Brush polymer, photoresist composition including the same, and method of manufacturing integrated circuit device

1 . A brush polymer for a photoresist, the brush polymer comprising a core and a plurality of side polymer chains, the plurality of side polymer chains being bonded to the core and extending from the core to form a bottle-brush polymer or a star-brush polymer, together with the core,

wherein:

each of the plurality of side polymer chains includes a first repeating unit represented by Formula 1 and a second repeating unit represented by Formula 2:

in Formulae 1 and 2,

R 1 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group,

R 2 is a C3 to C30 fluoroaliphatic group including a hydroxyl group,

R 3 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group, and

R 4 is a C2 to C20 organic group including an oxygen atom,

wherein the first repeating unit represented by Formula 1 is different than the second repeating unit represented by Formula 2, and

wherein each of the plurality of side polymer chains has a terminal group distal to the core.

2 . The brush polymer as claimed in claim 1 , wherein:

in Formula 1, R 2 is represented by Chemical Formula 1:

*—R 21 —(R 22 ) k   [Chemical Formula 1]

in Chemical Formula 1,

R 21 is a C1 to C20 substituted or unsubstituted linear alkylene group, a C3 to C20 substituted or unsubstituted branched alkylene group, a C3 to C20 substituted or unsubstituted cycloalkylene group, or a combination thereof,

R 22 is a C3 to C6 hydroxyalkyl group in which at least one hydrogen atom of the alkyl group of the hydroxyalkyl group is substituted with a fluorine atom, and

k is 1 or 2.

3 . The brush polymer as claimed in claim 1 , wherein, in Formula 1, R 2 is —C(CF 3 ) 2 OH, —C(C 2 F 5 ) 2 OH, —C(CF 3 )(CH 3 )OH, or —CH(CF 3 )OH.

4 . The brush polymer as claimed in claim 1 , wherein, in Formula 2, R 4 is a hydroxyl group (OH), a hydroxyalkyl group, an oxyethylene group, a carboxyl group (COOH), a carbonyl group (CO), an aldehyde group (CHO), a lactone group, a phenol group, an oxo group (O═), or a combination thereof.

5 . The brush polymer as claimed in claim 1 , wherein:

the brush polymer is the bottle-brush polymer,

the core has a main chain including polynorbornene, and

a maximum length of the main chain is greater than a maximum length of each of the plurality of side polymer chains.

6 . The brush polymer as claimed in claim 1 , wherein:

each of the plurality of side polymer chains has a terminal group at a terminal end thereof, and

the terminal group includes a bromine atom or an organic group including a sulfur atom.

7 . The brush polymer as claimed in claim 1 , wherein:

the brush polymer is the star-brush polymer,

the core has a pentaerythritol core structure, and

each of the plurality of side polymer chains extends from the core in a radial direction.

8 . The brush polymer as claimed in claim 1 , wherein:

the brush polymer has a structure represented by Formula 3:

in Formula 3,

R 1 to R 4 are defined the same as those of Formulae 1 and 2,

m is an integer of 5 to 100,

p and q are each independently an integer of 1 to 50, and

T is a bromine atom or an organic group including a sulfur atom.

9 . The brush polymer as claimed in claim 1 , wherein:

the brush polymer has a structure represented by Formula 4:

in Formula 4,

R 1 to R 4 are defined the same as those of Formulae 1 and 2,

m is an integer of 5 to 100,

p and q are each independently an integer of 1 to 50, and

T is a bromine atom or an organic group including a sulfur atom.

10 . The brush polymer as claimed in claim 1 , wherein:

the brush polymer has a structure represented by Formula 5:

in Formula 5,

R 1 to R 4 are defined the same as those of Formulae 1 and 2, and

p and q are each independently an integer of 1 to 50.

11 . The brush polymer as claimed in claim 1 , wherein:

the brush polymer has a structure represented by Formula 6:

in Formula 6,

R 1 to R 4 are defined the same as those of Formulae 1 and 2, and

p and q are each independently an integer of 1 to 50.

12 . A photoresist composition, comprising:

a brush polymer for a photoresist, the brush polymer including a core and a plurality of side polymer chains, the plurality of side polymer chains being bonded to the core and extending from the core to form a bottle-brush polymer or a star-brush polymer, together with the core;

a chemically amplified polymer;

a photoacid generator (PAG); and

a solvent,

wherein:

each of the plurality of side polymer chains includes a first repeating unit represented by Formula 1 and a second repeating unit represented by Formula 2:

in Formulae 1 and 2,

R 1 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group,

R 2 is a C3 to C30 fluoroaliphatic group including a hydroxyl group,

R 3 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group, and

R 4 is a C2 to C20 organic group including an oxygen atom,

wherein the first repeating unit represented by Formula 1 is different than the second repeating unit represented by Formula 2, and

wherein each of the plurality of side polymer chains has a terminal group distal to the core.

13 . The photoresist composition as claimed in claim 12 , wherein:

the brush polymer is the bottle-brush polymer,

the core has a main chain including polynorbornene,

each of the plurality of side polymer chains has a terminal group at a terminal end thereof, and

the terminal group includes a bromine atom or an organic group including a sulfur atom.

14 . The photoresist composition as claimed in claim 12 , wherein:

the brush polymer is the star-brush polymer,

the core has a pentaerythritol core structure, and

each of the plurality of side polymer chains extends from the core in a radial direction.

15 . The photoresist composition as claimed in claim 12 , wherein:

the brush polymer for photoresist has a structure represented by Formula 3:

in Formula 3,

R 1 to R 4 are defined the same as those of Formulae 1 and 2,

m is an integer of 5 to 100,

p and q are each independently an integer of 1 to 50, and

T is a bromine atom or an organic group including a sulfur atom.

16 . The photoresist composition as claimed in claim 12 , wherein:

the brush polymer has a structure represented by Formula 4:

in Formula 4,

R 1 to R 4 are defined the same as those of Formulae 1 and 2,

m is an integer of 5 to 100,

p and q are each independently an integer of 1 to 50, and

T is a bromine atom or an organic group including a sulfur atom.

17 . The photoresist composition as claimed in claim 12 , wherein:

the brush polymer has a structure represented by Formula 5:

in Formula 5,

R 1 to R 4 are defined the same as those of Formulae 1 and 2, and

p and q are each independently an integer of 1 to 50.

18 . The photoresist composition as claimed in claim 12 , wherein:

the brush polymer has a structure represented by Formula 6:

in Formula 6,

R 1 to R 4 are defined the same as those of Formulae 1 and 2, and

each of p and q is an integer ranging from 1 to 50.

19 . A method of manufacturing an integrated circuit device, the method comprising:

forming a photoresist film on an underlying film by using a photoresist composition that includes:

a brush polymer, the brush polymer including a core and a plurality of side polymer chains, the plurality of side polymer chains being bonded to the core and extending from the core to form a bottle-brush polymer or a star-brush polymer, together with the core,

a chemically amplified polymer,

a photoacid generator (PAG), and

a solvent;

forming a surface-modified photoresist film having a hydrophilic surface portion, the hydrophilic surface portion being formed by segregating the brush polymer from the chemically amplified polymer in the photoresist film and distributing the brush polymers at a surface of the photoresist film, which is distal to the underlying film;

generating an acid from the PAG by exposing a first area of the surface-modified photoresist film, which includes a portion of the hydrophilic surface portion, and deprotecting the chemically amplified polymer with the acid;

pre-wetting the hydrophilic surface portion of the exposed first area of the surface-modified photoresist film with deionized water;

removing the exposed first area of the surface-modified photoresist film by using a developer to form a photoresist pattern including a non-exposed area of the surface-modified photoresist film; and

processing the underlying film by using the photoresist pattern,

wherein:

each of the plurality of side polymer chains includes a first repeating unit represented by Formula 1 and a second repeating unit represented by Formula 2,

in Formulae 1 and 2,

R 1 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group,

R 2 is a C3 to C30 fluoroaliphatic group including a hydroxyl group,

R 3 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group, and

R 4 is a C2 to C20 organic group including an oxygen atom,

wherein the first repeating unit represented by Formula 1 is different than the second repeating unit represented by Formula 2, and

wherein each of the plurality of side polymer chains has a terminal group distal to the core.

20 . The method as claimed in claim 19 , wherein:

the brush polymer includes a brush polymer having a structure represented by Formula 3, Formula 4, Formula 5, Formula 6, or a combination thereof,

[Formula 3]

in Formulae 3 to 6,

m is an integer of 5 to 100,

p and q are each independently an integer of 1 to 50,

T is a bromine atom or an organic group including a sulfur atom,

R 1 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group,

R 2 is a C3 to C30 fluoroaliphatic group including a hydroxyl group,

R 3 is a hydrogen atom, an unsubstituted methyl group, a fluorine atom, or a trifluoromethyl group, and

R 4 is a C2 to C20 organic group including an oxygen atom.