Polymers, underlayer coating compositions comprising the same, and patterning methods
A polymer comprising a first repeating unit including an amino group protected by an alkoxycarbonyl group; a second repeating unit including a nucleophilic group; and a third repeating unit including a crosslinkable group, wherein the first repeating unit, the second repeating unit, and the third repeating unit are different from each other.
1. A coated substrate, comprising:
a layer of an underlayer coating composition disposed on a substrate; and
a photoresist layer disposed on the layer of the underlayer coating composition,
wherein the underlayer coating composition comprises a polymer comprising:
a first repeating unit comprising an amino group protected by an alkoxycarbonyl group;
a second repeating unit comprising a nucleophilic group; and
a third repeating unit comprising a crosslinkable group,
wherein the first repeating unit, the second repeating unit, and the third repeating unit are different from each other.
2. The coated substrate of claim 1 , wherein the first repeating unit is derived from a monomer of formula (1):
wherein,
R a is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
each R k is independently a halogen, a hydroxy, a carboxylic acid or ester, a thiol, a straight chain or branched C 1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 fluorocycloalkenyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a monocyclic or polycyclic C 6-20 aryl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted;
A is a single bond or a C 1-2 alkylene;
R 1 , R 2 , and R 3 are each independently a straight chain or branched C 1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a straight chain or branched C 2-20 alkenyl, a monocyclic or polycyclic C 3-20 cycloalkenyl, a monocyclic or polycyclic C 3-20 heterocycloalkenyl, a monocyclic or polycyclic C 6-20 aryl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted, and any two of R 1 , R 2 , and R 3 together optionally form a ring; and
n is an integer of 0 to 11.
3. The coated substrate of claim 1 , wherein the first repeating unit is derived from a monomer of formula (2):
wherein,
R b is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
L 1 is a linking group; and
R 4 , R 5 , and R 6 are each independently a straight chain or branched C 1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a straight chain or branched C 2-20 alkenyl, a monocyclic or polycyclic C 3-20 cycloalkenyl, a monocyclic or polycyclic C 3-20 heterocycloalkenyl, a monocyclic or polycyclic C 6-20 aryl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted, and any two of R 4 , R 5 , and R 6 together optionally form a ring.
4. The coated substrate of claim 1 , wherein the second repeating unit is derived from a monomer of formula (3):
wherein
R c is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
L 2 is a substituted or unsubstituted C 1-30 alkylene, a substituted or unsubstituted C 3-30 cycloalkylene, a substituted or unsubstituted C 3-30 heterocycloalkylene, a substituted or unsubstituted C 6-30 arylene, a substituted or unsubstituted divalent C 7-30 arylalkyl, a substituted or unsubstituted C 3-30 heteroarylene, or a substituted or unsubstituted divalent C 4-30 heteroarylalkyl; and
Z 1 is hydroxyl, carboxyl, thiol, amino, or amido.
5. The coated substrate of claim 1 , wherein the third repeating unit is derived from a monomer of formula (4):
wherein,
R d is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
L 3 is a single bond, a substituted or unsubstituted C 1-30 alkylene, a substituted or unsubstituted C 3-30 cycloalkylene, a substituted or unsubstituted C 3-30 heterocycloalkylene, a substituted or unsubstituted C 6-30 arylene, a substituted or unsubstituted divalent C 7-30 arylalkyl, a substituted or unsubstituted C 3-30 heteroarylene, or a substituted or unsubstituted divalent C 4-30 heteroarylalkyl; and
Z 2 is epoxy or lactone.
6. The coated substrate of claim 1 , wherein the polymer comprises:
5 to 60 mole percent of the first repeating unit;
20 to 65 mole percent of the second repeating unit; and
20 to 65 mole percent of the third repeating unit,
each based on 100 mole percent of total repeating units in the polymer.
7. The coated substrate of claim 1 , wherein the underlayer coating composition further comprises:
an acid catalyst; and
a solvent.
8. The coated substrate of claim 1 , wherein the underlayer coating composition further comprises an additional polymer that is different from the polymer.
9. A patterning method, comprising:
applying a layer of an underlayer coating composition on a substrate;
baking the underlayer coating composition to form an underlayer film;
applying a layer of a photoresist composition on the underlayer film to form a photoresist layer;
pattern-wise exposing the photoresist layer to activating radiation; and
developing the exposed photoresist layer to provide a resist relief image,
wherein the underlayer coating composition comprises a polymer comprising:
a first repeating unit comprising an amino group protected by an alkoxycarbonyl group;
a second repeating unit comprising a nucleophilic group; and
a third repeating unit comprising a crosslinkable group,
wherein the first repeating unit, the second repeating unit, and the third repeating unit are different from each other.
10. The method of claim 9 , wherein the first repeating unit is derived from a monomer of formula (1):
wherein,
R a is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
each R k is independently a halogen, a hydroxy, a carboxylic acid or ester, a thiol, a straight chain or branched C 1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 fluorocycloalkenyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a monocyclic or polycyclic C 6-20 aryl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted;
A is a single bond or a C 1-2 alkylene;
R 1 , R 2 , and R 3 are each independently a straight chain or branched C 1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a straight chain or branched C 2-20 alkenyl, a monocyclic or polycyclic C 3-20 cycloalkenyl, a monocyclic or polycyclic C 3-20 heterocycloalkenyl, a monocyclic or polycyclic C 6-20 aryl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted, and any two of R 1 , R 2 , and R 3 together optionally form a ring; and
n is an integer of 0 to 11.
11. The method of claim 9 , wherein the first repeating unit is derived from a monomer of formula (2):
wherein,
R b is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
L 1 is a linking group; and
R 4 , R 5 , and R 6 are each independently a straight chain or branched C 1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, a monocyclic or polycyclic C 3-20 heterocycloalkyl, a straight chain or branched C2-20 alkenyl, a monocyclic or polycyclic C 3-20 cycloalkenyl, a monocyclic or polycyclic C 3-20 heterocycloalkenyl, a monocyclic or polycyclic C 6-20 aryl, or a monocyclic or polycyclic C 4-20 heteroaryl, each of which is substituted or unsubstituted, and any two of R 4 , R 5 , and R 6 together optionally form a ring.
12. The method of claim 9 , wherein the second repeating unit is derived from a monomer of formula (3):
wherein
R c is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
L 2 is a substituted or unsubstituted C 1-30 alkylene, a substituted or unsubstituted C 3-30 cycloalkylene, a substituted or unsubstituted C 3-30 heterocycloalkylene, a substituted or unsubstituted C 6-30 arylene, a substituted or unsubstituted divalent C 7-30 arylalkyl, a substituted or unsubstituted C 3-30 heteroarylene, or a substituted or unsubstituted divalent C 4-30 heteroarylalkyl; and
Z 1 is hydroxyl, carboxyl, thiol, amino, or amido.
13. The method of claim 9 , wherein the third repeating unit is derived from a monomer of formula (4):
wherein,
R d is hydrogen, fluorine, a substituted or unsubstituted C 1-5 alkyl, or a substituted or unsubstituted C 1-5 fluoroalkyl;
L 3 is a single bond, a substituted or unsubstituted C 6-30 alkylene, a substituted or unsubstituted C 3-30 cycloalkylene, a substituted or unsubstituted C 3-30 heterocycloalkylene, a substituted or unsubstituted C 6-30 arylene, a substituted or unsubstituted divalent C 7-30 arylalkyl, a substituted or unsubstituted C 3-30 heteroarylene, or a substituted or unsubstituted divalent C 4-30 heteroarylalkyl; and
Z 2 is epoxy or lactone.
14. The method of claim 9 , wherein the polymer comprises:
5 to 60 mole percent of the first repeating unit;
20 to 65 mole percent of the second repeating unit; and
20 to 65 mole percent of the third repeating unit,
each based on 100 mole percent of total repeating units in the polymer.
15. The method of claim 9 , wherein the underlayer coating composition further comprises:
an acid catalyst; and
a solvent.
16. The method of claim 9 , wherein the underlayer coating composition further comprises an additional polymer that is different from the polymer.
17. The method of claim 9 , wherein the activating radiation comprises a wavelength of 193 nanometers.
18. The method of claim 9 , wherein the activating radiation comprises an EUV wavelength.