KR20140083844A - Monomer for hardmask composition and hardmask composition including the monomer and method of forming patterns using the hardmask composition - Google Patents

Abstract

The present invention relates to a monomer for a hard mask composition represented by formula 1, a hard mask composition including the monomer, and a method for forming a pattern using the hard mask composition. In formula 1, A, A′, A″, L, L′, X^1 to X^3, and n are the same as defined in the specification.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard mask composition comprising a monomer for a hard mask composition, a hard mask composition comprising the monomer, and a pattern forming method using the hard mask composition. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

A hard mask composition comprising the monomer, and a pattern forming method using the hard mask composition.

BACKGROUND ART [0002] In recent years, the semiconductor industry has developed into an ultrafine technology having a pattern of a few to a few nanometers in a pattern of a size of several hundred nanometers. Effective lithographic techniques are essential to realize this ultrafine technology.

A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist layer to form a photoresist pattern, and etching the material layer using the photoresist pattern as a mask do.

In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile only by the typical lithographic technique described above. Accordingly, a layer called a hardmask layer may be formed between the material layer to be etched and the photoresist layer to form a fine pattern.

The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer is required to have properties such as chemical resistance, heat resistance and etching resistance so as to withstand the multiple etching process. As the coverage of the hard mask layer becomes wider, it is possible to form a hard mask layer on a predetermined pattern. In this case, a gap-fill characteristic and a planarization characteristic capable of filling a gap between the patterns need.

Meanwhile, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method. The spin-on coating method can use a hard mask composition having solubility in solvents.

However, there is a need for a hard mask composition capable of satisfying both of the above-mentioned properties and solubility required for a hard mask layer in a trade-off relationship with each other.

One embodiment provides a monomer for a hard mask composition capable of satisfying gap-fill characteristics, planarization characteristics, chemical resistance, heat resistance and etching resistance while securing solubility in a solvent.

Another embodiment provides a hardmask composition comprising the monomer.

Another embodiment provides a method of pattern formation using the hardmask composition.

According to one embodiment, there is provided a monomer for a hard mask composition represented by Formula 1 below.

[Chemical Formula 1]

In Formula 1,

A, A 'and A " are each independently an aliphatic cyclic group or an aromatic cyclic group,

X ¹ to X ³ each independently represent hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,

L and L 'are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group,

n is an integer of 1 to 5;

In formula (1), A, A 'and A "each independently represent a substituted or unsubstituted cyclic group selected from the following group 1.

[Group 1]

In the group 1,

Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR ^a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom or a combination thereof,

Z ³ to Z ¹⁷ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.

At least one of A, A 'and A " may be a polycyclic aromatic group.

The A may be a benzene group, a naphthalene group or a biphenyl group, the A 'may be a pyrene group, a perylene group, a benzopyrylene group or a coronene group, and the A "may be a substituted or unsubstituted aromatic ring group .

In Formula 1, the monomer may be represented by the following Formulas 1-1, 1-2, 1-3, or 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1, 1-2, 1-3, and 1-4,

La, Lb, Lc, Ld, Le, Lf, Lg, Lh, L'a, L'b, L'c, L'd, Or a substituted or unsubstituted C1 to C6 alkylene group,

xa, xb, yc, yd, ze and zf are each independently an integer of 0 to 5,

Tg and Th are each independently an integer of 0 to 9;

The monomer for the hard mask composition may be represented by the following formula (1-1a), (1-1b), (1-2a), (1-3a) or (1-4a).

[Formula 1-1a]

[Formula 1-1b]

[Formula 1-2a]

[Formula 1-3a]

[Chemical Formula 1-4a]

The monomer for the hard mask composition may have a molecular weight of 500 to 3,000.

According to another embodiment, there is provided a hard mask composition comprising a monomer as described above and a solvent.

The monomer may be included in an amount of 0.1% to 50% by weight based on the total content of the hard mask composition.

According to another embodiment, there is provided a method of manufacturing a hard mask, comprising the steps of providing a layer of material on a substrate, applying the hardmask composition described above on the layer of material, heat treating the hardmask composition to form a hardmask layer, Containing thin film layer, a step of forming a photoresist layer on the silicon-containing thin film layer, a step of exposing and developing the photoresist layer to form a photoresist pattern, a step of forming the silicon- Selectively removing the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

The step of applying the hard mask composition may be performed by a spin-on coating method.

The step of forming the hard mask layer may include a heat treatment at about 100 ° C to 500 ° C.

Excellent heat resistance and etching resistance can be secured while satisfying gap-fill and planarization characteristics.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a cyano group, A C3 to C30 cycloalkyl group, a C3 to C30 cycloalkyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C4 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, Substituted with a substituent selected from the group consisting of a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.

The monomers for the hard mask composition according to one embodiment will be described below.

The hard mask composition according to one embodiment may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

A, A 'and A " are each independently an aliphatic cyclic group or an aromatic cyclic group,

X ¹ to X ³ each independently represent hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,

L and L 'are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group,

n is an integer of 1 to 5;

At least one of A, A 'and A " may be a polycyclic aromatic group.

For example, A may be a benzene group, a naphthalene group, or a biphenyl group, and A 'may be a pyrene group, a perylene group, a benzopyrylene group or a coronene group, and the A "may be a substituted or unsubstituted aromatic ring group .

The monomers may have rigid properties by having polycyclic aromatic groups.

Further, the monomer is a structure having an alkylene group, and the alkylene group is represented by X ¹ and X ² When substituted with an appropriate functional group, amplification crosslinking is possible based on the condensation reaction with X ³ .

Therefore, the above-mentioned monomers can exhibit properties required in a hard mask layer such as excellent mechanical properties, heat resistance characteristics, chemical resistance, and etching resistance by crosslinking in the form of a polymer upon heat treatment.

The monomer includes a flexible alkylene group and a plurality of functional groups, so that the solubility in a solvent is also high and can be prepared in a solution form and formed by a spin-on coating method.

In addition, the monomer has excellent gap-fill characteristics and planarization characteristics that can fill gaps between patterns when formed on a lower film having a predetermined pattern by a spin-on coating method.

In formula (1), A, A 'and A "each independently represent a substituted or unsubstituted cyclic group selected from the following group 1.

[Group 1]

In the group 1,

Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR ^a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom or a combination thereof,

Z ³ to Z ¹⁷ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.

The monomer may be represented by, for example, the following formulas 1-1, 1-2, 1-3, or 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1, 1-2, 1-3, and 1-4,

La, Lb, Lc, Ld, Le, Lf, Lg, Lh, L'a, L'b, L'c, L'd, Or a substituted or unsubstituted C1 to C6 alkylene group,

xa, xb, yc, yd, ze and zf are each independently an integer of 0 to 5,

Tg and Th are each independently an integer of 0 to 9;

The monomer may be represented, for example, by the following general formulas 1-1a, 1-1b, 1-2a, 1-3a or 1-4a.

[Formula 1-1a]

[Formula 1-1b]

[Formula 1-2a]

[Formula 1-3a]

[Chemical Formula 1-4a]

The monomer may have a molecular weight of about 500 to 3,000. By having a molecular weight in the above range, the monomer having a high carbon content has a good solubility in a solvent, and a good thin film by spin-on coating can be obtained.

The hard mask composition according to one embodiment will be described below.

The hard mask composition according to one embodiment comprises the above-mentioned monomers and a solvent.

The above-mentioned monomers are as described above, and one kind of monomers may be contained singly or two or more kinds of monomers may be mixed and contained.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility to the monomer. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) At least one selected from methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, methylpyrrolidone, acetylacetone and ethyl 3-ethoxypropionate One can be included.

The monomer may be included in an amount of about 0.1% to 50% by weight based on the total amount of the hard mask composition. By incorporating the monomer in the above range, it can be coated with a thin film having a desired thickness.

The hard mask composition may further comprise a surfactant.

The surfactant may be, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

The surfactant may be included in an amount of about 0.001 part by weight to about 3 parts by weight based on 100 parts by weight of the hard mask composition. By including it in the above range, the solubility can be secured without changing the optical properties of the hard mask composition.

Hereinafter, a method of forming a pattern using the hard mask composition described above will be described.

A patterning method according to one embodiment includes the steps of providing a layer of material on a substrate, applying a hard mask composition comprising the above-mentioned monomers and a solvent on the material layer, heat treating the hard mask composition to form a hard mask layer Containing thin film layer on the hard mask layer; forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the silicon-containing thin film layer and the hard mask layer using a mask to expose a portion of the material layer, and etching the exposed portion of the material layer.

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be finally patterned and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer may be formed by, for example, a chemical vapor deposition method.

The hard mask composition may be prepared in the form of a solution and applied by a spin-on coating method. In this case, the coating thickness of the hard mask composition is not particularly limited, but may be, for example, about 50 Å to 50,000 Å thick.

The heat treatment of the hard mask composition may be performed at a temperature of, for example, about 100 캜 to 500 캜 for about 10 seconds to about 10 minutes. In the heat treatment step, the monomer may cause self-crosslinking and / or cross-linking reaction.

The silicon-containing thin film layer may be made of, for example, silicon nitride or silicon oxide.

Further, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer.

The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. Further, a heat treatment process may be performed at about 100 ° C to 500 ° C after exposure.

The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied to various patterns in a semiconductor integrated circuit device, for example.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Monomeric  synthesis

Synthetic example  One

Step 1: Horse short  Introduction reaction

A solution was prepared by adding 40.4 g (0.1345 mol) of coronene, 22.94 g (0.1345 mol) of 4-methoxybenzoyl chloride and 731 g of 1,2-dichloroethane to the flask. 17.9 g (0.1345 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 2: Pairing reaction

To the flask was added 10.0 g (0.02302 mol) of the compound obtained in the first step, 2.34 g (0.01151 mol) of terephthaloyl chloride and 194 g of 1,2-dichloroethane. 9.21 g (0.06906 mol) of aluminum chloride was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 3: Methyl group removal ( demethylation ) reaction

10.00 g (0.01001 mol) of the compound obtained in the second step, 10.13 g (0.05005 mol) of 1-dodecan sulfate, 3.37 g (0.06006 mol) of potassium hydroxide and 35.3 g of N, N-dimethylformamide were added to the flask Followed by stirring at 120 ° C for 8 hours. The mixture was cooled and neutralized to about pH 6 to about pH 7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried.

Step 4: Reduction reaction

To the flask was added 4.00 g (0.004120 mol) of the compound obtained in the third step and 28.5 g of tetrahydrofuran. To this solution was slowly added 3.12 g (0.08240 mol) of sodium borohydride and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction solution was neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by Formula 1-1a.

[Formula 1-1a]

Synthetic example  2

In Synthesis Example 1, except that 10.0 g (0.02302 mol) of the compound obtained in the first step was reacted with 2.34 g (0.01151 mol) of isophthaloyl chloride, the compound represented by Formula 1-1b ≪ / RTI >

[Formula 1-1b]

Synthetic example  3

Step 1: Horse short  Introduction reaction

To the flask, 20.0 g (0.07239 mol) of benzoperylene, 12.4 g (0.07239 mol) of 4-methoxybenzoyl chloride and 378 g of 1,2-dichloroethane were added to prepare a solution. Subsequently, 9.65 g (0.07239 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 2: Pairing reaction

To the flask was added 9.77 g (0.02380 mol) of the compound obtained in the first step, 2.42 g (0.01190 mol) of isophthaloyl chloride and 195 g of 1,2-dichloroethane. To the solution was slowly added 9.52 g (0.07140 mol) of aluminum chloride, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 3: Methyl group removal ( demethylation ) reaction

To the flask was added 5.94 g (0.006250 mol) of the compound obtained in the second step, 6.33 g (0.03125 mol) of 1-dodecan sulfate, 2.10 g (0.03750 mol) of potassium hydroxide and 21.6 g of N, N- dimethylformamide Followed by stirring at 120 ° C for 8 hours. The mixture was cooled and neutralized to about pH 6 to about pH 7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried. .

Step 4: Reduction reaction

To the flask was added 2.85 g (0.003090 mol) of the compound obtained in the third step and 20.8 g of tetrahydrofuran. An aqueous solution of 2.34 g (0.06180 mol) of sodium borohydride was slowly added to the solution, and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction mixture was neutralized to about pH 7 with a 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by the following Formula 1-2a.

[Formula 1-2a]

Synthetic example  4

Step 1: Horse short  Introduction reaction

To the flask, 18.5 g (0.07330 mol) of perylene, 12.5 g (0.07330 mol) of 4-methoxybenzoyl chloride and 367 g of 1,2-dichloroethane were added to prepare a solution. To the solution was slowly added 9.77 g (0.07330 mol) of aluminum chloride, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 2: Pairing reaction

To the flask was added 7.00 g (0.01812 mol) of the compound obtained in the first step, 1.84 g (0.009060 mol) of isophthaloyl chloride and 145 g of 1,2-dichloroethane. 7.25 g (0.05436 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 3: Methyl group removal ( demethylation ) reaction

7.00 g (0.007750 mol) of the compound obtained in the second step, 7.84 g (0.03875 mol) of 1-dodecane syll, 2.61 g (0.04650 mol) of potassium hydroxide and 26.2 g of N, N- dimethylformamide were added to the flask Followed by stirring at 120 ° C for 8 hours. The mixture was cooled and neutralized to about pH 6 to about pH 7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried.

Step 4: Reduction reaction

To the flask was added 5.00 g (0.005720 mol) of the compound obtained in the third step and 37.3 g of tetrahydrofuran. To this solution was slowly added an aqueous solution of 4.33 g (0.1144 mol) of sodium borohydride and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction mixture was neutralized to about pH 7 with a 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by Formula 1-3a.

[Formula 1-3a]

Synthetic example  5

Step 1: Horse short  Introduction reaction

A solution was prepared by adding 10.0 g (0.03329 mol) of coronene, 8.81 g (0.03329 mol) of 1-pyrenecarbonyl chloride and 209 g of 1,2-dichloroethane to the flask. Then, 4.44 g (0.03329 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 2: Pairing reaction

To the flask was added 10.0 g (0.01892 mol) of the compound obtained in the first step, 1.92 g (0.00946 mol) of isophthaloyl chloride and 175 g of 1,2-dichloroethane. 7.57 g (0.05675 mol) of aluminum chloride was slowly added to the solution, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 3: Reduction reaction

To the flask was added 5.00 g (0.004211 mol) of the compound obtained in the second step and 32.7 g of tetrahydrofuran. To this solution was slowly added 3.19 g (0.08423 mol) of sodium borohydride and the mixture was stirred at room temperature for 24 hours. When the reaction was completed, the reaction solution was neutralized to about pH 7 with a 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by the following Formula 1-4a.

[Chemical Formula 1-4a]

Comparative Synthetic Example  One

Step 1: Pairing reaction

To the flask was added 50.0 g (0.166 mol) of coronene, 46.8 g (0.333 mol) of benzoyl chloride and 330 g of 1,2-dichloroethane. To this solution, 44.4 g (0.333 mol) of aluminum chloride was slowly added at room temperature, and the temperature was raised to 60 ° C and the mixture was stirred for 8 hours. When the reaction was completed, methanol was added to the solution, and the resulting precipitate was filtered and dried.

Step 2: Reduction reaction

To the flask was added 25.0 g (0.0492 mol) of the compound obtained in the first step and 174 g of tetrahydrofuran. 18.6 g (0.492 mol) of sodium borohydride aqueous solution was slowly added to the solution, and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction solution was neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a polymer represented by the following formula (2).

(2)

Comparative Synthetic Example  2

To the flask was added 8.75 g (0.05 mol) of alpha, alpha '-dichloro-p-xylene, 26.66 g aluminum chloride and 200 g gamma -butyrolactone. A solution prepared by dissolving 35.03 g (0.10 mol) of 4,4 '- (9-fluorenylidene) diphenol in 200 g of? -Butyrolactone was slowly added to the solution, followed by stirring at 120 ° C for 12 hours. After the polymerization, the acid was removed using water and then concentrated. Subsequently, the polymerization product was diluted with methyl amyl ketone and methanol, and the concentration was adjusted by adding a solution of methyl amyl ketone / methanol = 4/1 (weight ratio) at a concentration of 15% by weight. This solution was placed in a separating funnel and n-heptane was added to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (3).

(3)

The polymer had a weight average molecular weight of 12,000 and a degree of dispersion of 2.04.

Hard mask  Preparation of composition

Example  One

The monomer obtained in Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)) and filtered to prepare a hard mask composition.

Example  2

A hard mask composition was prepared in the same manner as in Example 1, except that the monomer obtained in Synthesis Example 2 was used instead of the monomer obtained in Synthesis Example 1.

Example  3

A hard mask composition was prepared in the same manner as in Example 1, except that the monomer obtained in Synthesis Example 3 was used instead of the monomer obtained in Synthesis Example 1.

Example  4

A hard mask composition was prepared in the same manner as in Example 1, except that the monomer obtained in Synthesis Example 4 was used instead of the monomer obtained in Synthesis Example 1.

Example  5

A hard mask composition was prepared in the same manner as in Example 1, except that the monomer obtained in Synthesis Example 5 was used instead of the monomer obtained in Synthesis Example 1.

Comparative Example  One

A hard mask composition was prepared in the same manner as in Example 1, except that the monomer obtained in Comparative Synthesis Example 1 was used instead of the monomer obtained in Synthesis Example 1.

Comparative Example  2

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 2 was used in place of the monomer obtained in Synthesis Example 1.

Evaluation 1: Heat resistance

A hard mask composition having a monomer content of 5.0% by weight according to Examples 1 to 5 and Comparative Example 1 was applied on a silicon wafer by a spin-on coating method and then heat-treated at 240 캜 for 1 minute on a hot plate to form a thin film. The thickness of the initial thin film was measured with a K-MAC thin film thickness gauge. Subsequently, the thin film was heat-treated again at 400 ° C for 2 minutes, and the thickness of the thin film was measured, and then the thin film thickness reduction rate was calculated.

Thin film thickness reduction ratio = (thin film thickness after baking at 240 占 폚 - thin film thickness after baking at 400 占 폚) / thin film thickness X100 (%) after baking at 240 占 폚

On the other hand, the hard mask composition according to Examples 1 to 5 and Comparative Example 1 was coated on a silicon wafer by a spin-on coating method, pre-baked at 180 DEG C for 60 seconds, (Quartz Crystal Microbalance).

The thin film thickness reduction rate and outgas evaluation results are shown in Table 1.

Thin film thickness reduction rate (%) The amount of outgas (ng) Example 1 -5.75 24 Example 2 -5.87 20 Example 3 -8.82 25 Example 4 -9.98 37 Example 5 -10.32 52 Comparative Example 1 -34.08 180

Referring to Table 1, it can be seen that the hard mask composition according to Examples 1 to 5 has a smaller thickness reduction rate after heat treatment at 400 ° C than the thin film formed from the hard mask composition according to Comparative Example 1.

Also, it can be seen that the hard mask composition according to Examples 1 to 5 can stably perform a high-temperature process because the amount of outgas generated is low during baking at a high temperature (400 ° C). On the other hand, the hard mask composition according to Comparative Example 1 has a relatively large amount of outgas, which is not suitable for a high temperature process.

From the results, it can be seen that the hard mask composition according to Examples 1 to 5 has higher heat resistance even at a high temperature of 400 캜 because of the high degree of crosslinking of the thin film as compared with the hard mask composition according to Comparative Example 1.

Evaluation 2: Awareness of corrosion

A hard mask composition having a monomer or polymer content of 13.0% by weight in accordance with Examples 1 to 5 and Comparative Example 2 was applied on a silicon wafer by a spin-on coating method and then heat-treated at 400 ° C for 2 minutes on a hot plate to form a thin film The thickness of the thin film was measured.

Subsequently, the thin film was dry-etched for 60 seconds using an N ₂ / O ₂ mixed gas, and then the thickness of the thin film was measured. Further, the thin film was dry-etched for 100 seconds using a CFx mixed gas, and then the thickness of the thin film was measured. The bulk etch rate (BER) was calculated from the film thickness before and after etching. The results are shown in Table 2.

The etching rate (N ₂ / O ₂ ) The etching rate (CF _x ) Example 1 22.5 26.1 Example 2 22.3 25.7 Example 3 22.5 26.7 Example 4 23.9 28.8 Example 5 24.2 26.5 Comparative Example 2 26.7 32.0

The bulk etch rate (BER)

: (Initial thin film thickness - thin film thickness after etching) / etching time (seconds)

Referring to Table 2, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 5 has a lower etching rate than the thin film formed from the hard mask composition according to Comparative Example 2. [ From this, it can be seen that the hard mask composition according to Examples 1 to 5 has higher corrosion resistance than the hard mask composition according to Comparative Example 2.

Evaluation 3: Pattern formation

A silicon oxide (SiO ₂ ) layer with a thickness of 3,000 Å was formed on a silicon wafer by a chemical vapor deposition method. Next, the hard mask composition according to Examples 1 to 5 and Comparative Examples 1 and 2 was coated on the silicon oxide layer by a spin-on coating method, and then heat-treated at 400 ° C for 2 minutes on a hot plate to form a hard mask layer . Subsequently, a silicon nitride (SiN) layer was formed on the hard mask layer by a chemical vapor deposition method. Subsequently, the photoresist for KrF was coated and heat-treated at 110 ° C. for 60 seconds, exposed using ASML (XT: 1400, NA 0.93) exposure equipment, and developed with tetramethylammonium hydroxide (2.38 wt% TMAH aqueous solution). Subsequently, the silicon nitride layer was dry-etched using a mixed gas of CHF ₃ / CF ₄ using the patterned photoresist as a mask. Then, the hard mask layer was dry-etched using a N ₂ / O ₂ mixed gas using the patterned silicon nitride layer as a mask. Then, the silicon oxide layer was dry-etched using a CHF ₃ / CF ₄ mixed gas using the patterned hard mask layer as a mask, and then the remaining organic substances were removed using O ₂ gas.

Sectional view of the hard mask layer and the silicon oxide layer pattern was observed using an electron microscope (SEM). The results are shown in Table 3.

Hard mask layer pattern shape Silicon oxide layer pattern shape Example 1 Vertical shape Vertical shape Example 2 Vertical shape Vertical shape Example 3 Vertical shape Vertical shape Example 4 Vertical shape Vertical shape Example 5 Vertical shape Vertical shape Comparative Example 1 Tapered shape Tapered shape Comparative Example 2 Tapered shape Tapered shape

Referring to Table 3, the hard mask layer formed from the hard mask composition according to Examples 1 to 5 and the silicon oxide layer thereunder were all patterned in a vertical shape, while the hard mask layer formed with the hard mask composition according to Comparative Examples 1 and 2 It can be seen that the mask layer can not be patterned in a vertical shape and is patterned in a tapered shape.

From this, it can be seen that when the hard mask composition according to Examples 1 to 5 is used, a material layer having a better etching resistance than that of the hard mask composition according to Comparative Examples 1 and 2 is formed thereon, It can also be seen that a good pattern is formed.

Evaluation 4: Gap-fill and planarization characteristics

A hard mask composition having a monomer content of 13.0% by weight according to Examples 1 to 5 and Comparative Example 1 was applied to a patterned wafer by a spin-on coating method and heat-treated at 400 ° C for 2 minutes. Respectively.

The gap-fill characteristic was determined by observing the pattern section of a width of 40 nm and a depth of 500 nm and determining the void formation. The planarization characteristic was obtained by observing a pattern section having a width of 180 nm and a depth of 500 nm, . The planarization property is better as the difference between h ₁ and h ₂ is smaller, and therefore, the smaller the value, the better the planarization characteristic.

[Equation 1]

The results are shown in Table 4.

Gap-fill characteristic Planarization characteristics Example 1 void None 6.5 Example 2 void None 5.8 Example 3 void None 7.8 Example 4 void None 6.8 Example 5 void None 7.5 Comparative Example 1 void occurrence 17.4

Referring to Table 4, when the hard mask composition according to Examples 1 to 5 was used, voids were not observed as compared with the case of using the hard mask composition according to Comparative Example 1, and not only excellent gap-fill characteristics were exhibited, It can be seen that it is excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (12)

A monomer for a hard mask composition represented by Formula 1:
[Chemical Formula 1]

In Formula 1,
A, A 'and A " are each independently an aliphatic cyclic group or an aromatic cyclic group,
X ¹ to X ³ each independently represent hydrogen, a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group or a combination thereof,
L and L 'are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group,
n is an integer of 1 to 5; The method of claim 1,
Wherein A, A 'and A "are each independently a substituted or unsubstituted ring group selected from the following group 1:
[Group 1]

In the group 1,
Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR ^a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom or a combination thereof,
Z ³ to Z ¹⁷ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof. The method of claim 1,
Wherein at least one of A, A 'and A " is a polycyclic aromatic group. The method of claim 1,
Wherein A is a benzene group, a naphthalene group or a biphenyl group, A 'is a pyrene group, a perylene group, a benzopyrylene group or a coronene group, and A "is a substituted or unsubstituted aromatic ring group. The method of claim 1,
Wherein the monomer is represented by the following formula (1-1), (1-2), (1-3) or (1-4)
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1, 1-2, 1-3, and 1-4,
La, Lb, Lc, Ld, Le, Lf, Lg, Lh, L'a, L'b, L'c, L'd, Or a substituted or unsubstituted C1 to C6 alkylene group,
xa, xb, yc, yd, ze and zf are each independently an integer of 0 to 5,
Tg and Th are each independently an integer of 0 to 9; The method of claim 5,
The monomer may be a monomer for a hard mask composition represented by the following formula (1-1a), (1-1b), (1-2a)
[Formula 1-1a]

[Formula 1-1b]

[Formula 1-2a]

[Formula 1-3a]

[Chemical Formula 1-4a]

The method of claim 1,
Wherein the monomer has a molecular weight of from 500 to 3,000. A composition according to any one of claims 1 to 7,
menstruum
≪ / RTI > 9. The method of claim 8,
Wherein the monomer is comprised between 0.1% and 50% by weight relative to the total hard mask composition content. Providing a layer of material over the substrate,
Applying a hard mask composition according to claim 8 on said material layer,
Heat treating the hard mask composition to form a hard mask layer,
Forming a silicon-containing thin film layer on the hard mask layer,
Forming a photoresist layer on the silicon-containing thin film layer,
Exposing and developing the photoresist layer to form a photoresist pattern,
Selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
≪ / RTI > 11. The method of claim 10,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method. 11. The method of claim 10,
Wherein the forming of the hard mask layer is performed at a temperature of 100 ° C to 500 ° C.