KR20080089182A - Anti-reflective composition - Google Patents

Abstract

A composition for an anti-reflective film is provided to absorb well far UV rays passing through a photoresist film, thereby reducing sine waves, and to form a pattern having an excellent pattern shape. A composition for an anti-reflective film comprises a polymer having repeating units selected from the group consisting of the following formulae 1-6 and a combination thereof. In formula 1, R1 is anthracene methyl; R2 and R3 are the same or different and each represents H, methyl or ethyl; R4, R5 and R6 are the same or different. and represent H or methyl; the weight ratio of l:m;n is 0.1-8:0.1-3:1 when n is not 0, or the weight ratio of l:m is 1-10:1 when n is 0. In formula 2, R7 is anthracene methyl; R8, R9 and R10 are the same or different, and represent methyl or ethyl; and the weight ratio of a:b:c is 0.1-8:1:0.1-5. In formula 3, R11 is anthracene methyl; R12 and R13 are the same or different, and represent H, methyl or ethyl; and the weight ratio of d:e is 1:0.1-5. In formula 4, R14 is H, methyl, ethyl or t-butyl; R15 is H, methyl or t-butyl; R16 is H, methyl or ethyl, and the weight ratio of f:g:h is 1-10:1_1-10 when g is not 0, or the weight ratio of f:h is 1:0.1-10 when g is 0. In formula 5, R17 is anthracene methyl; R18 is a fluorine-containing C1-C20 alkyl; R19, R20 and R21 are the same or different, and represent H, methyl or ethyl; x is an integer of 1-5; and the weight ratio of I:j:k is1:0.01-1:0.1-10. In formula 6, R22 is a fluorine-containing C1-C20 alkyl; r23 and R24 are the same or different, and represent H, methyl or ethyl; and the weight ratio of o:p is 1:0.1-10.

Description

Anti-reflective composition

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer for an antireflection film that can prevent reflection in a lower layer of a photoresist film during an ultrafine pattern formation process in a semiconductor manufacturing process, and more particularly to an antireflection film composition comprising such a polymer. The present invention relates to a polymer having excellent ultraviolet absorption and capable of significantly reducing a standing wave effect and a composition for an antireflection film comprising the same.

In the ultra-fine pattern forming process, CD (Critical Dimension) by standing wave and reflective notching due to the optical properties of the lower layer of the photoresist layer and the variation of the resist thickness and diffraction and reflected light from the lower layer Fluctuations inevitably occur. Therefore, an anti-reflection film that can prevent reflection in the lower layer by introducing a material that absorbs light well in the wavelength range of light used as the exposure source can be used in the microfabrication process by laminating it under the photoresist.

When the ultraviolet light is received from the light source, light penetrating the photoresist film is scattered or reflected on the lower part of the photoresist film. The organic anti-reflective film absorbs the scattered or reflected light and directly affects the microprocessing of the photoresist. Given.

The anti-reflection film can be largely classified into an inorganic antireflection film and an organic antireflection film according to the type of material, and can be divided into an absorption antireflection film and an interferometer antireflection film according to the mechanism.

In the micropattern forming process using i line (365 nm), an inorganic antireflection film has been mainly used. Among these, TiN and amorphous carbon are used as the absorption antireflection film, and SiON is mainly used as the interferometer antireflection film. In addition, in the ultrafine pattern formation using KrF light (248 nm), SiON, which is an inorganic antireflection film, was mainly used, but an organic antireflection film was often used.

However, in the ultrafine pattern formation process using ArF light, no suitable antireflection film has been developed yet. In the case of the inorganic anti-reflection film, a material for controlling the interference phenomenon at 193 nm as a light source has not been announced yet, and efforts have recently been made to develop an organic material that can be used as an anti-reflection film.

Generally, the basic conditions that the organic anti-reflective coating should have are as follows.

First, there should be no phenomenon that the antireflection film is dissolved and peeled off by the photoresist solvent during the process application. To this end, the molded film must be designed to achieve a crosslinked structure, and chemicals should not be generated at this time.

Second, there should be no entry of chemicals such as acids or amines from the anti-reflection film. In the case of positive photoresist, when acid is migrated from the anti-reflection film to the photoresist film of the non-exposed part, undercutting occurs at the bottom of the photoresist pattern, and when base such as amine is transferred to the photoresist film, footing is performed. ) Tends to cause symptoms.

Third, the anti-reflection film must have a relatively fast etching rate compared to the upper photoresist film, so that the etching process can be performed smoothly using the photoresist film as a mask during etching.

Fourth, the anti-reflection film should be able to function as an anti-reflection film sufficiently thin as possible.

Accordingly, the present inventors have continued research to develop a suitable organic antireflection film resin, and have completed the present invention by developing an antireflection film resin that satisfies all the above requirements.

An object of the present invention is to provide an antireflection film polymer suitable for a lithography process, an antireflection film composition comprising the same, and a method of forming a photoresist pattern using the same.

The present invention provides an anti-reflection film polymer having excellent far-ultraviolet absorption power, which can significantly reduce sinusoidal effects, an anti-reflection film composition comprising the same, and a method of forming a photoresist pattern using the same.

When the antireflection film is formed by using the composition for antireflection film of the present invention, the sine wave effect is absorbed very well by absorbing the light in the far ultraviolet region that has passed through the photoresist film without being affected by dissolution in the photoresist solution applied thereon. Can be significantly reduced.

Therefore, the patterns formed by using the anti-reflection film of the present invention have a very excellent pattern shape, thereby further contributing to the high integration of the semiconductor.

In the present invention, first, a polymer for an antireflection film including a repeating unit selected from the group consisting of the following Chemical Formulas 1 to 6 and combinations thereof is provided:

[Formula 1]

In Chemical Formula 1,

R ₁ is an anthracene methyl group,

R ₂ and R ₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl;

R ₄ , R ₅ and R ₆ are the same as or different from each other, and each is hydrogen or a methyl group,

When n = 0, l: m: n is 0.1 to 8: 0.1 to 3: 1 by weight,

When n = 0, l: m is 1-10: 1 by weight ratio.

[Formula 2]

In Chemical Formula 2,

R ₇ is an anthracene methyl group,

R ₈ , R ₉ and R ₁₀ are the same as or different from each other, and each is hydrogen, methyl or ethyl;

a: b: c is 0.1-8: 1: 0.1-5 by weight ratio.

[Formula 3]

In Chemical Formula 3,

R ₁₁ is an anthracene methyl group,

R ₁₂ and R ₁₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl;

d: e is 1: 0.1-5 by weight ratio.

[Formula 4]

In Chemical Formula 4,

R ₁₄ is hydrogen, methyl group, ethyl group or t-butyl group,

R ₁₅ is hydrogen, methyl or t-butyl group,

R ₁₆ is hydrogen, a methyl group or an ethyl group,

If g = 0 is not, f: g: h is 1 to 10: 1: 1 to 10 by weight,

When g = 0, f: h is 1: 0.1-10 by weight ratio.

[Formula 5]

In Chemical Formula 5,

R ₁₇ is an anthracene methyl group,

R ₁₈ is a C ₁ to C ₂₀ alkyl group containing fluorine,

R ₁₉ , R ₂₀ and R ₂₁ are the same as or different from each other, and are each hydrogen, methyl or ethyl group,

x represents an integer between 1 and 5,

i: j: k is 1: 0.01-1: 0.1-10 by weight ratio.

[Formula 6]

In Chemical Formula 6,

R ₂₂ is a C ₁ to C ₂₀ alkyl group containing fluorine,

R ₂₃ and R ₂₄ are the same as or different from each other, and each is hydrogen, methyl or ethyl;

o: p is 1: 0.1-10 by weight ratio.

The C ₁ to C ₂₀ alkyl group containing the fluorine may be an eicossafluorodecyl group, a heptadecafluorodecyl group, a heptafluorobutyl group, a hexafluorobutyl group, a hexafluoroisopropyl group or an octafluorophene. It is preferable that they are a methyl group, a pentadecafluorooctyl group, a pentafluoropropyl group, a tetrafluoropropyl group, a trifluoroethyl group, a dodecafluoroheptyl group, or a pentafluorooctyl group.

In addition, the repeating unit is poly (9-anthracene methyl methacrylate / methyl methacrylate / acrolein dimethyl acetal), poly (9- anthracene methyl methacrylate / methyl methacrylate / acrolein), poly (acrolein / methyl methacrylate) Acrylate), polyhydroxystyrene, poly (9-anthracenemethylmethacrylate / 2-hydroxyethylmethacrylate / hexafluorobutylmethacrylate) or poly (acrolein / hexafluorobutylmethacrylate) It may include one or more polymers selected.

In addition, the present invention provides a composition for an anti-reflection film comprising at least one polymer, a thermal acid generator and an organic solvent comprising a repeating unit selected from the group consisting of Formulas 1 to 6 and combinations thereof.

In particular, the polymer of Formula 1 and Formula 2 is a form in which the monomer that acts as a crosslinking is directly bonded in the polymer chain.

The polymer of Formula 3 is a polymer that acts as a crosslinking agent.

It is preferable that the polymer of Formula 4 is polyhydroxystyrene corresponding to the case where g and h which are repeating units are 0.

The polymer of Chemical Formula 5 is a resin which is planarized well while absorbing light having wavelengths of 248 nm and 193 nm.

The polymer of the formula (6) is a resin that facilitates the cross-linking and planarization well, because it contains a fluorine-based monomer has a small surface tension and has a feature that is well embedded in the contact hole when raised to a high temperature after coating. In addition, the fluorine-based monolayer slows down the crosslinking reaction rate, thereby providing time for sufficiently filling the contact holes.

In addition, the composition comprises a mixture of a polymer comprising a repeating unit of formula 1 and a polymer comprising a repeating unit of formula 4;

Or a mixture of a polymer comprising a repeating unit of formula 2 and a polymer comprising a repeating unit of formula 4;

A mixture comprising a polymer comprising a repeating unit of formula 3, a polymer comprising a repeating unit of formula 4 and a polymer comprising a repeating unit of formula 5;

A mixture comprising a polymer comprising a repeating unit of formula 1, a polymer comprising a repeating unit of formula 3 and a polymer comprising a repeating unit of formula 4;

It is preferred to include a mixture of a polymer comprising a repeating unit of formula (5) and a polymer comprising a repeating unit of formula (6).

The thermal acid generator is preferably a compound of the formula (7).

[Formula 7]

In Formula 7, R is a fluorine group, a chlorine group, hydrogen, a methyl group, or an ethyl group.

The organic solvent is a solvent such as methyl 3-methoxypropionate (MMP), ethyl 3-ethoxypropionate (EEP), propylene glycol methyl ether acetate (PGMEA) or cyclohexanone, these solvents It may be used alone or in combination.

In the present invention,

(a) applying an antireflection film composition comprising the antireflection film polymer, a thermal acid generator, and an organic solvent of the present invention on an etched layer;

(b) hardening by baking process to form an anti-reflection film;

(c) applying a photoresist on the antireflection film, exposing the photoresist, and developing the photoresist pattern to form a photoresist pattern; And

and (d) etching the anti-reflection film and the etched layer using the photoresist pattern as an etch mask to form an etched layer pattern.

In the process, the baking process of step (b) is preferably carried out for 1 to 5 minutes at a temperature of 150 to 250 ℃.

The exposure process is performed using a light source such as ArF, KrF, F ₂ , EUV, E-beam, X-ray or ion beam.

In addition, the present invention provides a semiconductor device manufactured by the pattern forming method.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the content of the present invention is not limited by the following examples.

Example 1 Poly (9- Anthracenemethylmethacrylate  Of Methyl methacrylate  / Acrolein dimethylacetal) Synthesis

Into a 500 mL four-neck flask, 40 g of 9-anthracene methyl methacrylate, 15 g of methyl methacrylate, 15 g of acrolein dimethylacetal, 150 g of tetrahydrofuran, 150 g of methyl ethyl ketone, and 4 g of azobisisobutylonitrile were added in a nitrogen gas atmosphere. After dissolving, the mixture was reacted at a temperature of 65 ° C for 24 hours. The polymer was precipitated in 2000 mL of diethyl ether after completion | finish of reaction. This was filtered and dried in a vacuum oven for 24 hours to give a pale yellow polymer of poly (9-anthracenemethyl methacrylate / methyl methacrylate / acrolein dimethylacetal) (polymer of formula 1, R ₁ = anthracenemethyl, R ₂ , R ₃ , R ₄ and R ₆ = methyl, R ₅ = hydrogen) were obtained (yield 86% by weight).

1 is a graph showing the molecular weight distribution of the poly (9-anthracenemethyl methacrylate / methyl methacrylate / acrolein dimethylacetal) by GPC, the number average molecular weight (Mn) is 5370, the weight average molecular weight (Mw) This 10963 indicates that the molecular weight distribution (Mw / Mn) is 2.04.

Example 2. Poly (9- Anthracenemethylmethacrylate  Of Methyl methacrylate  / Acrolein) Synthesis

In a 500 mL four-necked flask, 40 g of 9-anthracenemethyl methacrylate, 15 g of methyl methacrylate, 15 g of acrolein, 150 g of tetrahydrofuran, 150 g of methyl ethyl ketone, and 4 g of azobisisobutylonitrile were dissolved in a nitrogen gas atmosphere. After making it react, it was made to react at the temperature of 65 degreeC for 24 hours. The polymer was precipitated in 2000 mL of diethyl ether after completion | finish of reaction. After filtering this polymer is dried for 24 hours to a pale yellow within a vacuum oven to poly (9-anthracenemethyl methacrylate / methyl methacrylate / acrolein) (a polymer of formula 2, R ₇ = methyl anthracene, R ₈ and R ₁₀ = methyl, R ₉ = hydrogen) was obtained (yield 90% by weight).

2 is a graph showing the molecular weight distribution of the poly (9-anthracenemethyl methacrylate / methyl methacrylate / acrolein) by GPC, wherein the number average molecular weight (Mn) is 2514 and the weight average molecular weight (Mw) is 5706 As a result, the molecular weight distribution (Mw / Mn) is 2.27.

Example 3. Poly (Acrolein / Methyl methacrylate ) synthesis

Into a 500 mL four-necked flask, 50 g of acrolein, 15 g of methyl methacrylate, 200 g of propylene glycol monomethyl ether acetate, and 4 g of azobisisobutylonitrile were dissolved in a nitrogen gas atmosphere and allowed to react at a temperature of 65 ° C. for 24 hours. . The reaction proceeded uniformly. The polymer was precipitated in 1500 mL of diethyl ether after completion | finish of reaction. This was filtered and dried in a vacuum oven for 24 hours to obtain a white polymer methyl methacrylate (R ₁₁ and R ₁₂ = methyl, R ₁₃ = hydrogen as a polymer of Formula 3) (yield 85% by weight).

3 is a graph showing the molecular weight distribution of the poly (acrolein / methyl methacrylate) by GPC, wherein the number average molecular weight (Mn) is 3404, the weight average molecular weight (Mw) is 8774, and the molecular weight distribution (Mw / Mn ) Is 2.58

Example 4. Poly (9- Anthracenemethylmethacrylate  / 2- Hydroxyethyl methacrylate  Of Hexafluorobutyl methacrylate ) synthesis

6 g of 9-anthracene methyl methacrylate, 2 g of 2-hydroxyethyl methacrylate, 2 g of hexafluorobutyl methacrylate and 0.5 g of azobisisobutylonitrile were dissolved in 50 g of propylene glycol monomethyl ether acetate. After dissolution it was reacted at a temperature of 70 ℃ for 12 hours. After completion of the reaction, precipitated in ethyl ether, filtered and dried in vacuo to give poly (9-anthracenemethyl methacrylate / 2-hydroxyethyl methacrylate / hexafluorobutyl methacrylate) (R ₁₇ = Anthracenemethyl, R ₁₈ = hexafluorobutyl, R ₁₉ , R ₂₀ and R ₂₁ = methyl, x = 2) (yield 85% by weight).

4 is an IR spectrum of the poly (9-anthracenemethylmethacrylate / 2-hydroxyethylmethacrylate / hexafluorobutylmethacrylate), showing absorption of light at wavelengths of 248 nm and 193 nm.

Example 5. Poly (Acrolein / Hexafluorobutyl methacrylate ) synthesis

7 g of acrolein, 3 g of hexafluorobutyl methacrylate and 0.5 g of azobisisobutylonitrile were dissolved in 50 g of propylene glycol monomethyl ether acetate. After dissolution, the reaction was carried out at a temperature of 70 ° C for 12 hours. After the reaction was completed, the precipitate was caught in ethyl ether and filtered. The polymer obtained after the filtration was dissolved in 200 g of methanol, and then 0.2 g of paratoluene sulfonic acid was added, followed by reaction at 50 ° C. for 12 hours. After completion of the reaction, the precipitate was caught in water, filtered and dried in vacuo to obtain poly (acrolein / hexafluorobutylmethacrylate) (as a polymer of Formula 6, R ₂₂ = hexafluorobutyl, R ₂₃ = methyl, R ₂₄ = hydrogen). Was obtained (yield 83% by weight).

Example 6. Antireflection film  Composition Preparation (1)

3 g of the polymer of Example 1, 2 g of polyhydroxystyrene, and 0.5 g of 2-hydroxyethyl p-toluenesulfonate were dissolved in 30 g of propylene glycol monomethyl ether acetate to prepare an antireflection film composition.

Example 7. Antireflection film  Composition Preparation (2)

3 g of the polymer of Example 2, 2 g of polyhydroxystyrene, and 0.5 g of 2-hydroxyethyl p-toluenesulfonate were dissolved in 30 g of propylene glycol monomethyl ether acetate to prepare an antireflection film composition.

Example 8. Antireflection film  Composition Preparation (3)

0.5 g of the polymer of Example 3, 3 g of the polymer of Example 4, 3 g of polyhydroxystyrene, and 0.5 g of 2-hydroxyethyl p-toluenesulfonate were dissolved in 30 g of propylene glycol monomethyl ether acetate to prepare an antireflection film composition. It was.

Example 9. Antireflection film  Composition Preparation (4)

5 g of the polymer of Example 1, 3 g of polyhydroxystyrene, and 0.5 g of 2-hydroxyethyl p-toluenesulfonate were dissolved in 30 g of propylene glycol monomethyl ether acetate to prepare an antireflection film composition.

Example 10. Antireflection film  Composition Preparation (5)

6 g of the polymer of Example 4, 4 g of the polymer of Example 5, and 0.5 g of 2-hydroxyethyl p-toluenesulfonate were dissolved in 30 g of propylene glycol monomethyl ether acetate to prepare an antireflection film composition.

Example 11. Pattern Formation

After coating the antireflection film composition prepared in Example 10 on the semiconductor substrate on which the contact hole was formed, it was baked at 220 ° C. for 90 seconds to form an antireflection film. At this time, since the polymer of Example 4 and the polymer of Example 5 constituting the antireflection film composition prepared in Example 10 is a resin that is well planarized, the composition is uniformly embedded in the contact hole to form a flattened antireflection film Form (see FIG. 5). On the other hand, when coating on a semiconductor substrate in which a contact hole is formed using a conventional antireflection film composition, voids are generated (see FIG. 6).

Then, after forming a photoresist film on the antireflection film, a series of exposure processes were performed to obtain a vertical pattern without a sine wave effect (see FIG. 7).

1 is a graph showing the molecular weight distribution by GPC of the polymer prepared in Example 1. FIG.

2 is a graph showing the molecular weight distribution by GPC of the polymer prepared in Example 2. FIG.

3 is a graph showing the molecular weight distribution by GPC of the polymer prepared in Example 3. FIG.

4 shows the IR spectrum of the polymer prepared by Example 4.

5 is a SEM photograph showing the result of coating the antireflection film composition in Example 11.

6 is a SEM photograph showing a result of coating of a conventional antireflective coating composition.

7 is an SEM photograph of the pattern formed by Example 11. FIG.

Claims (15)

A polymer for antireflection film comprising a repeating unit selected from the group consisting of the following Chemical Formulas 1 to 6 and combinations thereof: [Formula 1]

In Chemical Formula 1, R ₁ is an anthracene methyl group, R ₂ and R ₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl; R ₄ , R ₅ and R ₆ are the same as or different from each other, and each is hydrogen or a methyl group, When n = 0, l: m: n is 0.1 to 8: 0.1 to 3: 1 by weight, When n = 0, l: m is 1-10: 1 by weight ratio. [Formula 2]

In Chemical Formula 2, R ₇ is an anthracene methyl group, R ₈ , R ₉ and R ₁₀ are the same as or different from each other, and each is hydrogen, methyl or ethyl; a: b: c is 0.1-8: 1: 0.1-5 by weight ratio. [Formula 3]

In Chemical Formula 3, R ₁₁ is an anthracene methyl group, R ₁₂ and R ₁₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl; d: e is 1: 0.1-5 by weight ratio. [Formula 4]

In Chemical Formula 4, R ₁₄ is hydrogen, methyl group, ethyl group or t-butyl group, R ₁₅ is hydrogen, methyl or t-butyl group, R ₁₆ is hydrogen, a methyl group or an ethyl group, If g = 0 is not, f: g: h is 1 to 10: 1: 1 to 10 by weight, When g = 0, f: h is 1: 0.1-10 by weight ratio. [Formula 5]

In Chemical Formula 5, R ₁₇ is an anthracene methyl group, R ₁₈ is a C ₁ to C ₂₀ alkyl group containing fluorine, R ₁₉ , R ₂₀ and R ₂₁ are the same as or different from each other, and are each hydrogen, methyl or ethyl group, x represents an integer between 1 and 5, i: j: k is 1: 0.01-1: 0.1-10 by weight ratio. [Formula 6]

In Chemical Formula 6, R ₂₂ is a C ₁ to C ₂₀ alkyl group containing fluorine, R ₂₃ and R ₂₄ are the same as or different from each other, and each is hydrogen, methyl or ethyl; o: p is 1: 0.1-10 by weight ratio. The method according to claim 1, The C ₁ to C ₂₀ alkyl group containing the fluorine may be an eicossafluorodecyl group, a heptadecafluorodecyl group, a heptafluorobutyl group, a hexafluorobutyl group, a hexafluoroisopropyl group or an octafluorophene. It is a fluoroalkyl group selected from the group consisting of a methyl group, pentadecafluorooctyl group, pentafluoropropyl group, tetrafluoropropyl group, trifluoroethyl group, dodecafluoroheptyl group and pentafluorooctyl group A polymer for antireflection films. The method according to claim 1, The repeating unit is poly (9-anthracenemethyl methacrylate / methyl methacrylate / acrolein dimethylacetal), poly (9-anthracene methyl methacrylate / methyl methacrylate / acrolein), poly (acrolein / methyl methacrylate) ), Polyhydroxystyrene, poly (9-anthracenemethyl methacrylate / 2-hydroxyethyl methacrylate / hexafluorobutyl methacrylate) and poly (acrolein / hexafluorobutyl methacrylate) Anti-reflection film polymer, characterized in that. A composition for antireflection film comprising at least one antireflection film polymer, a thermal acid generator, and an organic solvent comprising a repeating unit selected from the group consisting of Formulas 1 to 6 and combinations thereof: [Formula 1]

In Chemical Formula 1, R ₁ is an anthracene methyl group, R ₂ and R ₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl; R ₄ , R ₅ and R ₆ are the same as or different from each other, and each is hydrogen or a methyl group, When n = 0, l: m: n is 0.1 to 8: 0.1 to 3: 1 by weight, When n = 0, l: m is 1-10: 1 by weight ratio. [Formula 2]

In Chemical Formula 2, R ₇ is an anthracene methyl group, R ₈ , R ₉ and R ₁₀ are the same as or different from each other, and each is hydrogen, methyl or ethyl; a: b: c is 0.1-8: 1: 0.1-5 by weight ratio. [Formula 3]

In Chemical Formula 3, R ₁₁ is an anthracene methyl group, R ₁₂ and R ₁₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl; d: e is 1: 0.1-5 by weight ratio. [Formula 4]

In Chemical Formula 4, R ₁₄ is hydrogen, methyl group, ethyl group or t-butyl group, R ₁₅ is hydrogen, methyl or t-butyl group, R ₁₆ is hydrogen, a methyl group or an ethyl group, If g = 0 is not, f: g: h is 1 to 10: 1: 1 to 10 by weight, When g = 0, f: h is 1: 0.1-10 by weight ratio. [Formula 5]

In Chemical Formula 5, R ₁₇ is an anthracene methyl group, R ₁₈ is a C ₁ to C ₂₀ alkyl group containing fluorine, R ₁₉ , R ₂₀ and R ₂₁ are the same as or different from each other, and are each hydrogen, methyl or ethyl group, x represents an integer between 1 and 5, i: j: k is 1: 0.01-1: 0.1-10 by weight ratio. [Formula 6]

In Chemical Formula 6, R ₂₂ is a C ₁ to C ₂₀ alkyl group containing fluorine, R ₂₃ and R ₂₄ are the same as or different from each other, and each is hydrogen, methyl or ethyl; o: p is 1: 0.1-10 by weight ratio. The method according to claim 4, The composition is an anti-reflective coating composition comprising a mixture of a polymer comprising a repeating unit of formula (1) and a polymer comprising a repeating unit of formula (4). The method according to claim 4, The composition is an antireflection film composition comprising a mixture of a polymer comprising a repeating unit of formula (2) and a polymer comprising a repeating unit of formula (4). The method according to claim 4, The composition is an anti-reflection film composition comprising a mixture of a polymer comprising a repeating unit of formula 3, a polymer comprising a repeating unit of formula 4 and a polymer comprising a repeating unit of formula 5. The method according to claim 4, The composition is an antireflection film composition comprising a mixture of a polymer comprising a repeating unit of formula 1, a polymer comprising a repeating unit of formula 3 and a polymer comprising a repeating unit of formula (4). The method according to claim 4, The composition is an antireflection film composition comprising a mixture of a polymer comprising a repeating unit of formula 5 and a polymer comprising a repeating unit of formula (6). The method according to claim 4, The thermal acid generator is a compound for anti-reflection film of the formula [Formula 7]

In Formula 7, R is a fluorine group, a chlorine group, hydrogen, a methyl group, or an ethyl group. The method according to claim 4, The organic solvent is a reflection, characterized in that selected from the group consisting of methyl 3-methoxypropionate (MMP), ethyl 3-ethoxypropionate (EEP), propylene glycol methyl ether acetate (PGMEA) and cyclohexanone Composition for prevention film. (a) Applying an antireflection film composition comprising at least one antireflection film polymer, a thermal acid generator, and an organic solvent comprising a repeating unit selected from the group consisting of the following Chemical Formulas 1 to 6 and combinations thereof on top of the etching layer Making; (b) hardening by baking process to form an anti-reflection film; (c) applying a photoresist on the antireflection film, exposing the photoresist, and developing the photoresist pattern to form a photoresist pattern; And (d) etching the anti-reflection film and the etched layer using the photoresist pattern as an etch mask to form an etched layer pattern; [Formula 1]

In Chemical Formula 1, R ₁ is an anthracene methyl group, R ₂ and R ₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl; R ₄ , R ₅ and R ₆ are the same as or different from each other, and each is hydrogen or a methyl group, When n = 0, l: m: n is 0.1 to 8: 0.1 to 3: 1 by weight, When n = 0, l: m is 1-10: 1 by weight ratio. [Formula 2]

In Chemical Formula 2, R ₇ is an anthracene methyl group, R ₈ , R ₉ and R ₁₀ are the same as or different from each other, and each is hydrogen, methyl or ethyl; a: b: c is 0.1-8: 1: 0.1-5 by weight ratio. [Formula 3]

In Chemical Formula 3, R ₁₁ is an anthracene methyl group, R ₁₂ and R ₁₃ are the same as or different from each other, and each is hydrogen, methyl or ethyl; d: e is 1: 0.1-5 by weight ratio. [Formula 4]

In Chemical Formula 4, R ₁₄ is hydrogen, methyl group, ethyl group or t-butyl group, R ₁₅ is hydrogen, methyl or t-butyl group, R ₁₆ is hydrogen, a methyl group or an ethyl group, If g = 0 is not, f: g: h is 1 to 10: 1: 1 to 10 by weight, When g = 0, f: h is 1: 0.1-10 by weight ratio. [Formula 5]

In Chemical Formula 5, R ₁₇ is an anthracene methyl group, R ₁₈ is a C ₁ to C ₂₀ alkyl group containing fluorine, R ₁₉ , R ₂₀ and R ₂₁ are the same as or different from each other, and are each hydrogen, methyl or ethyl group, x represents an integer between 1 and 5, i: j: k is 1: 0.01-1: 0.1-10 by weight ratio. [Formula 6]

In Chemical Formula 6, R ₂₂ is a C ₁ to C ₂₀ alkyl group containing fluorine, R ₂₃ and R ₂₄ are the same as or different from each other, and each is hydrogen, methyl or ethyl; o: p is 1: 0.1-10 by weight ratio. The method according to claim 12, The baking process of step (b) is a pattern formation method performed for 1 to 5 minutes at a temperature of 150 to 250 ℃. The method according to claim 12, And the exposure process is performed using a light source selected from the group consisting of ArF, KrF, F ₂ , EUV, E-beam, X-ray and ion beam. A semiconductor device manufactured by the method of claim 12.

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