Polymer for preparing resist underlayer film, resist underlayer film composition containing the polymer and method for manufacturing semiconductor device using the composition

1. A resist underlayer film composition comprising:

a polymer for preparing a resist underlayer film including a repeating unit represented by Chemical Formula 1 below;

an organic solvent; and

a crosslinking agent comprising at least one selected from compounds represented by Chemical Formulas 4 to 10 below:

in Chemical Formula 1,

Ar is (C10-C100)arylene, wherein the arylene of Ar may be further substituted with one or more substituents selected from the group consisting of (C1-C20)alkyl, (C3-C20)cycloalkyl, (C2-C20)alkenyl, (C3-C20)cycloalkenyl, (C2-C20)alkynyl, 4- to 10-membered heterocycloalkyl, (C6-C20)aryl, (C3-C20)heteroaryl, halogen, cyano, hydroxy, (C1-C20)alkoxy, (C3-C20)cycloalkoxy, (C6-C20)aryloxy, (C1-C20)alkylthio, (C3-C20)cycloalkylthio, (C6-C20)arylthio, (C1-C20)alkylcarbonyl, (C2-C20)alkenylcarbonyl, (C6-C20)arylcarbonyl, (C3-C20)cycloalkylcarbonyl, and (C3-C20)cycloalkenylcarbonyl;

L is

Ar 1 and Ar 2 are each independently (C6-C30)arylene;

Ar 3 is a trivalent (C6-C30)arylene;

Ar 4 is (C6-C30)aryl;

the arylene of Ar 1 , Ar 2 and Ar 3 , and the aryl of Ar 4 may be further substituted with one or more substituents selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C6-C20)aryl, (C1-C10)alkoxy, (C6-C20)aryloxy, (C1-C10)alkyl(C6-C20)aryl and (C6-C20)aryl(C1-C10)alkyl,

R is (C1-C20)alkyl or (C3-C10)cycloalkyl, and the alkyl or cycloalkyl of R may be further substituted with one or more substituents selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl and (C6-C20)aryl;

w is an integer of 1 to 5; and

the heteroaryl and the heterocycloalkyl include one or more heteroatoms selected from B, N, O, S, P(═O), Si, Se and P,

in Chemical Formula 6, R 21 and R 22 are each independently hydroxy or (C1-C3)alkoxy, and R 23 is (C1-C10)alkyl,

in Chemical Formula 8, R 24 , R 25 , R 26 and R 27 are each independently hydroxy or (C1-C3)alkoxy, and R 28 and R 29 are each independently hydrogen, (C1-C10)alkyl or halo(C1-C10)alkyl,

in Chemical Formula 9, R 30 , R 31 , R 32 and R 33 are each independently hydroxy or (C1-C3)alkoxy,

in Chemical Formula 10, R 34 , R 35 , R 36 , R 37 , R 38 and R 39 are each independently hydroxy or (C1-C3)alkoxy.

2. The resist underlayer film composition of claim 1 , wherein the polymer for preparing a resist underlayer film includes a repeating unit represented by Chemical Formula 2 or 3 below:

in Chemical Formula 2 or 3, Ar 1 , Ar 2 , Ar 3 , Ar 4 , R and w are the same as defined in Chemical Formula 1 above of claim 1 ;

Ar 11 , Ar 12 , Y and Z are each independently (C6-C20)arylene;

the arylene of Ar 11 and Ar 12 may be further substituted with one or more substituents selected from the group consisting of (C1-C20)alkyl, hydroxy, (C1-C20)alkoxy, and (C6-C20)aryl, and

the arylene of Y and Z may be further substituted with one or more substituents selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C2-C10)alkenyl, (C3-C10)cycloalkenyl, (C2-C10)alkynyl, 4- to 10-membered heterocycloalkyl, (C6-C20)aryl, (C3-C20)heteroaryl, halogen, cyano, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C6-C20)aryloxy, (C1-C10)alkylthio, (C3-C10)cycloalkylthio, (C6-C20)arylthio, (C1-C10)alkylcarbonyl, (C2-C10)alkenylcarbonyl, (C6-C20)arylcarbonyl, (C3-C10)cycloalkylcarbonyl, and (C3-C10)cycloalkenylcarbonyl.

3. The resist underlayer film composition of claim 1 , wherein the polymer for preparing a resist underlayer film including the repeating unit represented by Chemical Formula 1 has an amount of 0.5 to 50 wt % and the organic solvent has an amount of 50 to 99.5 wt %, based on total amount of the resist underlayer film composition.

4. The resist underlayer film composition of claim 1 , wherein the organic solvent is at least one selected from cyclohexanone, 2-heptanone, propyleneglycol monomethyl ether, propyleneglycol monomethyl acetate, propyleneglycol monomethyl ether acetate, gamma-butyrolactone, ethyl lactate, dimethyl sulfoxide, dimethyl acetamide, and N-methyl pyrrolidone.

5. The resist underlayer film composition of claim 1 , further comprising at least one additive selected from acid catalysts, acid generators, antifoaming agents, and surfactants.

6. The resist underlayer film composition of claim 5 , wherein the acid catalyst or the acid generator is at least one selected from compounds represented by Chemical Formulas 11 to 16 below:

7. A method for manufacturing semiconductor device comprising:

1) forming a resist underlayer film by applying and heating the resist underlayer film composition of claim 1 on a substrate;

2) forming a photoresist film on the resist underlayer film of step 1);

3) forming photoresist patterns by exposing and developing the photoresist film of step 2);

4) etching the resist underlayer film by using the photoresist patterns of step 3) as an etching mask to thereby expose the substrate in a form of the patterns; and

5) etching an exposed part of the substrate,

wherein the exposing is performed by using at least one selected from the group consisting of an excimer laser scanner, electron beam, X-ray, and ion beam, and

wherein the development is performed by using an alkaline aqueous solution.

8. The method for manufacturing semiconductor device of claim 7 , further comprising, before step 2), forming an inorganic resist underlayer film or a bottom anti-refractive coating (BARC) film on the resist underlayer film of step 1).

9. The method for manufacturing semiconductor device of claim 7 , wherein in the forming of the photoresist patterns of step 3), heating is performed before and/or after the exposing, respectively.

10. A polymer for preparing a resist underlayer film comprising:

a repeating unit represented by Chemical Formula 2 or 3 below:

in Chemical Formula 2 or 3

is selected from the following structures:

R 1 and R 2 are hydroxy;

R 3 and R 4 are each independently hydrogen, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C2-C10)alkenyl, (C3-C10)cycloalkenyl, (C2-C10)alkynyl, 4- to 10-membered heterocycloalkyl, (C6-C20)aryl, (C3-C20)heteroaryl, halogen, cyano, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C6-C20) aryloxy, (C1-C10)alkylthio, (C3-C10)cycloalkylthio, (C6-C20) arylthio, (C1-C10)alkylcarbonyl, (C2-C10)alkenylcarbonyl, (C6-C20)arylcarbonyl, (C3-C10)cycloalkylcarbonyl, or (C3-C10)cycloalkenylcarbonyl;

m and n are each independently an integer of 0 to 4;

Ar 1 and Ar 2 are each independently (C6-C30)arylene;

Ar 3 is a trivalent (C6-C30)arylene;

Ar 4 is (C6-C30)aryl;

the arylene of Ar 1 , Ar 2 and Ar 3 , and the aryl of Ar 4 may be further substituted with one or more substituents selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C6-C20)aryl, (C1-C10)alkoxy, (C6-C20)aryloxy, (C1-C10)alkyl(C6-C20)aryl and (C6-C20)aryl(C1-C10)alkyl,

R is (C1-C20)alkyl or (C3-C10)cycloalkyl, and the alkyl or cycloalkyl of R may be further substituted with one or more substituents selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl and (C6-C20)aryl;

w is an integer of 1 to 5; and

the heteroaryl and the heterocycloalkyl include one or more heteroatoms selected from B, N, O, S, P(═O), Si, Se and P.

11. A polymer for preparing a resist underlayer film comprising:

a repeating unit represented by Chemical Formula 2 or 3 below:

in Chemical Formula 2 or 3,

is the following structure:

R 1 and R 2 are hydroxy;

R 3 and R 4 are each independently hydrogen, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C2-C10)alkenyl, (C3-C10)cycloalkenyl, (C2-C10)alkynyl, 4- to 10-membered heterocycloalkyl, (C6-C20)aryl, (C3-C20)heteroaryl, halogen, cyano, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C6-C20)aryloxy, (C1-C10)alkylthio, (C3-C10)cycloalkylthio, (C6-C20)arylthio, (C1-C10)alkylcarbonyl, (C2-C10)alkenylcarbonyl, (C6-C20)arylcarbonyl, (C3-C10)cycloalkylcarbonyl, or (C3-C10)cycloalkenylcarbonyl; and

m and n are each independently an integer of 0 to 4;

Ar 1 and Ar 2 are each independently (C6-C30)arylene;

Ar 3 is a trivalent (C6-C30)arylene;

Ar 4 is (C6-C30)aryl;

the arylene of Ar 1 , Ar 2 and Ar 3 , and the aryl of Ar 4 may be further substituted with one or more substituents selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C6-C20)aryl, (C1-C10)alkoxy, (C6-C20)aryloxy, (C1-C10)alkyl(C6-C20)aryl and (C6-C20)aryl(C1-C10)alkyl,

R is (C1-C20)alkyl or (C3-C10)cycloalkyl, and the alkyl or cycloalkyl of R may be further substituted with one or more substituents selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl and (C6-C20)aryl;

w is an integer of 1 to 5; and

the heteroaryl and the heterocycloalkyl include one or more heteroatoms selected from B, N, O, S, P(═O), Si, Se and P.