KR102441290B1 - Composition for forming bottom anti-reflective coating layer - Google Patents

Abstract

[화학식 2]

상기 화학식 1에서, R은 수소 또는 메틸기이고, R₁은 0 내지 6의 헤테로 원자를 포함하는 탄소수 1 내지 12의 사슬형 또는 고리형의 포화 또는 불포화 탄화수소기이고, R₂, R₃ 및 R₄는 각각 독립적으로 수소, 0 내지 6의 헤테로 원자를 포함하는 탄소수 1 내지 12의 사슬형 또는 고리형의 포화 또는 불포화 탄화수소기이고, R₅는 0 내지 8의 헤테로 원자를 포함하는 탄소수 1 내지 18의 사슬형 또는 고리형 포화 또는 불포화 탄화수소기이며, 상기 화학식 2에서, R₆ 및 R₇은 각각 독립적으로 수소, 0 내지 3의 헤테로 원자를 포함하는 탄소수 1 내지 8의 사슬형 또는 고리형의 포화 또는 불포화 탄화수소기이고, R₈ 및 R₉는 각각 독립적으로, 0 내지 4의 헤테로 원자를 포함하는 탄소수 1 내지 16의 사슬형 또는 고리형의 포화 또는 불포화 탄화수소기이다.Disclosed is a composition for forming an organic antireflection film capable of suppressing gas generation during formation of the organic antireflection film and forming an organic antireflection film having a high refractive index. The composition for forming an organic anti-reflection film may include a first isocyanurate-based polymer having a repeating unit represented by the following Chemical Formula 1; a second isocyanurate-based polymer having a repeating unit represented by the following formula (2); and solvents.
[Formula 1]

[Formula 2]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including 0 to 6 hetero atoms, R ₂ , R ₃ and R ₄ are each independently hydrogen, a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including 0 to 6 heteroatoms, and R ₅ is 0 to 8 carbon atoms including hetero atoms of 1 to 18 carbon atoms. a chain or cyclic saturated or unsaturated hydrocarbon group, and in Formula 2, R ₆ and R ₇ are each independently hydrogen, 0 to 3 C1 to C8 chain or cyclic saturated or cyclic saturated or an unsaturated hydrocarbon group, and R ₈ and R ₉ are each independently a C 1 to C 16 chain or cyclic saturated or unsaturated hydrocarbon group containing a 0 to 4 hetero atom.

Description

Composition for forming an organic anti-reflective film {Composition for forming bottom anti-reflective coating layer}

The present invention relates to a composition for forming an organic antireflection film, and more particularly, to a composition for forming an organic antireflection film capable of suppressing gas generation during formation of the organic antireflection film and forming an organic antireflection film having a high refractive index.

In a photolithography process, an ArF (193 nm) excimer laser with a short wavelength is used as an exposure light source in order to improve the resolution limit of the photoresist pattern. However, when the wavelength of the exposure light source is shortened, the interference effect due to light reflected from the etched layer of the semiconductor substrate is increased, and the pattern profile is deteriorated or the size uniformity is reduced due to undercutting and notching. occurs To prevent this, an organic bottom anti-reflective coatings (BARCs) for absorbing exposure light (reflected light) is typically formed between the etched layer and the photoresist layer.

The organic anti-reflection film is usually composed of a polymer containing a cross-linkable functional group, a cross-linker that is a single molecule, a thermal acid generator that generates an acid by heat to cause cross-linking, and a solvent. However, the crosslinking agent and the thermal acid generator are the main causes of out gassing by sublimation in a heating process such as baking after coating, and at this time, the generated gas is a defect in the process and It may cause equipment contamination.

Accordingly, it is an object of the present invention to provide a composition for forming an organic antireflection film having a high refractive index and preventing gas from being generated during the process.

Another object of the present invention is to provide a composition for forming an organic anti-reflection film, which eliminates the need to use a thermal acid generator and a cross-linking agent or can reduce the amount used.

The present invention relates to a first isocyanurate-based polymer having a repeating unit represented by the following formula (1); a second isocyanurate-based polymer having a repeating unit represented by the following formula (2); And it provides a composition for forming an organic anti-reflection film comprising a solvent.

[Formula 1]

[Formula 2]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including 0 to 6 hetero atoms, R ₂ , R ₃ and R ₄ are each independently hydrogen, a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including 0 to 6 heteroatoms, and R ₅ is 0 to 8 carbon atoms including hetero atoms of 1 to 18 carbon atoms. a chain or cyclic saturated or unsaturated hydrocarbon group, and in Formula 2, R ₆ and R ₇ are each independently hydrogen, 0 to 3 C1 to C8 chain or cyclic saturated or cyclic saturated or an unsaturated hydrocarbon group, and R ₈ and R ₉ are each independently a C 1 to C 16 chain or cyclic saturated or unsaturated hydrocarbon group containing a 0 to 4 hetero atom.

The composition for forming an organic anti-reflection film according to the present invention does not use a crosslinking agent and a thermal acid generator, so it is possible to suppress the generation of fume when the organic anti-reflection film is formed, and cross-linking by heat is possible.

In addition, the composition for forming an organic anti-reflection film according to the present invention has a high refractive index of 1.90 or more at a wavelength of 193 nm, and thus has a small reflectivity even if the thickness of the coating is small, and contains a large amount of hetero atoms. It is possible to shorten the etching time for the removal of the pattern, so that the pattern can be deeply transferred to the lower layer.

Hereinafter, the present invention will be described in detail.

The composition for forming an organic anti-reflection film according to the present invention is capable of suppressing the generation of gas when the organic anti-reflection film is formed, and includes a first isocyanurate-based polymer, a second isocyanurate-based polymer and a solvent. do.

The first isocyanurate-based polymer serves to maintain a high refractive index and increase adhesion to the upper layer, and has a repeating unit represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including 0 to 6 hetero atoms, R ₂ , R ₃ and R ₄ are each independently hydrogen, a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including a hetero atom having 0 to 6 carbon atoms.

Specifically, R ₁ is an alkyl group having 1 to 10 carbon atoms including 0 to 4 nitrogen (N), oxygen (O) and/or sulfur (S), more specifically, an ether group having 2 to 8 carbon atoms, R ₂ is hydrogen, R ₃ and R ₄ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, most specifically, an alkyl group having 1 to 5 carbon atoms.

Wherein R ₅ is a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms including a hetero atom of 0 to 8, specifically nitrogen (N), oxygen (O) and / or sulfur (S) 0 an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, a 4 to 8 membered cyclic hydrocarbon group or an amine group including 4 to 4 carbon atoms.

Specific examples of the repeating unit represented by Chemical Formula 1 may include the following Chemical Formulas 1a to 1k.

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

[Formula 1g]

[Formula 1h]

[Formula 1i]

[Formula 1j]

[Formula 1k]

The weight average molecular weight of the first isocyanurate-based polymer is 1,500 to 10,000, specifically 2,000 to 9,000, and more specifically 2,500 to 8,000. When the weight average molecular weight is within the above range, the solubility of the first isocyanurate-based polymer in the solvent is good, the organic antireflection film using the same is not dissolved by the solvent, and the etching rate in the dry etching process is preferable. The first isocyanurate-based polymer preferably includes the repeating unit represented by Formula 1, but other repeating units may be included as long as the function of the first isocyanurate-based polymer is not disturbed.

As shown in Scheme 1 below, the first isocyanurate-based polymer is (i) tris(1,3-oxathioran-2-thion-5-ylmethyl)isocyanurate (tris(1,3) -oxathiolane-2-thion-5-ylmethyl)isocyanurate) or tris(5-methyl-1,3-oxathiolan-2-thion-5-ylmethyl)isocyanurate (tris(5-methyl-1, 3-oxathiolane-2-thion-5-ylmethyl)isocyanurate) at room temperature (25 ℃) in a solvent such as dimethyl formamide (DMF), one or more amine groups (-NH ₂ ) and the R ₃ or After reacting with a compound containing R ₄ to form a polymer including an isocyanurate-based repeating unit represented by (a) below, (ii) an isocyanurate-based repeating unit represented by the following formula (a) It can be obtained by dissolving in a solvent such as tetrahydrofuran (THF), and reacting with an acyl chloride or acyl bromide containing R ₅ .

[Scheme 1]

In Scheme 1, R, R ₁ to R ₅ are as defined in Formula 1, and X is chlorine (Cl) or bromine (Br).

The second isocyanurate-based polymer provides a fast etch rate and serves as a crosslinking agent, and has a repeating unit represented by the following formula (2).

[Formula 2]

In Formula 2, R ₆ and R ₇ are each independently hydrogen, a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms including 0 to 3 heteroatoms, specifically hydrogen, and R ₈ and R ₉ is each independently a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 16 carbon atoms including 0 to 4 heteroatoms, specifically, 1 to 10 carbon atoms including 0 to 4 hydroxyl groups an alkyl group, an alkenyl group, a carbonyl group, or an ester group.

In addition, specific examples of the repeating unit represented by Chemical Formula 2 may include the following Chemical Formulas 2a to 2e.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

The weight average molecular weight of the second isocyanurate-based polymer is 1,500 to 10,000, specifically 1,500 to 7,500, and more specifically 2,000 to 5,000. When the weight average molecular weight of the second isocyanurate-based polymer is within the above range, physical properties such as uniformity of the organic anti-reflection film formed while crosslinking is smoothly performed are excellent. The second isocyanurate-based polymer preferably includes the repeating unit represented by Formula 2, but other repeating units may be included as long as the function of the second isocyanurate-based polymer is not disturbed.

In addition, the second isocyanurate-based polymer is (i) tris(2-hydroxyethyl)isocyanurate or tris(2,3-dihydroxypropyl)isocyanurate in 1,4-dioxane solvent Under, after reacting the powderlink 1174 at a temperature of 60 to 150 ° C. for 10 to 90 minutes, a catalyst such as para-toluene sulfonic acid is added to further react for 6 to 18 hours. After lowering the temperature of the reaction solution to room temperature (25° C.), it can be obtained by dropwise addition to butyl acetate.

The solvent may be a conventional solvent used in the composition for forming an organic antireflection film, for example, cyclohexanone, cyclopentanone, butyrolactone, dimethylacetamide ), dimethylformamide, dimethylsulfoxide, N-methyl pyrrolidone (NMP), tetrahydro furfural alcohol, methyl 2-hydroxyisobutyrate ( Methyl 2-hydroxyisobutyrate: HBM), Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl lactate, mixtures thereof, etc. can be used

In the composition for forming an organic antireflection film according to the present invention, the content of the first isocyanurate-based polymer is 0.05 to 5.00% by weight, specifically 0.10 to 4.00% by weight, more specifically 0.20 to 3.00% by weight, and , The content of the second isocyanurate-based polymer is 0.05 to 5.00% by weight, specifically 0.10 to 4.00% by weight, more specifically 0.20 to 3.00% by weight, the content of the solvent is 90.00 to 99.90% by weight, Specifically, 92.00 to 99.50% by weight, more specifically 94.00 to 99.30% by weight. When the content of the first isocyanurate-based polymer, the second isocyanurate-based polymer, and the solvent are within the above ranges, the organic antireflection film is smoothly formed and has excellent physical properties such as uniformity.

The organic anti-reflection film according to the present invention can be formed by performing the steps of applying the composition for forming an organic anti-reflection film on an upper portion of an etched layer such as a silicon wafer or an aluminum substrate and crosslinking the applied composition for forming an organic anti-reflection film. have. The step of applying the composition for forming an organic antireflection film may be performed by a conventional method such as spin coating or roller coating, and the step of crosslinking the applied composition for forming an organic antireflection film comprises applying the applied composition to a high-temperature plate, It can be carried out by heating in a device such as a convection oven. The crosslinking is carried out at 90 to 240 ° C, specifically 150 to 210 ° C. When the heating temperature is within the above range, the crosslinking reaction is sufficiently performed while the solvent contained in the composition for forming an organic antireflection film is sufficiently removed, The composition for forming an organic antireflection film and the organic antireflection film are chemically stable.

Hereinafter, the present invention will be described in more detail through Examples, but the present invention is not limited by the Examples.

[Preparation Example 1] Preparation of isocyanurate compound

297.6 g of triglycidyl isocyanurate, 8.7 g of lithium bromide, and 762.8 g of acetonitrile were added to a round-bottom flask reactor and stirred for 30 minutes. After lowering the temperature of the stirring solution to 10 °C, 456.8 g of carbon disulfide was added dropwise, the temperature was slowly raised to room temperature, and stirred under a nitrogen stream for 24 hours to prepare a compound represented by the following formula (3) did.

[Formula 3]

[Preparation Example 2] Preparation of a polymer having a repeating unit represented by Formula 4

20 g of the compound (Formula 3) prepared in Preparation Example 1, 1,2-bis(2-aminoethoxy)ethane) 4.2 g, propylamine 3.4 g and 156.4 g of dimethylformamide were put into a reactor and reacted with stirring at room temperature (25° C.) for 8 hours to prepare a polymer having a repeating unit represented by the following formula (4). (Weight average molecular weight (Mw): about 5,500, PolyDispersity Index (PDI): 1.5)

[Formula 4]

[Preparation Example 3] Preparation of a polymer having a repeating unit represented by Formula 5

Except for using 5.8 g of dipropylamine instead of 3.4 g of propylamine, the preparation method of Preparation Example 2 was the same, and as a result, a polymer having a repeating unit represented by the following Chemical Formula 5 was prepared. (Weight average molecular weight (Mw): about 6,300, polydispersity index (PDI): 1.5)

[Formula 5]

[Preparation Example 4] Preparation of a polymer having a repeating unit represented by Formula 1a

10 g of the compound (Formula 4) prepared in Preparation Example 2 and 81.6 g of tetrahydrofuran (THF) were put in a reactor, dissolved at room temperature, and then 6.1 g of triethylamine was added dropwise while stirring continuously. After stirring at room temperature for 1 hour, the temperature was lowered to 0 °C, acetyl chloride 4.3 g was added dropwise, and after reacting for 30 minutes, the temperature was slowly raised to room temperature (25 °C) and the reaction was continued for 12 hours. did it After removing the solid produced after the reaction, the reaction solution was added dropwise to diethyl ether, and then the precipitate was dried to prepare a polymer having a repeating unit represented by the following Chemical Formula 1a. (Weight average molecular weight (Mw): about 5,700, polydispersity index (PDI): 1.5)

[Formula 1a]

[Preparation Example 5] Preparation of a polymer having a repeating unit represented by Formula 1k

The same method as in Preparation Example 4 except that the compound (Formula 5) prepared in Preparation Example 3 was used instead of the compound prepared in Preparation Example 2 (Formula 4), and as a result, a polymer having a repeating unit represented by the following Chemical Formula 1k was prepared. (Weight average molecular weight (Mw): about 6,500, polydispersity index (PDI): 1.5)

[Formula 1k]

[Preparation Example 6] Preparation of a polymer having a repeating unit represented by Formula 1b

It was the same as in Preparation Example 4 except that 5.2 g of methyl chloroformate was used instead of 4.3 g of acetyl chloride, and as a result, a polymer having a repeating unit represented by the following Chemical Formula 1b was prepared. (Weight average molecular weight (Mw): about 5,800, polydispersity index (PDI): 1.5)

[Formula 1b]

[Preparation Example 7] Preparation of a polymer having a repeating unit represented by Formula 1g

It was the same as in Preparation Example 4 except that 5.9 g of dimethylcarbamyl chloride was used instead of 4.3 g of acetyl chloride, and as a result, a polymer having a repeating unit represented by the following Chemical Formula 1g was prepared. (Weight average molecular weight (Mw): about 5,800, polydispersity index (PDI): 1.5)

[Formula 1g]

[Preparation Example 8] Preparation of a polymer having a repeating unit represented by Formula 2a

Tris (2-hydroxyethyl) isocyanurate (Tris (2-hydroxyethyl) isocyanurate) 16.4 g, powderlink (powderlink) 1174 (manufacturer: Cytec Industries Inc.) 30.0 g, 1,4-dioxane (1,4) -dioxane) 95.2 g was put into a round bottom flask reactor and stirred at a temperature of 90 °C for 30 minutes. 0.2 g of Para Toluene Sulfonic Acid (PTSA) was added to the stirred solution and reacted for 10 hours. After lowering the temperature of the reaction solution to room temperature (25° C.), it was added dropwise to butyl acetate to obtain a precipitate, and then dried to prepare a polymer having a repeating unit represented by the following Chemical Formula 2a. (Weight average molecular weight (Mw): about 2,000, polydispersity index (PDI): 1.5)

[Formula 2a]

[Preparation Example 9] Preparation of a polymer having a repeating unit represented by Formula 2e

Preparation Example except that 22.08 g of tris (2,3-dihydroxypropyl) isocyanurate was used instead of 16.4 g of tris (2-hydroxyethyl) isocyanurate 8, and as a result, a polymer having a repeating unit represented by the following Chemical Formula 2e was prepared. (Weight average molecular weight (Mw): about 3,000, polydispersity index (PDI): 1.7)

[Formula 2e]

[Example 1] Preparation of a composition for forming an organic anti-reflection film

0.45 g of the polymer (Formula 1a) prepared in Preparation Example 4, and 0.05 g of the polymer (Formula 2a) in Preparation Example 8 were mixed with 1-methoxy-2-propanol and 2-hydroxyisobutylate in a 1:1 ratio. After it was sufficiently dissolved in 49.50 g of the mixed solvent, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 2] Preparation of a composition for forming an organic anti-reflection film

0.35 g of the polymer (Formula 1a) prepared in Preparation Example 4, 0.15 g of the polymer (Formula 2a) in Preparation Example 8, 1-methoxy-2-propanol and 2-hydroxyisobutylate in a 1:1 ratio After it was sufficiently dissolved in 49.50 g of the mixed solvent, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 3] Preparation of a composition for forming an organic anti-reflection film

0.25 g of the polymer (Formula 1a) prepared in Preparation Example 4, 0.25 g of the polymer (Formula 2a) prepared in Preparation Example 8, 1-methoxy-2-propanol and 2-hydroxyisobutylate were 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 4] Preparation of a composition for forming an organic anti-reflection film

0.15 g of the polymer (Formula 1a) prepared in Preparation Example 4, 0.35 g of the polymer (Formula 2a) prepared in Preparation Example 8, 1-methoxy-2-propanol and 2-hydroxyisobutylate were 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 5] Preparation of a composition for forming an organic anti-reflection film

0.05 g of the polymer (Formula 1a) prepared in Preparation Example 4 and 0.45 g of the polymer (Formula 2a) prepared in Preparation Example 8 were mixed with 1-methoxy-2-propanol and 2-hydroxyisobutylate 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 6] Preparation of a composition for forming an organic anti-reflection film

0.25 g of the polymer (Formula 1k) prepared in Preparation Example 5, 0.25 g of the polymer (Formula 2a) prepared in Preparation Example 8, 1-methoxy-2-propanol and 2-hydroxyisobutylate were 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 7] Preparation of a composition for forming an organic anti-reflection film

0.25 g of the polymer (Formula 1b) prepared in Preparation Example 6, 0.25 g of the polymer (Formula 2a) prepared in Preparation Example 8, 1-methoxy-2-propanol and 2-hydroxyisobutylate were 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 8] Preparation of a composition for forming an organic anti-reflection film

0.25 g of the polymer (Formula 1g) prepared in Preparation Example 7, 0.25 g of the polymer (Formula 2a) prepared in Preparation Example 8, 1-methoxy-2-propanol and 2-hydroxyisobutylate were 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 9] Preparation of a composition for forming an organic anti-reflection film

0.25 g of the polymer (Formula 1a) prepared in Preparation Example 4, 0.25 g of the polymer (Formula 2e) prepared in Preparation Example 9, 1-methoxy-2-propanol and 2-hydroxyisobutylate were 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Example 10] Preparation of a composition for forming an organic anti-reflection film

0.25 g of the polymer (Formula 1g) prepared in Preparation Example 7, 0.25 g of the polymer (Formula 2e) prepared in Preparation Example 9, 1-methoxy-2-propanol and 2-hydroxyisobutylate were 1: After sufficiently dissolved in 49.50 g of the solvent mixed with 1, it was filtered using a 0.45 μm filter to prepare a composition for forming an organic antireflection film.

[Comparative Example 1] Preparation of a composition for forming an organic anti-reflection film

0.50 g of the polymer (Formula 1a) prepared in Preparation Example 4, 0.10 g of powder link 1174, and 0.02 g of triethylammonium nonaflate (thermal acid dissipating agent) were mixed with 1-methoxy-2-propanol and 2-hydride. A composition for forming an organic antireflection film was prepared by sufficiently dissolving in 49.38 g of a solvent in which oxyisobutylate was mixed at a ratio of 1:1, and then filtration using a 0.45 μm filter.

[Comparative Example 2] Preparation of a composition for forming an organic anti-reflection film

A composition for forming an organic antireflection film was prepared in the same manner as in Comparative Example 1, except that 0.02 g of triethylammonium nonaflate (thermal acid dissipating agent) was not used.

[Experimental Example 1] Formation and characteristic evaluation of organic anti-reflection film

Each of the compositions prepared in Examples 1 to 10 and Comparative Examples 1 and 2 was spin-coated on a silicon wafer, and then baked at 205° C. for 60 seconds to form an organic anti-reflection film having a thickness of 250 Å, and each The organic anti-reflection film was etched with dry etching gas (Ar, O ₂ , CF ₄ mixed) for 10 seconds using a Dielectric Etcher (product name: Exelan HPT) of Lam Research, and then the thickness was measured again to determine the etching rate of the organic anti-reflection film ( Etch rate, Å/sec) was calculated. In addition, by using an ellipsometer (Ellipsometer, manufacturer: JA Woolam, product name: VUV-303) equipment, the refractive index and extinction coefficient of the organic anti-reflection film at a wavelength of 193 nm were measured and shown in Table 1 below.

refractive index extinction coefficient etch rate Example 1 1.97 0.26 9.2 Example 2 2.01 0.26 11.5 Example 3 1.98 0.25 12.2 Example 4 1.97 0.25 13.3 Example 5 1.95 0.25 14.3 Example 6 1.93 0.25 10.1 Example 7 1.94 0.25 13.6 Example 8 2.02 0.26 12.7 Example 9 1.96 0.26 12.1 Example 10 2.00 0.25 13.5 Comparative Example 1 1.93 0.30 8.3 Comparative Example 2 1.93 0.29 8.6

As can be seen from Table 1, the organic antireflection film according to the present invention had a refractive index greater than 1.9 at a wavelength of 193 nm, a relatively low extinction coefficient, and a high etching rate of 9.2 or more.

[Experimental Example 2] Evaluation of organic anti-reflection film lithography performance

After skin coating DARC-A125 (Dongjin Semichem Co., Ltd.) on a silicon wafer and baking at 240° C. for 60 seconds to form a film having a thickness of 440 Å, in Examples 1 to 10 and Comparative Examples 1 and 2 on the film An organic anti-reflection film including the prepared composition was respectively formed. After applying the photoresist DHA-HD150 (Dongjin Semichem Co., Ltd.) to a thickness of 1,300 Å, it was soft-baked at 110° C. for 60 seconds. Thereafter, using an exposure mask having a line-and-space (L/S) pattern, exposure was performed using 193 nm ArF exposure equipment, ASML 1200B, 0.85NA), and post-baked at 120° C. for 80 seconds. Next, it was developed with 2.38 wt% of an aqueous solution of TetraMethylAmmonium Hydroxide (TMAH) to form a 1:1.25 line and space (L/S) pattern with a line width of 70 nm. The patterns were observed using a scanning electron microscope, and the results are shown in Table 2 below.

pattern shape Example 1 vertical shape Example 2 vertical shape Example 3 vertical shape Example 4 vertical shape Example 5 vertical shape Example 6 vertical shape Example 7 vertical shape Example 8 vertical shape Example 9 vertical shape Example 10 vertical shape Comparative Example 1 Weak Footing and Weak Scum Comparative Example 2 Cannot form organic anti-reflection film
intermixing with PR

As can be seen from Table 2, the organic anti-reflection film according to the present invention was formed in a vertical pattern, and in Comparative Example 1 using a general crosslinking agent, footing and scum were weak, and the thermal acid generator was not used. In Example 2, an organic antireflection film was not formed.

Claims (6)

A first isocyanurate-based polymer having a repeating unit represented by the following Chemical Formula 1;
a second isocyanurate-based polymer having a repeating unit represented by the following formula (2); and
A composition for forming an organic antireflection film comprising a solvent.
[Formula 1]

[Formula 2]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including a hetero atom of 0 to 6, R ₂ , R ₃ and R ₄ are each independently hydrogen, a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms including 0 to 6 heteroatoms, and R ₅ is 0 to 8 carbon atoms including hetero atoms of 1 to 18 carbon atoms. a chain or cyclic saturated or unsaturated hydrocarbon group,
In Formula 2, R ₆ and R ₇ are each independently hydrogen, a chain or cyclic saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms including 0 to 3 hetero atoms, and R ₈ and R ₉ are each Independently, it is a C1-C16 chain or cyclic saturated or unsaturated hydrocarbon group containing a 0-4 hetero atom. According to claim 1, wherein the content of the first isocyanurate-based polymer is 0.05 to 5.00% by weight, the content of the second isocyanurate-based polymer is 0.05 to 5.00% by weight, the solvent is 90.00 to 99.90 The composition for forming an organic anti-reflection film in weight %. The organic antireflection film formation according to claim 1, wherein the weight average molecular weight of the first isocyanurate-based polymer is 1,500 to 10,000, and the weight average molecular weight of the second isocyanurate-based polymer is 1,500 to 10,000. for composition. According to claim 1, wherein R ₁ in Formula 1 is an alkyl group having 1 to 10 carbon atoms including 0 to 4 nitrogen, oxygen and/or sulfur, R ₂ is hydrogen, R ₃ and R ₄ are each independently hydrogen or An alkyl group having 1 to 10 carbon atoms, R ₅ is an alkyl group having 1 to 10 carbon atoms containing 0 to 4 nitrogen, oxygen and/or sulfur, an alkenyl group, an alkoxy group, a 4 to 8 membered cyclic hydrocarbon group or an amine group,
In Formula 2, R ₆ and R ₇ are hydrogen, and R ₈ and R ₉ are an alkyl group having 1 to 10 carbon atoms including 0 to 4 hydroxyl groups, an alkenyl group, a carbonyl group, or an ester group. composition. According to claim 1, wherein the repeating unit represented by the formula (1)

(Formula 1a),

(Formula 1b),

(Formula 1c),

(Formula 1d),

(Formula 1e),

(Formula 1f),

(Formula 1g),

(Formula 1h),

(Formula 1i),

(Formula 1j) and

(Formula 1k) is selected from the group represented,
The repeating unit represented by Formula 2 is

(Formula 2a),

(Formula 2b),

(Formula 2c),

(Formula 2d) and

A composition for forming an organic anti-reflection film, which is selected from the group represented by (Formula 2e). According to claim 1, wherein the solvent is cyclohexanone, cyclopentanone, butyrolactone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofurfural alcohol, methyl 2-hydr A composition for forming an organic antireflection film, which is selected from the group consisting of hydroxyisobutyrate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and mixtures thereof.