KR20180133230A - Composition for forming organic anti-reflection coating layer having high etch rate - Google Patents

Abstract

Disclosed are a composition for forming an organic antireflection film which has an antireflection function, is useful for simplification of the process, and has excellent pattern profile and a high etching ratio, and a method for forming the same. The composition for forming the organic antireflection film comprises: an antireflection polymer comprising a repeating unit represented by chemical formula 1-1, chemical formula 1-2 and chemical formula 1-3; an isocyanurate compound containing at least one moiety represented by chemical formula 2; and an organic solvent for dissolving the aforementioned components. In chemical formula 1-1 to 1-3, R_1 is hydrogen or a methyl group, R_2 is hydrogen, a methyl group, or a hydrocarbon group of 1 to 5 carbon atoms containing 0 to 2 hetero atoms, and R_3 is a hydrocarbon group of 1 to 12 carbon atoms containing 0 to 2 hetero atoms not including a chromophore.

Description

TECHNICAL FIELD The present invention relates to a composition for forming an organic anti-reflection coating having a high etching rate,

The present invention relates to an organic antireflection film, and more particularly, to a composition for forming an organic antireflection film which not only has a high etching ratio, but also simplifies the process and reduces photoresist damage after etching.

In the photolithography process, an ArF (193 nm) excimer laser having a short wavelength is used as an exposure source in order to improve the critical resolution of the photoresist (PR) pattern. However, if the wavelength of the exposure light source is short, the light interference effect due to the reflected light reflected by the etching layer 30 of the semiconductor substrate is increased and the pattern profile becomes poor due to undercutting, notching, There arises a problem that the uniformity of the size is lowered. In order to prevent this, bottom anti-reflective coatings (BARCs) for absorbing exposure light (reflected light) are usually formed between the etching layer and the photoresist film. Such an antireflection film is classified into an inorganic antireflection film such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon and the like and an organic antireflection film made of a polymer material, depending on the kind of the material used. In general, the organic antireflection film is superior to the inorganic antireflection film in that it does not require a vacuum evaporation apparatus for forming a film, a chemical vapor deposition (CVD) apparatus, a sputtering apparatus, , And a low molecular weight material is not diffused from the organic antireflection film to the photoresist film during heating, coating, and drying, and an etch rate (etch rate) is relatively excellent in the dry etching process for the photoresist .

In the conventional organic antireflective film, a scum remains after the exposure process in a substrate having a step. In order to solve such a problem, as shown in FIG. 1, a metal layer 21 such as a Spin-on-Carbon (SOC) 22 or an Amorphous Carbon Layer (ACL) 22, Complex processes have been introduced. This scheme takes a long time to produce a single pattern due to complicated processes, and it has a limitation in the process due to damage to the photoresist in the etch process, It is required to develop a composition for forming an organic anti-reflection film effectively.

Accordingly, an object of the present invention is to provide a composition for forming an organic antireflection film having an antireflection function while having a high etching ratio during an etching process.

Another object of the present invention is to provide a composition for forming an organic antireflection film which has a high etching ratio to simplify the process and which has little damage to the photoresist after etching.

In order to accomplish the above object, the present invention provides an antireflection polymer comprising a repeating unit represented by the following formulas 1-1, 1-2, and 1-3; An isocyanurate compound containing at least one moiety represented by the following formula (2); And an organic solvent for dissolving the above components.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

(2)

Wherein R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a hydrocarbon group of 1 to 5 carbon atoms containing a heteroatom of 0 to 2, R ₃ is a carbon number not having a chromophore 1 to 12, R ₄ is a saturated or unsaturated, saturated or unsaturated hydrocarbon group having 6 to 20 carbon atoms and containing 0 to 2 hetero atoms, and x, y and z constitute a polymer X is in the range of 30 to 60 mol%, y is in the range of 0 to 50 mol%, and z is in the range of 10 to 50 mol%.

R is hydrogen or a methyl group, R 'is independently a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms or a cyclic saturated or unsaturated hydrocarbon group having 3 to 15 carbon atoms and containing 0 to 6 hetero atoms, R Quot; is a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms and 0 to 8 heteroatoms having a chain or a carbon number of 3 to 15, and each of R '' 'is independently NH or O. Each R * is independently S or O, and adjacent functional groups have the same element.

The organic antireflection film having the antireflection function and the high etching ratio can be provided by the composition for forming an organic anti-reflective film according to the present invention. In addition, since the organic antireflection film has a high etching ratio, the process can be simplified, and the damage of the photoresist after etching can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a simplified process of an organic anti-reflective film according to the present invention for a conventional organic anti-reflective film. FIG.
2 is a diagram showing that there is almost no difference in critical dimension (CD) before and after an etch process;
3 is a graph showing a comparison of etch ratios of a photoresist and an organic anti-reflective film according to the present invention.

Hereinafter, the present invention will be described in more detail.

The composition for forming an organic antireflection film according to the present invention is a composition for forming an organic antireflection film which has an antireflection film function and simultaneously has a high etching ratio to simplify the process. The antireflection polymer, isocyanurate compound and organic Solvent.

The present invention has an anti-reflection film function at 193 nm and 248 nm wavelength including a gap-fill (void free) property for use in a step-wise process and a chromophore including a benzene ring or an anthracene structure, (1), which improves the profile of a pattern by effectively suppressing undercutting, notching, and footing caused by the reflected light, and a carbon-heteroatom Isocyanurate-based polymer represented by the following Chemical Formula 2 having a high etch rate by including a C-heteroatom bond, particularly a carbon-oxygen bond (CO bond). -0028763). When only the antireflection polymer is used, the etch rate is slow, so that damage to the photoresist (PR) occurs during the etching process, the scum remains in the y-th portion. In addition, when the isocyanurate polymer alone is used, there is a problem that a photoresist performance problem (PR performance issue) may occur due to insufficient antireflection function. These two kinds of polymers are used in combination to form an effective composition in terms of process simplification through a rapid etch ratio while having antireflection function.

The antireflection polymer according to the present invention includes the repeating units represented by the following formulas (1-1) to (1-3).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the general formulas 1-1 to 1-3, R ₁ is independently hydrogen or a methyl group, R ₂ is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms containing 0 to 2 hetero atoms, Specifically, it is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms containing 0 to 2 hetero atoms, for example, a hydrogen or a hydrocarbon group having 1 to 3 carbon atoms including a hydroxy group (-OH) and / or an epoxy group, and R ₃ is a hydrocarbon group having 1 to 12 carbon atoms which contains no heteroatom and contains a heteroatom of 0 to 2, and specifically includes hydrocarbons having 1 to 10 carbon atoms containing 0 to 2 hetero atoms More specifically a hydrocarbon group having 1 to 8 carbon atoms and containing 0 to 2 hetero atoms, and still more specifically 0 to 2 hetero atoms A hydrocarbon group having 4 to 8 carbon atoms, which.

R ₄ is a hydrocarbon group containing a chromophore which functions to absorb exposed light and is a chain or cyclic saturated or unsaturated hydrocarbon group having 6 to 20 carbon atoms and containing 0 to 2 hetero atoms , Specifically a chain or cyclic saturated or unsaturated hydrocarbon group having 6 to 16 carbon atoms and containing 0 to 2 hetero atoms, and more specifically, an aryl group having 6 to 16 carbon atoms containing 0 to 2 hetero atoms And most specifically an aryl group having 6 to 16 carbon atoms containing 1 to 2 hetero atoms.

,

등을 예시할 수 있고, 상기 R₃의 구체적인 예로써,

,

,

,

등을 예시할 수 있고, 상기 발색단을 포함하는 R₄의 구체적인 예로써, 벤젠 또는 안트라센을 포함하는 작용기, 구체적으로는

,

,

,

,

,

등을 예시할 수 있으며, 벤젠링 또는 안트라센 구조를 포함하여, 193nm, 248nm의 노광 조건에서 흡광하여 반사방지기능을 가진다.As a specific example of R ₂ , -H, -CH ₃ ,

,

As specific examples of R < _{3 &} gt ;, R < ₃ &

,

,

,

Specific examples of R ₄ including the chromophore include a functional group containing benzene or anthracene, specifically,

,

,

,

,

,

And includes benzene ring or anthracene structure, absorbs light under exposure conditions of 193 nm and 248 nm, and has an antireflection function.

X is 0 to 70 mol%, specifically 30 to 60 mol%, y is 0 to 70 mol%, specifically 0 to 50 mol%, z is 0 to 70 mol% Mol%, specifically 10 to 50 mol%.

In addition, the weight average molecular weight of the antireflection polymer is 1000 to 5000, specifically 2000 to 4000. If the weight average molecular weight of the antireflection polymer is too low, the yield of the antireflection polymer decreases and the production cost increases. When the antireflection polymer is too large, the etch rate is slowed. When the antireflection polymer is gap-filled in the topology, (void) may occur. The antireflection polymer may contain other components than those of the above formulas 1-1 to 1-3.

The antireflection polymer may include a structure represented by the following general formula (3).

(3)

X, y, and z are mole% of the repeating units constituting the antireflection polymer, and x is 1 to 3, 0 to 70 mol%, specifically 30 to 60 mol%, y is 0 to 70 mol%, specifically 0 to 50 mol%, and z is 0 to 70 mol%, specifically 10 to 50 mol%. If the content of x is too small, a film loss may occur. If the content of x is too high, the yield may be decreased. If the content of y is out of the range, the antireflection function may be deteriorated Spacer serves to replenish the rest of the x and z contents. If the content of z is deviated, the antireflection function may be deteriorated.

Representative examples of the polymer represented by the formula (3) include the following formulas (1a) to (1f). In the following formulas (1a) to (1f), x, y and z are as defined in the above formula (3).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

The isocyanurate compound has a good etch rate by containing a carbon-oxygen bond, and is represented by the following formula (2).

(2)

In Formula 2, R is hydrogen or a methyl group, and R 'may have at least one bonding site, and each independently represents a straight or branched chain having from 1 to 15 carbon atoms and containing from 0 to 6 hetero atoms, Saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms and 0 to 3 nitrogen (N) and / or oxygen (O) atoms in the form of a cyclic saturated or unsaturated hydrocarbon group, And R " are each independently a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 15 carbon atoms and containing 0 to 8 hetero atoms, and R ''' NH or O. Each of R ^{* s} is independently S or O, and adjacent functional groups have the same element.

More specifically, each R 'is independently an alkyl group having 0 to 2 hetero atoms, specifically an oxygen atom having 1 to 10 carbon atoms, specifically 1 to 8 carbon atoms, and R " An alkyl group having 1 to 10 carbon atoms, specifically having 1 to 6 carbon atoms, containing 2 hetero atoms, specifically oxygen and / or sulfur atoms, or 0 to 2 hetero atoms, specifically oxygen and / or sulfur atoms A cycloalkyl group, an aryl group or a heterocyclic group having 4 to 10 carbon atoms, specifically 5 to 6 carbon atoms.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

(여기서, 굴곡선(

)은 결합 부위를 나타낸다) 등을 예시할 수 있고, 상기 R"의 구체적인 예로는,

,

,

,

,

,

,

(여기서, 굴곡선()은 결합 부위를 나타낸다) 등을 예시할 수 있다. 여기서, 상기 R'의 결합부위가 둘 이상인 경우, 상기 R'에, 둘 이상의 상기 화학식 2로 표시되는 이소시아누레이트 화합물 중 R'을 제외한 나머지가 연결될 수 있으며(예를 들면, 상기 이소시아누레이트 화합물이 둘 이상일 경우, 하나의 이소시아누레이트 화합물 내의 R'와 다른 이소시아누레이트 화합물 내의 다른 위치에 있는 R'가 결합되는 등) 그에 따라, 상기 이소시아누레이트 화합물은 고분자의 구조를 가질 수 있다.Specific examples of the R '

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

(Here,

) Represents a bonding site), and specific examples of R "

,

,

,

,

,

,

(Where the bending line () represents a bonding site), and the like. When the bonding site of R 'is two or more, the R' may be connected to the remainder of the isocyanurate compounds represented by the formula (2) except R '(for example, the isocyanurate When the rate compound is more than two, R 'in one isocyanurate compound is combined with R' in another position in the other isocyanurate compound, etc.) Accordingly, the isocyanurate compound has a structure of the polymer Lt; / RTI >

The isocyanurate compound used in the present invention may be prepared by reacting an isocyanurate compound having two or more bonding sites using a compound containing R 'to form a polymer. Alternatively, the isocyanurate compound may be crosslinked by a crosslinking agent in the process of forming an organic anti- It is more effective to exist. At this time, the weight average molecular weight (Mw) of the isocyanurate compound is 2,000 to 10,000, specifically 4,000 to 8,000. If the weight average molecular weight is too small, the organic antireflection film may be dissolved by the photoresist solvent. If the weight average molecular weight is too large, solubility in solvents may be low and the etching rate of the organic antireflection film may be lowered in the dry etching process.

Specific examples of the isocyanurate compound represented by the formula (2) include compounds having a repeating unit represented by the following formulas (2a) to (2h).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

(2i)

(2j)

[Chemical Formula 2k]

≪ EMI ID =

[Formula 2m]

(2n)

(2o)

[Chemical Formula 2p]

The organic solvent may be a conventional organic solvent used in a composition for forming an organic anti-reflective coating. Examples of the organic solvent include cyclohexanone, cyclopentanone, butyrolactone, dimethylacetamide dimethylformamide, dimethylsulfoxide, N-methyl pyrrolidone (NMP), tetrahydrofurfural alcohol, propylene glycol monomethyl ether, and the like. Specific examples thereof include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether acetate (PGMEA), glycerol monomethyl ether (PGME), propylene glycol monomethyl ether acetate Organic solvents such as monomethyl ether (PGME), cyclopentanone, and mixtures thereof can be used .

In the composition for forming an organic anti-reflective coating film according to the present invention, the content of the antireflection polymer is 1 to 10 wt%, specifically 1 to 5 wt%, more specifically 2 to 4 wt% The content of the compound is 1 to 10 wt%, specifically 1 to 5 wt%, more specifically 2 to 4 wt%, the solvent is 85 to 97.5 wt%, specifically 88 to 96.5 wt%, more specifically, Is 89.35 to 94.8 wt%. If the content of the isocyanurate compound is out of the above range, the efficiency may be lowered due to a low etching rate. If the content of the polymer is out of the above range, there may be a problem in antireflection ability.

The composition for forming an organic anti-reflective coating film according to the present invention may further comprise a crosslinking agent or an acid generator. The crosslinking agent is capable of forming an organic antireflection film by cross-linking the polymer compound and the isocyanurate compound to form a polymer, and a conventional crosslinking agent can be used. For example, a melamine-based crosslinking agent Etc. may be used.

The acid generator accelerates the crosslinking reaction between the antireflection polymer compound and the isocyanurate compound, and a conventional acid generator can be used. For example, a sulfonium salt-based or iodonium salt-based compound or a mixture thereof may be used. Specific examples thereof include triphenylsulfonium nonaflate, dodecylbenzenesulfonic acid, p-toluenesulfonic acid ( paratoluenesulfonic acid) and the like. The content of the acid generator is 0.01 to 0.5 wt%, specifically 0.05 to 0.2 wt%. If the content of the acid generator is less than 0.01 wt%, the organic antireflection film may not be formed, %, A fume may be generated during the heating process, and the equipment may be contaminated.

The content of the crosslinking agent is 0.1 to 1.5 wt%, specifically 0.5 to 1 wt%, based on the total amount of the composition for forming an organic anti-reflective coating film according to the present invention. If the content of the crosslinking agent is too small, If it is too large, footing or the like may occur in the pattern profile.

The organic antireflection film according to the present invention may be formed by applying the composition for forming an organic antireflection film to an upper portion of a crystallization layer such as a silicon wafer or an aluminum substrate and crosslinking the applied composition for forming an organic antireflection film . The step of applying the composition for forming an organic anti-reflective layer may be performed by a conventional method such as spin coating or roller coating, and the step of crosslinking the coated composition for forming an organic anti- A convection oven or the like. The crosslinking is carried out at 90 to 240 캜, specifically 150 to 240 캜. When the heating temperature is lower than 90 캜, the solvent contained in the composition for forming an organic anti-reflective coating is not sufficiently removed, If the heating temperature exceeds 240 ° C, the composition for forming an organic anti-reflective film and the organic anti-reflective film may be chemically unstable .

The organic antireflective film formed from the composition for forming an organic anti-reflective film according to the present invention may have an etching rate of 1.5 times or more than that of a general photoresist when Cl ₂ / HBr / O ₂ is used as a dry etching gas, When CFx is used, the etching rate can be 2.2 times or more. The photoresist specifically refers to a polyhydroxylic clock photoresist.

It is possible to improve the anti-reflection and gap-fill performance by including the polymer 1 of formula (1), and by including the polymer 2 of formula (2), it has a high etch rate characteristic. -free organic antireflection film can be formed.

The organic antireflective film 40 of the present invention can be applied to the SOC 22 or the ACL 22 which has been used between the conventional photoresist 10 and the etching layer 30 as shown in FIG. By using the oxide layer 21 instead of the photoresist, it is possible to reduce the damage of the photoresist after etching by using a high etching rate as compared with that of the photoresist, and is useful as a new interlayer having an antireflection function and can simplify the process Thereby reducing the cost, thereby solving economical and scumming problems on the topology.

The organic antireflective film of the present invention has an etching rate higher than that of the photoresist. As shown in FIG. 2, there is almost no difference in the critical dimension (CD) 50 before and after the etching process, .

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

[Production Examples 1 to 6] Preparation of antireflection polymer

Each of the reactants 1 to 3 in the contents shown in the following Table 1 was placed in a 500 ml round-bottomed flask and then Methyl ethyl ketone (MEK) was added thereto to prepare a reaction product 1 (Hydroxyethyl methacrylate (HEMA), Gamma-Butyrolactone , GBL) and Reactant 3 (see Table 1). Next, the temperature was raised to 80 ° C using an oil bath, 7.87 g of dimethyl 2,2'-azobis (isobutyrate) (V-601) was added as an initiator, and the mixture was reacted for 15 hours. After the reaction was completed, the temperature was lowered to room temperature, and precipitated in Heptane, and the resulting powder was filtered and dried to obtain polymers (Production Examples 1 to 6) (yield, weight average molecular weight (Mw) And the polydispersity index (PDI) are shown in Table 1 below).

product Reactant 1
(HEMA) Reactant 2
(GBL) Reactant 3 Initiator yield(%) Mw PDI Kinds usage Production Example 1
(1a) 15g 3.97 g

3.54 g 7.8 g 84% 3684 1.80 Production Example 2
(1b) 15g 3.97 g

4.08 g 7.8 g 76% 4023 1.79 Production Example 3
(Formula 1c) 15g 3.97 g

5.99 g 7.8 g 83% 3988 1.78 Production Example 4
(1d) 15g 3.97 g

6.47 g 7.8 g 84% 3797 1.82 Production Example 5
(Formula 1e) 15g 3.97 g

7.01 g 7.8 g 82% 3910 1.79 Production Example 6
(1f) 15g 3.97 g

9.4 g 7.8 g 86% 3621 1.76

[Preparation Example 7] Preparation of isocyanurate compound

A-1. Preparation of isocyanurate compound

) 1.41 g(0.0095 몰), 화합물(

) 3.46 g(0.0285 몰) 및 디메틸포름아미드(DMF) 55.91g을 넣은 후, 상온(25℃)에서 24시간 동안 교반하며 반응시켜, 하기 화학식 3으로 표시되는 이소시아누레이트 화합물을 제조하였다(하기 화학식 4에서, R₅는

또는

(전체 화합물 내의 몰비율:

:

= 1:3)이며, R₅가

인 경우, 하기 화학식 3으로 표시되는 이소시아누레이트 화합물 중 상기 R₅를 제외한 나머지 두 개가

에 연결되어 고분자를 형성한다. 수율: 85%, 중량평균분자량(Mw): 4,905, 다분산 지수(PDI): 1.83).5 g (0.0095 mol) of tris (1,3-oxathiolane-2-thion-5-ylmethyl) isocyanurate (tris (1,3- , Compound (

), 1.41 g (0.0095 mol) of the compound (

), And 55.91 g of dimethylformamide (DMF) were placed and reacted with stirring at room temperature (25 ° C) for 24 hours to prepare an isocyanurate compound represented by the following formula (3) In Formula 4, R < ₅ >

or

(Molar ratio in total compound:

:

= 1: 3), and R < ₅ >

, The remaining two of the isocyanurate compounds represented by the following general formula (3) except R ₅

To form a polymer. Yield: 85%, weight average molecular weight (Mw): 4,905, polydispersity index (PDI): 1.83).

[Chemical Formula 4]

B-1. Preparation of isocyanurate compound represented by formula (2h)

76.29 g of tetrahydrofuran (THF) was added to a reactor (250 ml round-bottomed flask), 10 g of the isocyanurate compound represented by the formula (4) was added thereto and then 5.01 g of triethylamine (TEA) The temperature was lowered to 0 ° C using an icebath. 3.89 g of acetyl chloride was slowly added dropwise to the solution, and the reaction was allowed to proceed for 30 minutes. After the ice-bath was removed, the reaction was further performed for 15 hours. After completion of the reaction, the solid was filtered, and the remaining solution was precipitated in diethyl ether, followed by filtration and drying to give an isocyanurate compound represented by the formula (2h) (yield: 51, weight average Molecular weight (Mw): 3000, polydispersity index (PDI): 1.32).

A-2. Preparation of isocyanurate compound

) 1.41 g(0.0095 몰), 화합물(

) 3.46 g(0.0285 몰) 및 디메틸포름아미드(DMF) 55.91g을 넣은 후, 상온(25℃)에서 24시간 동안 교반하며 반응시켜, 하기 화학식 3-2로 표시되는 이소시아누레이트 화합물을 제조하였다(하기 화학식 3-2에서, R5는

또는

(전체 화합물 내의 몰비율:

:

= 1:3)이며, R5가

인 경우, 하기 화학식 3-2로 표시되는 이소시아누레이트 화합물 중 상기 R₅를 제외한 나머지 두 개가

에 연결되어 고분자를 형성한다. (수율: 76%, 중량평균분자량(Mw): 4,613, 다분산 지수(PDI): 1.81)The reactor was charged with 1,3,5-tris ((2-oxo-1,3-dioxolan-4-yl) methyl) -1,3,5- 5 g (0.0095 mol) of 3,5-tris ((2-oxo-1,3-dioxolan-4-yl) methyl) -1,3,5-triazinane-

), 1.41 g (0.0095 mol) of the compound (

) And 55.91 g of dimethylformamide (DMF) were placed and reacted with stirring at room temperature (25 ° C) for 24 hours to prepare an isocyanurate compound represented by the following formula 3-2 (In the formula 3-2, R5 represents

or

(Molar ratio in total compound:

:

= 1: 3), and R5 is

, The remaining two of the isocyanurate compounds represented by the following general formula (3-2) except for R < ₅ >

To form a polymer. (Yield: 76%, weight average molecular weight (Mw): 4,613, polydispersity index (PDI): 1.81)

[Formula 3-2]

B-2. Preparation of isocyanurate compound represented by formula (2p)

76.29 g of tetrahydrofuran (THF) was added to a reactor (250 ml round bottom flask), 10 g of the isocyanurate compound represented by the above formula (3-1) was added thereto and then 5.01 g of triethylamine (TEA) And the temperature was lowered to 0 ° C using an ice bath. 3.89 g of the compound (acetyl chloride) was slowly added dropwise to the solution, and the reaction was allowed to proceed for 30 minutes. Then, the ice-bath was removed and further reacted for 15 hours. After completion of the reaction, the solid was filtered, and the remaining solution was precipitated in diethyl ether, followed by filtration and drying to give the isocyanurate compound represented by Formula 3-2 (yield: 44, Weight average molecular weight (Mw): 2881, polydispersity index (PDI): 1.30).

[Examples 1 to 12 and Comparative Example 1] Preparation of a composition for forming an organic antireflection film

2 wt% of each of the polymers prepared in Preparation Examples 1 to 6, 2 wt% of the isocyanurate compound A-1 prepared in Preparation Example 7, 2-hydroxyhexyl paratoluene sulfonate (2- 0.2 wt% of hydroxyhexyl p-toluenesulfonate) and 1 wt% of Powderlink 1174 (1,3,4,6-Tetrakis (methoxymethyl) glycoluril) as a crosslinking agent were dissolved in 94.8 wt% of solvent PGMEA, Hydroxypropyl p-toluenesulfonate, and 1 wt% of a crosslinking agent Powderlink 1174 were dissolved in 94.8 wt% of solvent PGMEA. To prepare a composition for forming an organic anti-reflective coating film of Comparative Example 1. [

In addition, 2 wt% of each of the polymers prepared in Preparation Examples 1 to 6, 2 wt% of the isocyanurate compound A-2 prepared in Preparation Example 7, 2-hydroxyhexyl paratoluene sulfonate 0.2 wt% of 2-hydroxyhexyl p-toluenesulfonate and 1 wt% of Powderlink 1174 (1,3,4,6-Tetrakis (methoxymethyl) glycoluril) as a crosslinking agent were dissolved in 94.8 wt% of solvent PGMEA, Thereby preparing a composition for forming a protective film.

[Experimental Examples 1 and 2] [ 0100 ] An organic antireflection film (BARC) Dry etching (CL ₂ / HBr / O ₂ , CFx) evaluation

The organic antireflection film is formed by spin coating the compositions of Examples 1 to 12 and Comparative Example 1 on a silicon wafer at 1500 rpm and then baking at 220 DEG C for 60 seconds to form an organic antireflection film. The organic antireflection film was etched for 10 seconds with a dry etching gas (Cl ₂ / HBr / O ₂ ) and (CF x) using a Dielectric Etcher (product name: Exelan HPT) The etch rate (nm / sec) of the organic antireflection film was measured by measuring the thickness before and after the etching, and the results are shown in Table 2 below. The photoresist was a polyhydroxide clock photoresist.

BARC Experimental Example 1 Experimental Example 2 Furtherance Cl ₂ / HBr / O ₂
Etch rate (nm / sec) CFx
Etch rate (nm / sec) Photoresist 25.1 37.1 Example 1 (1a) + (2h) 39.1 87.1 Example 2 1b + 2h 38.2 83.6 Example 3 Formula 1c + Formula 2h 38.8 86.0 Example 4 1d + 2h 38.1 82.9 Example 5 1e + 2h 37.9 85.1 Example 6 (1f) + 2h 37.5 80.2 Example 7 Formula 1a + Formula 2p 33.6 82.8 Example 8 Formula 1b + Formula 2p 32.9 79.9 Example 9 Formula 1c + 2p 33.2 83.1 Example 10 1d + 2p 33.5 80.2 Example 11 Formula 1e + Formula 2p 32.6 83.1 Example 12 Formula 1f + 2p 32.7 84.2 Comparative Example 1 Formula 1a 23.2 68.4

3 is a graph showing etching ratios of a photoresist and an organic anti-reflection film (BARC) according to the present invention as a result of dry etching using Cl ₂ / HBr / O ₂ and CFx as dry etching gases, respectively. The general antireflection film during the etching process has a complicated process, which takes a long time to produce a single pattern. Since the etch rate is lower than that of the photoresist, the photoresist is damaged in the etch process, However, as can be seen from Table 2 and FIG. 3, the organic antireflection film according to the present invention has a high etching ratio to the photoresist, simplifying the process, and reducing the photoresist damage after etching. Accordingly, the composition for forming an organic anti-reflective layer according to the present invention forms an organic anti-reflective layer composition effective for simplifying the process through a rapid etching rate. The organic anti-reflective layer formed of the composition for forming an organic anti-reflective layer has an etching rate of 1.5 times or more higher than that of the photoresist when Cl ₂ / HBr / O ₂ is used as a dry etching gas, and CF x is used as the dry etching gas , It has an etching rate of 2.2 times or more. The organic antireflective film formed using only the antireflection film polymer as in Comparative Example 1 had a slow etch rate as compared with the photoresist when Cl ₂ / HBr / O ₂ was used as the dry etching gas, and CF x was used as the dry etching gas , It shows a faster etch rate than the photoresist but a slower etch rate than the organic antireflective films of Examples 1 to 6.

Claims (16)

An antireflection polymer comprising a repeating unit represented by the following formulas (1-1), (1-2), and (1-3);
An isocyanurate compound containing at least one moiety represented by the following formula (2); And
A composition for forming an organic antireflective film comprising an organic solvent.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

(2)

Wherein R ₁ is independently hydrogen or a methyl group, R ₂ is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms containing 0 to 2 hetero atoms, and R ₃ is a group containing a chromophore And R < ₄ > is a saturated or unsaturated, saturated or unsaturated hydrocarbon group having 6 to 20 carbon atoms and containing a heteroatom of 0 to 2, , X is from 30 to 60 mol%, y is from 0 to 50 mol%, z is from 10 to 50 mol%
R is hydrogen or a methyl group, R 'is independently a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms or a cyclic saturated or unsaturated hydrocarbon group having 3 to 15 carbon atoms and containing 0 to 6 hetero atoms, R Quot; is a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms and containing a hetero atom of 0 to 8 in the form of a cyclic or cyclic saturated or unsaturated hydrocarbon group having 3 to 15 carbon atoms, and each of R '''is independently NH or O. Each R ^* is independently S or O, and adjacent functional groups have the same element. 2. The antireflection film-forming composition according to claim 1, wherein the antireflection polymer comprises a composition for forming an antireflection film,
(3)

X, y, and z are mole% of the repeating units constituting the polymer, x is an integer of from 30 to 100, and R < 2 > 60 mol%, y is 0 to 50 mol%, and z is 10 to 50 mol%. The composition for forming an organic antireflection film according to claim 1, wherein the content of the antireflection polymer is 1 to 10% by weight. The composition for forming an organic antireflection film according to claim 1, wherein the content of the isocyanurate compound is 1 to 10% by weight. The composition for forming an organic antireflection film according to claim 1, wherein the composition for forming an organic anti-reflective layer further comprises 0.1 to 1.5% by weight of a crosslinking agent for crosslinking the isocyanurate compound. The composition for forming an organic antireflection film according to claim 1, further comprising 0.01 to 0.5% by weight of an acid generator that promotes the crosslinking reaction. According to claim 1, R ₂ of Formula 1-1 to 1-3 is the number of carbon atoms of 1 to 3 hydrocarbon groups containing hydrogen or from 0 to 2 heteroatoms, R ₃ is from 0 to 2 that does not contain the chromophore And R < ₄ > is a hydrocarbon group containing a chromophore which is an aryl group having 6 to 16 carbon atoms and contains 0 to 2 hetero atoms. [3] The method of claim 1, wherein R 'in Formula 2 is independently an alkyl group having 1 to 10 carbon atoms containing 0 to 2 hetero atoms, and R " is independently an alkyl group having 0 to 2 heteroatoms Or an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms, an aryl group or a heterocyclic group containing 0 to 2 hetero atoms. The composition for forming an organic antireflection film according to claim 1, wherein the antireflection polymer has a weight average molecular weight of 1,000 to 5,000. The composition for forming an organic antireflection film according to claim 1, wherein the isocyanurate compound has a weight average molecular weight of 2,000 to 10,000. [3] The method of claim 2, wherein the anti-reflection polymer comprises

(Formula 1a),

(1b),

(Formula 1c),

(1d),

(1e),

(1f), and mixtures thereof. ≪ / RTI > The isocyanurate compound according to claim 1, wherein the isocyanurate compound represented by formula (2)

(Formula 2a),

(Formula 2b),

(Formula 2c),

(Formula 2d),

(Formula 2e),

(2f),

(Formula 2g),

(2h),

(2i),

(Chemical chamber 2j),

(Formula 2k),

(Formula II),

(Formula 2m),

(2n),

(2o),

(Formula 2p), and a mixture thereof. 3. The method of claim 1, wherein the organic solvent is selected from the group consisting of cyclohexanone, cyclopentanone, butyrolactone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofurfural alcohol, propylene glycol mono Wherein the organic solvent is an organic solvent selected from the group consisting of methyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and mixtures thereof. The composition for forming an organic anti-reflective coating according to claim 1, wherein the organic antireflection film formed of the composition for forming an organic anti-reflective film has an etching rate higher than that of the photoresist. The organic antireflection film according to claim 1, wherein the organic antireflection film formed of the composition for forming an organic anti-reflective film has an etch rate of 1.5 times or more than that of the photoresist when Cl ₂ / HBr / O ₂ is used as a dry etching gas. / RTI > The composition for forming an organic anti-reflective coating according to claim 1, wherein the organic anti-reflective layer formed of the composition for forming an organic anti-reflective layer has an etching rate of 2.2 times or more higher than that of the photoresist when CFx is used as a dry etching gas.

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