted or unsubstituted C 3-30 fluoroalkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 fluorocycloalkoxy, substituted or unsubstituted C 5-30 fluorocycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 fluorocycloalkoxycarbonylalkoxy, substituted or unsubstituted C 6-30 aryl, C 6-30 fluoroaryl, substituted or unsubstituted C 6-30 aryloxy, or substituted or unsubstituted C 6-30 fluoroaryloxy;
each R aa is independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 fluoroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 fluorocycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 fluoroalkenyl, substituted or unsubstituted C 6-30 aryl group, substituted or unsubstituted C 6-30 fluoroaryl, substituted or unsubstituted C 6-30 iodoaryl, substituted or unsubstituted C 4-30 heteroaryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 fluoroarylalkyl, substituted or unsubstituted C 5-30 heteroarylalkyl, or substituted or unsubstituted C 5-30 fluoroheteroarylalkyl, wherein each R aa is either separate or connected to another group R aa via a single bond or a divalent linking group to form a ring;
when X is I, p is 2, and R 1 is a lone pair of electrons;
when X is S, p is 3, and R 1 is a substituted or unsubstituted C 6-20 aryl group;
q and r are each independently an integer from 0 to 5; and
s and t are each independently an integer from 0 to 4.
6. The coated substrate of claim 1 , wherein the second repeating unit of the second polymer is derived from a monomer of formula (9):
wherein, in formula (9),
R a is hydrogen, halogen, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
L 2 is a single bond or a divalent linking group;
Y comprises a hydroxy-substituted C 1-30 alkyl group, a hydroxy-substituted C 3-30 cycloalkyl group, a hydroxy-substituted C 6-30 aryl group, a hydroxy-substituted C 5-30 heteroaryl group, or a combination thereof, each of which is optionally further substituted.
7. The coated substrate of claim 1 ,
wherein the crosslinkable group of the first polymer comprises hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amido, vinyl, or a combination thereof.
8. The coated substrate of claim 1 , wherein the second polymer further comprises a third repeating unit comprising an unsubstituted C 1-30 alkyl group, a fluorine-substituted C 1-30 alkyl group, a C 1-30 alkyl group substituted with a polymerizable group, a C 3-30 cycloalkyl group substituted with a polymerizable group, or a C 6-30 aryl group substituted with a polymerizable group, wherein the polymerizable group is reactive to self-crosslink the second polymer.
9. A method of forming a pattern, the method comprising:
applying a layer of the photoresist underlayer composition on the substrate;
curing the applied layer of the photoresist underlayer composition to form an underlayer film;
applying a layer of the photoresist composition on the underlayer film to form the photoresist layer and provide the coated substrate of claim 1 ;
pattern-wise exposing the applied photoresist layer to activating radiation; and
developing the exposed photoresist layer to provide a resist relief image.
10. The method of claim 9 , wherein the first polymer comprises an isocyanurate repeating unit derived from a monomer of formula (1):
wherein, in formula (1),
K, L, and M are each independently a linear or branched C 1-10 hydrocarbon group, a C 1-10 alkoxycarbonyl group, a C 1-10 alkanoyloxy group, each of which is optionally substituted with a carboxylic acid group, or a linear or branched C 1-10 hydroxyalkyl group optionally substituted with a C 1-5 alkoxycarbonyl group or a C 1-5 substituted alkoxy group, and
wherein at least one hydrogen atom of the first polymer is substituted with a functional group independently chosen from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amido, vinyl, and a combination thereof.
11. The method of claim 9 , wherein the second repeating unit of the second polymer is derived from a monomer of formula (9):
wherein, in formula (9),
R a is hydrogen, halogen, cyano, substituted or unsubstituted C 1-10 alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl;
L 2 is a single bond or a divalent linking group;
Y comprises a hydroxy-substituted C 1-30 alkyl group, a hydroxy-substituted C 3-30 cycloalkyl group, a hydroxy-substituted C 6-30 aryl group, a hydroxy-substituted C 5-30 heteroaryl group, or a combination thereof, each of which is optionally further substituted.
12. The method of claim 9 , wherein the first repeating unit of the second polymer comprises a repeating unit derived from a monomer of formula (2):
wherein, in formula (2),
R a is hydrogen, fluorine, cyano, a substituted or unsubstituted C 1-10 alkyl, or a substituted or unsubstituted C 1-10 fluoroalkyl,
L 1 is a single bond or a divalent linking group,
A is a divalent linking group;
Z − is an anionic moiety comprising sulfonate, an anion of a sulfonamide, an anion of a sulfonimide, or a methide anion; and
G + is an organic cation.
13. The method of claim 12 , wherein -L 1 -A-Z − is represented by one of formulae (3) to (5b):
wherein, in formulae (3) to (5b),
Q 1 and Q 2 are each independently a fluorine-substituted divalent linking group;
Q 3 is a divalent linking group;
Q 4 is a single bond or a divalent linking group; and
R f is a fluorine-substituted C 1-30 alkyl, a fluorine-substituted C 3-30 cycloalkyl, or a single bond forming a ring with Q 3 .
14. The method of claim 12 , wherein G + is a cation represented by one of formulae (6), (7), or (8):
wherein, in formulae (6), (7), and (8):
X is I or S;
R h , R i , R j , and R k are each independently hydroxy, nitrile, halogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 fluoroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 fluorocycloalkyl, substituted or unsubstituted C 1-30 alkoxy, substituted or unsubstituted C 3-30 alkoxycarbonylalkyl, substituted or unsubstituted C 3-30 alkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 cycloalkoxy, substituted or unsubstituted C 5-30 cycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 cycloalkoxycarbonylalkoxy, substituted or unsubstituted C 1-30 fluoroalkoxy, substituted or unsubstituted C 3-30 fluoroalkoxycarbonylalkyl, substituted or unsubstituted C 3-30 fluoroalkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 fluorocycloalkoxy, substituted or unsubstituted C 5-30 fluorocycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 fluorocycloalkoxycarbonylalkoxy, substituted or unsubstituted C 6-30 aryl, C 6-30 fluoroaryl, substituted or unsubstituted C 6-30 aryloxy, or substituted or unsubstituted C 6-30 fluoroaryloxy;
each R aa is independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 fluoroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 fluorocycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 fluoroalkenyl, substituted or unsubstituted C 6-30 aryl group, substituted or unsubstituted C 6-30 fluoroaryl, substituted or unsubstituted C 6-30 iodoaryl, substituted or unsubstituted C 4-30 heteroaryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 7-20 fluoroarylalkyl, substituted or unsubstituted C 5-30 heteroarylalkyl, or substituted or unsubstituted C 5-30 fluoroheteroarylalkyl, wherein each R aa is either separate or connected to another group R aa via a single bond or a divalent linking group to form a ring;
when X is I, p is 2, and R 1 is a lone pair of electrons;
when X is S, p is 3, and R 1 is a substituted or unsubstituted C 6-20 aryl group;
q and r are each independently an integer from 0 to 5; and
s and t are each independently an integer from 0 to 4.
15. The coated substrate of claim 1 , wherein the second repeating unit comprises a hydroxy-substituted C 1-30 alkyl group, or a hydroxy-substituted C 6-30 aryl group.