KR100871772B1 - Co-polymer comprising isocyante-based derivative, preparing method thereof, organic anti-reflective coating composition comprising the co-polymer and organic anti-reflective coating comprising the composition - Google Patents

Abstract

A copolymer having an isocyanate-based derivative, its preparation method, and an organic antireflective coating composition containing the copolymer are provided to improve adhesive force and cross-linking performance and to prevent the diffuse reflection from an underlayer in case of short wavelength exposure process. A copolymer having an isocyanate-based derivative contains a pyrazole group-protected isocyanate-based derivative represented by the formula 1 and a structural unit represented by the formula 4 as a monomer, and has a weight average molecular weight of 5,000-100,000, wherein R and R1 are independently H, a C1-C10 alkyl group, a C1-C10 alkoxyalkyl group or a C1-C10 hydroxyalkyl group; R3 is H, a C1-C6 alkyl group, a C1-C6 alkoxyalkyl group, a C1-C6 hydroxyalkyl group or a C1-C6 halogenated alkyl group; R4 is H or a methyl group; and R6 is H or a methyl group.

Description

Copolymer comprising an isocyanate derivative, a method for preparing the copolymer, an organic antireflective coating composition comprising the copolymer and an organic antireflective coating comprising the composition {co-polymer comprising isocyante-based derivative, preparing method approximately, organic anti-reflective coating composition comprising the co-polymer and organic anti-reflective coating comprising the composition}

The present invention, in photolithography, an exposure process for forming a microcircuit of a highly integrated semiconductor using short-wavelength ultraviolet light, suppresses reflective notching occurring in a substrate layer under a photoresist, A copolymer comprising a pyrazole-protected isocyanate crosslinking group capable of removing a standing wave effect due to a change in thickness of a resist, a method of preparing the copolymer, an organic antireflection film composition comprising the copolymer, and the It relates to an organic antireflection film using the composition.

Antireflective coating (ARC) is a very thin layer of light-absorbing photosensitive material, which is used to stably form the ultrafine circuit of 60 nm to 150 nm and below which is essential for producing a gigabit (Gb) class ultra-high density semiconductor. Used in circuit processing process. Therefore, the anti-reflection film should be well matched with the high-resolution photoresist (PR) materials (PR) materials used in the existing semiconductor production process and mutual adhesion interface and optical properties.

Among the anti-reflection films, the first coating on the bottom of the photoresist layer during the far ultraviolet ray exposure process is called a bottom anti-reflection film (BARC, bottom ARC). In the currently developed highly integrated semiconductor optical microfabrication process, a high absorbance organic bottom antireflection film is generally used.

Since the organic anti-reflection film must have high light absorption at a specific exposure wavelength, it must be able to cope with shortening of the light source (G-line, I-line, KrF, ArF, F2, etc.) according to the development of highly integrated semiconductor microfabrication technology process. [M. Padmanaban et al., Proc. SPIE, 3678, 550 (1999); G. E. Bailey et al. Proc. SPIE, 3999, 521 (2000); M. Padmanaban et al., Proc. SPIE, 333, 206 (1998).

Recently, technology in the field of ultra high-density semiconductor manufacturing has been remarkable. However, it is impossible to stably produce a 60 nm to 150 nm class ultrafine circuit using only conventional optical fine processing technology of rotating and exposing a photoresist as a photosensitive material on a silicon wafer. Therefore, it is necessary to apply a special thin film to prevent reflection in the exposure process before applying the photoresist layer.

The antireflection film prevents standing wave effects caused by interference of incident light and reflected light from the substrate inside the photoresist layer during exposure. It also serves to prevent or significantly reduce diffuse reflection at the edges or reflection due to topography resulting from circuit layers made in conventional processes. Thus, precise control of the desired critical dimension ("CD") is achieved, thereby increasing the process latitude of the manufacturing process conditions. The antireflection film includes an organic material based on its composition and an inorganic material using chemical vapor deposition. However, in recent years, most of the organic anti-reflection film that is convenient for the process is used.

The role of the anti-reflection film became more important among short wavelength far ultraviolet rays, especially after an optical microcircuit processing process using a krypton fluoride (KrF) excimer laser having a wavelength of 248 nm became full. In addition, organic polymer anti-reflective coating materials using chromophore-containing aromatic derivatives such as anthracene or naphthalene having high absorbance in the far-ultraviolet region are used widely for the fabrication of ultrafine circuits of 150 nm or less, that is, 100 nm [J. Meador et al., Proc. SPIE, 3678, 800 (1999); G. Taylor et al., Proc. SPIE, 3678, 174 (1999); X. Shao et al., J. Photopolym. Sci. Techonol., 14, 481 (2001); Myoung Soo Kim et al., Proc. SPIE, 5753, 644 (2005); K. Mizutani et al., Proc. SPIE, 3678, 518 (1999). Such techniques are disclosed in US Pat. Nos. 5693691, 5886102, 5919599, 6033830, 6080530, 6156479 and 6602652.

The organic bottom anti-reflective coating used in the ultra-violet exposure process for the fabrication of ultra-fine circuits must meet several requirements, such as [H. Yoshino et al., Proc. SPIE, 3333, 655 (1998); P. Trefonas et al., Proc. SPIE, 3678, 701 (1999); S. Malik et al., J. Photopolym. Sci. Techonol., 14, 489 (2001); R. Huang et al., Proc. SPIE, 5753, 637 (2005); C. Y. Chang et al., Proc. SPIE, 6153, 61530M (2006). First, it should have a refractive index (n) and a light absorption constant (k), which are optical constants suitable for light sources used in semiconductor manufacturing. Second, it should have a high selectivity at the plasma dry etching rate compared to the upper photoresist, and there should be no defects caused by dry etching. Third, intermixing should not occur between the photoresist layer and the anti-reflection film layer. For this purpose, a reactor capable of forming an appropriate crosslinked structure in the organic polymer chain should be included. Fourth, in the film forming process by rotational coating, suitable thin film thickness control ability, excellent coating film forming ability and coating film uniformity are required.

However, the stable implementation of the organic bottom anti-reflection film that satisfies all the above conditions is still insufficient.

The present invention is to provide a novel copolymer exhibiting better and more efficient performance under the technical background as described above and an object thereof, and an object of the present invention is krypton fluoride having a wavelength of 248 nm during the manufacturing process of an ultra-high density semiconductor device. KrF) and 193nm wavelength argon fluoride (ArF) excimer can be used in the ultra-fine circuit exposure process using a laser exposure source, it is possible to prevent diffuse reflection from the lower layer during the short wavelength exposure process, and excellent adhesion and crosslinking performance It is to provide a copolymer for an anti-reflection coating comprising an isocyanate cross-linker having a method and a method for producing the same.

Still another object of the present invention is to provide an organic antireflection film composition comprising the copolymer and a method of manufacturing the same.

Still another object of the present invention is to provide an organic antireflection film including the composition.

In order to achieve the above object, the present invention provides a polymer comprising an isocyanate derivative protected by a pyrazole group represented by the following formula (1) as a monomer, and containing an isocyanate derivative having a weight average molecular weight of 10,000 to 100,000.

<Formula 1>

In Formula 1, R and R ₁ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, and R ₆ represents hydrogen or methyl.

The present invention also provides a method for preparing the copolymer, wherein the derivative and the initiator are dissolved in a polymerization solvent and subjected to radical polymerization for 2 to 24 hours at a temperature of 50 to 90 ° C. under an inert gas atmosphere.

In addition, the present invention is a copolymer; And it provides an organic antireflection film composition comprising an organic solvent.

In another aspect, the present invention provides an organic antireflection film comprising the composition.

The organic antireflection film having a copolymer as a basic structure according to the present invention has no gas generated even at high temperature thermal crosslinking due to covalent bonding of a thermally crosslinkable isocyanate crosslinking group into the copolymer chain, thereby providing excellent thermal stability.

In addition, it has excellent adhesion with the substrate and has sufficient absorbance to have as an organic antireflection film. As a result, it is possible to suppress reflection occurring in the lower layer during the exposure process and to remove standing waves due to the change in thickness of the light source and the photoresist used. In addition, the high etching ability to the plasma allows a stable transfer of the circuit to the substrate. Therefore, when the polymer according to the present invention is used as an organic antireflection film in an exposure process using an excimer laser having an exposure wavelength of 248 nm, 193 nm, and 157 nm in semiconductor manufacturing, a memory device of 1 gigabit DRAM or more or 60 nm to 150 nm units Since the microcircuit fabrication of the system integrated circuit can be stably performed, the production yield of the semiconductor device can be increased.

The copolymer according to the present invention is a comonomer for controlling the properties of monomers and polymers including anthracene chromophores that cause high light absorption at exposure wavelengths of 248 nm and 193 nm and pyrazole-protected isocyanate groups for crosslinking in forming antireflective films. And dicopolymers, terpolymers or quaternary copolymers prepared from two or four different monomers.

Hereinafter, the present invention will be described in detail.

1. Copolymer containing isocyanate derivative

The copolymer of the present invention is a polymer including a pyrazole group, more specifically pyrazole or dimethylpyrazole-protected isocyanate derivative as a monomer, and may be represented by Formula 1. The derivative is a monomer having a pyrazole-protected chemical structure for ease of manufacture of the copolymer and crosslinking due to desorption of the protecting group by heat treatment during the exposure process.

<Formula 1>

In Formula 1, R and R ₁ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, and R ₆ represents hydrogen or a methyl group.

Here, when said R <_1> is an alkyl group, an alkoxyalkyl group, a halogenated alkyl group, or a hydroxyalkyl group, when C1-C10 is C, there exists an advantage which becomes excellent in crosslinking property.

The copolymer of the present invention may include one or two or more selected from structural units represented by the following Chemical Formulas 2 to 4 together with the derivative of Chemical Formula 1 as a comonomer.

The structural unit represented by the following formula (2) is an alkylmaleimide monomer including a hydroxy group, the structural unit represented by the following formula (3) is a (meth) acrylate monomer, and the structural unit represented by the following formula (4) is 9-anthracene Methyl methacrylate monomer.

<Formula 2>

<Formula 3>

<Formula 4>

In Chemical Formulas 2 to 4,

R ₂ represents hydrogen or an alkyl group having 1 to 6 carbon atoms,

R ₃ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 6 carbon atoms,

R ₄ and R ₅ each independently represent hydrogen or a methyl group,

x represents a natural number of 1 to 6,

In the copolymer, the mole fractions of the structural units represented by Chemical Formulas 1 to 4 are k, l, m and n, respectively, and k is 0.1 to 0.7, based on the total mole fraction k + l + m + n of the structural unit. 1 is 0-0.4, m is 0.1-0.7, n is 0.1-0.5.

When said R <_2> is an alkyl group, if it is C1-C6, there exists an advantage which becomes excellent in heat resistance. When said R <_3> is an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, or a halogenated alkyl group, it is an advantage that an optical property becomes excellent as it is C1-C6.

For example, the copolymer may be represented by a copolymer represented by the following Structural Formula 1. At this time, each structural unit of the following structural formula 1 is not limited to the following structural formula 1 can be located at random. In addition, all the variables described in Structural Formula 1 are the same as the variables of Formulas 1 to 4.

<Structure 1>

The copolymer including the isocyanate crosslinked end according to the present invention significantly improves the adhesion to the wafer and improves the crosslinking with the photoresist layer with excellent crosslinkability compared to the conventional hydroxy based crosslinked derivative. It shows the ability to form a coating film.

2. Method for producing a copolymer containing an isocyanate derivative

The copolymer according to the present invention dissolves the derivative represented by the formula (1) and the initiator in a polymerization solvent, a conventional radical polymerization method for 2 to 24 hours at a temperature of 50 to 90 ℃ under an inert gas atmosphere such as nitrogen, argon, etc. The reaction can be carried out according to the present invention. If the reaction temperature is lower than 50 ° C, a problem occurs that the polymer is not formed, and if the reaction temperature exceeds 90 ° C, a problem occurs in heat resistance. If the reaction time is less than 2 hours, there is a problem that the molecular weight is not controlled, if more than 24 hours, a problem in productivity occurs.

The radical polymerization initiator is not particularly limited, but azobisisobutyronitrile (AIBN), azobisvaleronitrile (AIVN), benzoyl peroxide (BPO) and di-t-butyloxide (DTBP) which are thermal polymerization initiators. 1 type, or 2 or more types selected from the group consisting of can be used. As the solvent of the polymerization reaction, one or two or more selected from the group consisting of dioxane, tetrahydrofuran and benzene which are aromatic solvents can be used. Although it does not specifically limit as a solvent of the said polymerization reaction, 1 type, or 2 or more types chosen from the group which consists of dioxane, tetrahydrofuran, and benzene which are aromatic solvents can be used.

In the present invention, by adjusting the weight ratio between the monomer and the polymerization solvent or by controlling the amount of the radical initiator, it is possible to produce a polymer of the appropriate molecular weight required in the semiconductor exposure step.

In more detail, the preparation method may be prepared using 1 to 50 moles of the polymerization solvent and 0.1 to 10 moles of the initiator with respect to 1 mole of the derivative represented by Chemical Formula 1.

When the polymerization solvent is included in 1 to 50 moles with respect to 1 mole of the derivative represented by Chemical Formula 1, there is an advantage of excellent meltability.

When the initiator is included in an amount of 0.1 to 10 moles with respect to 1 mole of the derivative represented by Formula 1, there is an advantage in that the reaction time can be easily adjusted.

The polymer may be prepared by dissolving 0.1 to 15 moles of one or two or more selected from monomers represented by Formulas 2 to 4 together with the derivative in the polymerization solvent. When the monomer is included in 0.1 to 15 moles with respect to 1 mole of the derivative represented by the formula (1), there is an advantage that can increase the polymerization yield.

The weight average molecular weight of the polymer according to the present invention can be appropriately selected by those skilled in the art according to the use and the case by adjusting the polymerization conditions, preferably measured by gel permeation chromatography (GPC) (sample material, polystyrene conversion). The polymerization is preferably such that the weight average molecular weight is 5,000 to 100,000. If the molecular weight is 5,000 to 100,000, there is an advantage that the coating thickness can be easily adjusted.

Among the polymers obtained by the same method as described above, a polymer having a molecular weight having an appropriate coating ability is used as the antireflection film material.

3. Organic Antireflection film  Composition

The organic antireflective coating composition of the present invention comprises the copolymer and the organic solvent.

The organic solvent can be used without limitation to the conventional solvent used in the semiconductor microcircuit processing process, preferably propylene glycol monomethyl ether acetate (PGMEA), ethyl 3-ethoxy propionate, ethyl One or two or more selected from the group consisting of lactate, methyl 3-methoxy propionate and cyclohexanone are used.

The copolymer is preferably included in 0.1 to 20% by weight based on the total weight of the composition. When the copolymer is included in an amount of 0.1 to 20 wt%, there is an advantage in that crosslinkability and optical properties are good.

In addition, the organic solvent is preferably included in 80 to 99.9% by weight based on the total weight of the composition. When the organic solvent is included in the 80 to 99.9% by weight, there is an advantage that the anti-reflection film thickness can be easily adjusted.

In addition, an additive may be further included in the composition. Examples of the additive may include, but are not particularly limited to, crosslinking reaction accelerators, surface leveling agents, adhesion promoters or antifoaming agents.

Among them, the crosslinking accelerator may be used to promote the crosslinking reaction and increase the efficiency of the reaction. One or two or more selected from the group consisting of a crosslinking agent, a stabilizer, a lower alcohol, an acid, and an acid generator may be used. Preferably, a thermal crosslinking agent, a thermal acid generator or a mixture thereof may be used. The thermal crosslinking agent is not particularly limited, but melamine-formaldehyde resin, benzoguanine-formaldehyde resin, glycoluril-formaldehyde resin, urea-formaldehyde resin, phenolic resin, benzyl alcohol, epoxy compound, isocyanate and alkoxy methyl It may be one kind or two or more kinds selected from the group consisting of melamine. The thermal acid generator is not particularly limited, but may be selected from other strong protic acids such as one or two or more selected from the group consisting of p-toluenesulfonic acid, phosphoric acid, phthalic acid, oxalic acid and dodecylbenzenesulfonic acid.

The additive is preferably included in 0.001 to 10% by weight relative to the total weight of the composition. If the additive is included in 0.001 to 10% by weight, there is an advantage that the pattern is formed vertically well.

4. Organic Antireflection film  Organic with the composition Antireflection film

The organic antireflective coating composition solution is filtered through a fine particle filtration apparatus, spun coated on a silicon wafer, and crosslinked at an appropriate temperature to obtain a desired antireflective coating. The anti-reflection film prepared in this manner serves to remove the problems caused by the reflection of light in the short wavelength far ultraviolet microcircuit processing process, so that the semiconductor device can be produced smoothly.

The copolymer including the pyrazole-protected isocyanate crosslinked group according to the present invention showed excellent performance as an organic antireflection film for forming a microcircuit in the exposure wavelength region of short wavelength far ultraviolet rays of 248 nm, 193 nm, and 157 nm. Since it has excellent adhesiveness and crosslinkability compared with the conventional anti-reflection film based on a hydroxy crosslinked end, it has been found to be useful for forming an ultrafine circuit when forming a semiconductor device.

Hereinafter, the present invention will be described in detail through examples. However, the embodiments are only illustrative of the present invention, and the scope of the present invention is not limited thereto.

Production Example  One: Pyrazole  Protected isocyanate monomers ( MOI - BP ) Synthesis

<Scheme 1>

In a 500 ml round bottom flask equipped with a reflux condenser, 2-isocyanate ethyl methacrylate (Formula 5) (100.00 g, 0.64 mol) and dimethylpyrazole (Formula 6) (61.52 g, 0.64 mol) were added. It was dissolved in 150 ml of pyridine and reacted at 40 ° C. for 2 hours. After the reaction, the resultant transparent liquid product was obtained, and the unreacted product was separated and purified by silica gel column, and then 2-[(3,5-dimethylpyrazole) carboxyamino] ethylmethacryl which is pure pyrazole protected isocyanate. The rate (2-[(3,5-dimethylpyrazolyl) carboxyamino] ethylmethacrylate (hereinafter referred to as “MOI-BP”) was recovered. 135.03 g (yield 83.6%) was obtained and the breaking point was 139 ° C.

Production Example  2: the above formula 4 and  The monomer represented by 7 Used Binary copolymer  synthesis

An anthracene methylmethacrylate (Formula 4) monomer (hereinafter referred to as “AMMA”, 10.22g, 36mmol), MOI-BP (Formula 7) monomer (18.09g, 72mmol) and 3 moles of AIBN radical initiator are placed in a polymerization vessel. (50 ml) and then polymerized for 10 hours at a polymerization temperature of 60 deg. The polymerization reaction was precipitated in excess methanol, and then filtered and dried to synthesize P (MOI-BP / AMMA), a binary copolymer. The yield of P (MOI-BP / AMMA) obtained was 85%, with data and graphs showing the GPC results for the polymer attached to FIG. 1.

Production Example  3: monomers represented by the formula (3), (4) and (7) Used Terpolymer  synthesis

Methyl methacrylate monomer (hereinafter referred to as “MMA”, 7.21 g, 72 mmol), 9-anthracenemethylmethacrylate (Formula 4) monomer (hereinafter referred to as “AMMA”, 10.22 g, 36 mmol in the polymerization vessel. ), MOI-BP (Formula 7) monomer (9.04g, 36mmol) and 3 mol of AIBN as a radical initiator were added and dissolved in dioxane (50ml), and then polymerized at a polymerization temperature of 60 ℃ under nitrogen atmosphere for 10 hours. The polymerization reactant was precipitated in excess methanol, and then filtered and dried to synthesize P (MOI-BP / MMA / AMMA), a terpolymer. The yield of the obtained P (MOI-BP / MMA / AMMA) was 87%, and data and graphs showing the GPC results for the polymer were attached to FIG. 2.

Production Example  4: using the monomer represented by the formula (2), (3), (4) and (7) Employee Copolymer  synthesis

Hydroxyethylmaleimide (Formula 2) monomers (hereinafter referred to as "HEMI", 5.08 g, 36 mmol), methyl methacrylate (Formula 3) monomers (hereinafter referred to as "MMA", 7.21 g, 72 mmol), 9-anthracene methyl methacrylate (Formula 4) monomer (hereinafter referred to as "AMMA", 10.22g, 36mmol), MOI-BP (Formula 7) monomer (9.04g, 36mmol) and 3 moles of AIBN radical initiator, dioxane ( 50 ml), and then polymerized under a nitrogen atmosphere at a polymerization temperature of 60 ° C. for 10 hours. The polymerization reaction was precipitated in excess methanol, and then filtered and dried to synthesize P (MOI-BP / HEMI / MMA / AMMA). The yield of P (MOI-BP / HEMI / MMA / AMMA) obtained was 88%, with data and graphs showing the GPC results for the polymer attached to FIG. 3.

Example  1 to Example  3 and Comparative example  1: organic Antireflection film  Preparation of the composition

To prepare a composition according to the components and composition ratios described in Table 1 below. In more detail, the copolymer was dissolved in a solvent, stirred by adding a thermal crosslinking binder and a stabilizer, and filtered through a microporous membrane filter to prepare a bottom anti-reflective coating composition.

Copolymer (% by weight) Thermal crosslinking agent (% by weight) Thermal acid generator (wt%) Organic Solvent (wt%) Example 1 a-1 4.8 b-1 1.1 c-1 0.1 d-1 94.0 Example 2 a-2 4.8 b-1 1.1 c-1 0.1 d-1 94.0 Example 3 a-3 4.8 b-1 1.1 c-1 0.1 d-1 94.0 Comparative Example 1 a-5 4.8 b-1 1.1 c-1 0.1 d-1 94.0

a-1: the copolymer prepared in Preparation Example 2

a-2: copolymer prepared in Preparation Example 3

a-3: copolymer prepared in Preparation Example 4

a-4: hydroxy type crosslinking group containing copolymer

b-1: Benzoguanamine-formaldehyde resin system

c-1: p-toluenesulfonic acid system

d-1: propylene glycol monomethyl ether acetate

Test Example  One: Organic anti-reflective coating  Manufacture and evaluation

The organic antireflective coating compositions of Examples 1 to 3 and Comparative Example 1 were spin-coated on a silicon wafer to prevent cross-mixing with the photoresist to be formed in a later process for 10 to 120 seconds at 100 ° C to 250 ° C. Crosslinked. Thereafter, the photoresist was spin-coated on the cured organic antireflection film, and soft baked at 80 ° C. or 120 ° C. for 30 to 120 seconds to remove the remaining solvent, followed by exposure through a 100 nm photomask, and 2.38 wt% tetramethyl. After the development process for 20 to 100 seconds using an alkaline developer such as ammonium hydroxide (TMAH), the results as shown in Table 2 are described.

Undercutting Putting CD change of pattern Example 1 ○ ◎ 130 nm Example 2 ○ ◎ 100 nm Example 3 ◎ ◎ 90 nm Comparative Example 1 × △ 200 nm

◎: Never occurs ○: 1 to 5% occurs

△: 5 to 10% occurs ×: defective

Referring to Table 2, the organic anti-reflective coating compositions of Examples 1 to 3 form acid equilibrium with the photoresist during development after the exposure process to form undercutting or footing at the bottom of the photoresist micropattern. In addition, the microcircuit dimensional change of the pattern due to the diffuse reflection is also very small, making it easy to form high resolution microcircuits of 60 nm to 150 nm.

4 is a photograph showing a 90 nm L / S pattern when a semiconductor pattern is formed using the organic antireflective coating composition of Example 3 of the present invention.

Referring to FIG. 4, in the case of the organic antireflection pattern manufactured using the organic antireflection film composition of Example 3 according to the present invention, it can be seen that the undercutting is not formed and the pattern is well formed vertically.

FIG. 5 is a photograph showing a 200 nm L / S pattern when a semiconductor pattern is formed using the organic antireflective coating composition of Comparative Example 1 of the present invention.

Referring to FIG. 5, in the case of the organic antireflection film manufactured using the organic antireflection film composition of Comparative Example 1, undercutting is formed in the pattern, and the pattern is not finely formed in comparison with the organic antireflection film pattern of Example 3 It can be seen that.

1 shows GPC results for polymers prepared according to Preparation Example 2 of the present invention.

Figure 2 shows the GPC results for the polymer prepared according to Preparation Example 3 of the present invention.

3 shows the GPC results for the polymer prepared according to Preparation Example 4 of the present invention.

4 is a photograph showing a 90 nm L / S pattern when a semiconductor pattern is formed using the organic antireflective coating composition of Example 3 of the present invention.

FIG. 5 is a photograph showing a 200 nm L / S pattern when a semiconductor pattern is formed using the organic antireflective coating composition of Comparative Example 1 of the present invention.

Claims (15)

A copolymer comprising an isocyanate derivative protected by a pyrazole group represented by Formula 1 below and a structural unit represented by Formula 4 below as a monomer, and having a weight average molecular weight of 5,000 to 100,000. <Formula 1>

<Formula 4>

In Formulas 1 and 4, R and R ₁ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, and R ₃ represents hydrogen and carbon atoms An alkyl group of 1 to 6, an alkoxyalkyl group of 1 to 6 carbon atoms, a hydroxyalkyl group of 1 to 6 carbon atoms or a halogenated alkyl group of 1 to 6 carbon atoms, R ₄ represents hydrogen or a methyl group, R ₆ represents hydrogen or a methyl group . The method according to claim 1, In addition to the derivative represented by the formula (1) and the structural unit represented by the formula (4), characterized in that it comprises one or two or more selected from the structural units represented by the formula (2) and formula (3) as a comonomer Copolymer: <Formula 2>

<Formula 3>

In Chemical Formulas 2 and 3, R ₂ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₅ each independently represent hydrogen or a methyl group, x represents a natural number of 1 to 6, In the copolymer, the mole fractions of the structural units represented by Chemical Formulas 1 to 4 are k, l, m and n, respectively, and k is 0.1 to 0.7, based on the total mole fraction k + l + m + n of the structural unit. 1 is 0-0.4, m is 0.1-0.7, n is 0.1-0.5. A derivative represented by the following formula (1), a structural unit represented by the following formula (4) and an initiator are dissolved in a polymerization solvent, Reacted according to the radical polymerization method for 2 to 24 hours at a temperature of 50 to 90 ° C. under an inert gas atmosphere, The initiator is selected from the group consisting of azobisisobutyronitrile (AIBN), di-t-butyloxide (DTBP), acetyl peroxide (APO), benzoyl peroxide (BPO) and azobisvaleronitrile (AIVN). 1 or 2 or more selected Method for producing a copolymer according to claim 1, wherein the polymerization solvent is one or two or more selected from the group consisting of dioxane, tetrahydrofuran and methyl ethyl ketone: <Formula 1>

<Formula 4>

In Formulas 1 and 4, R and R ₁ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms, and R ₃ represents hydrogen and carbon atoms An alkyl group of 1 to 6, an alkoxyalkyl group of 1 to 6 carbon atoms, a hydroxyalkyl group of 1 to 6 carbon atoms or a halogenated alkyl group of 1 to 6 carbon atoms, R ₄ represents hydrogen or a methyl group, R ₆ represents hydrogen or a methyl group . The method according to claim 3, For 1 mole of the derivative represented by Formula 1, 0.1 to 10 mol of the initiator is dissolved in 1 to 50 mol of the polymerization solvent. delete delete The method according to claim 3, For 1 mole of the derivative represented by Formula 1, Method for producing a copolymer, characterized in that the structural unit represented by the formula (4) and one or two selected from the structural units represented by the formula (2) and (3) in 0.1 to 15 moles in the polymerization solvent: <Formula 2>

<Formula 3>

In Chemical Formulas 2 and 3, R ₂ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, R ₅ each independently represent hydrogen or a methyl group, x represents the natural number of 1-6. delete Copolymers according to claim 1; And Containing an organic solvent, The organic solvent is butyrolactone, cyclopentanone, cyclohexanone, dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethyl lac Organic antireflection film composition, characterized in that one or two or more selected from the group consisting of tate. The method according to claim 9, 0.1 to 20% by weight of the copolymer; And Organic antireflection film composition comprising 80 to 99.9% by weight of the organic solvent. delete The method according to claim 9, The organic antireflection film composition further includes an additive, The additive is an organic antireflection film composition, characterized in that one or two or more selected from the group consisting of crosslinking reaction promoters, surface leveling agents, adhesion promoters and antifoaming agents. delete The method according to claim 12, An organic anti-reflective coating composition comprising the additive in an amount of 0.001 to 10% by weight based on the total weight of the composition. An organic antireflection film comprising an organic antireflection film composition according to claim 9.

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