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

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

a repeating unit represented by Chemical Formula 1 below:

in Chemical Formula 1,

Ar is

Z 1 to Z 4 are each independently C═O, NR a , O, S or CR b R c ; R a to R c are each independently hydrogen, (C1-C10)alkyl, halogen, (C3-C10)cycloalkyl, or (C6-C20)aryl, and the alkyl, cycloalkyl, and aryl may be further substituted with one or more substituents selected from the group consisting of halogen, (C1-C10)alkyl, halo(C1-C10)alkyl, (C3-C10)cycloalkyl, and (C6-C20)aryl;

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

L is

Ar 3 and Ar 4 are each independently (C6-C30)arylene;

Ar 5 is trivalent (C6-C30)arylene;

Ar 6 is (C6-C30)aryl;

the arylene of Ar 3 , Ar 4 and Ar 5 , and the aryl of Ar 6 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 hydrogen, (C1-C20)alkyl, (C3-C10)cycloalkyl or (C6-C20)aryl, and the alkyl, cycloalkyl, or aryl 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;

u is an integer of 0 or 1; and

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

2. The polymer for preparing a resist underlayer film of claim 1 , wherein the polymer includes a repeating unit represented by Chemical Formula 2, 3, or 4 below:

in Chemical Formula 2, 3, or 4, Ar, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , R, w and u are the same as defined in Chemical Formula 1 above of claim 1 .

3. The polymer for preparing a resist underlayer film of claim 2 , wherein Ar 3 and Ar 4 are each independently phenylene, naphthylene, biphenylene, fluorenylene, triphenylene, anthrylene, pyrenylene, chrysenylene or naphthacenylene; Ar 5 is trivalent phenylene, naphthylene, biphenylene, fluorenylene, triphenylene, anthrylene, pyrenylene, chrysenylene or naphthacenylene; Ar 6 is phenyl, naphthyl, biphenyl, fluorenyl, triphenyl, anthryl, pyrenyl, chrysenyl or naphthacenyl; R is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, benzyl, naphthylmethyl, anthrylmethyl, pyrenylmethyl, triphenylmethyl or tolyl; w is an integer 1 or 2; and u is an integer of 0 or 1.

4. The polymer for preparing a resist underlayer film of claim 1 , wherein the polymer has a weight average molecular weight of 500 or more.

5. A resist underlayer film composition comprising:

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

an organic solvent:

in Chemical Formula 1,

Ar is

Z 1 to Z 4 are each independently C═O, NR a , O, S or CR b R c ; R a to R c are each independently hydrogen, (C1-C10)alkyl, halogen, (C3-C10)cycloalkyl, or (C6-C20)aryl, and the alkyl, cycloalkyl, and aryl may be further substituted with one or more substituents selected from the group consisting of halogen, (C1-C10)alkyl, halo(C1-C10)alkyl, (C3-C10)cycloalkyl, and (C6-C20)aryl;

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

L is

Ar 3 and Ar 4 are each independently (C6-C30)arylene;

Ar 5 is trivalent (C6-C30)arylene;

Ar 6 is (C6-C30)aryl;

the arylene of Ar 3 , Ar 4 and Ar 5 , and the aryl of Ar 6 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 hydrogen, (C1-C20)alkyl, (C3-C10)cycloalkyl or (C6-C20)aryl, and the alkyl, cycloalkyl, or aryl 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;

u is an integer of 0 or 1; and

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

6. The resist underlayer film composition of claim 5 , wherein the polymer for preparing a resist underlayer film includes a repeating unit represented by Chemical Formula 2, 3 or 4 below:

in Chemical Formula 2, 3, or 4, Ar, Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , R, w and u are the same as defined in Chemical Formula 1 above of claim 5 .

7. The resist underlayer film composition of claim 5 , 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.

8. The resist underlayer film composition of claim 5 , 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.

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

10. The resist underlayer film composition of claim 9 , wherein the crosslinking agent is at least one selected from compounds represented by Chemical Formulas 5 to 11 below:

in Chemical Formula 7, R 21 and R 22 are each independently hydroxy or (C1-C3)alkoxy, and R 23 is (C1-C10)alkyl,

in Chemical Formula 9, 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 10, R 30 , R 31 , R 32 and R 33 are each independently hydroxy or (C1-C3)alkoxy,

in Chemical Formula 11, R 34 , R 35 , R 36 , R 37 , R 38 and R 39 are each independently hydroxy or (C1-C3)alkoxy.

11. The resist underlayer film composition of claim 9 , wherein the acid catalyst or the acid generator is at least one selected from compounds represented by Chemical Formulas 12 to 17 below:

12. A method for manufacturing semiconductor device comprising:

1) forming a resist underlayer film by applying and heating the resist underlayer film composition of claim 5 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 far-ultraviolet rays, electron beam, X-ray, and ion beam, and

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

13. The method for manufacturing semiconductor device of claim 12 , 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).

14. The method for manufacturing semiconductor device of claim 12 , wherein in the forming of the photoresist patterns of step 3), heating is performed before and/or after the exposing, respectively.