KR20130078745A - Monomer for hardmask composition and hardmask composition including the monomer and method of forming patterns using the hardmask composition - Google Patents

Abstract

PURPOSE: A monomer for a hard disk composition is provided to satisfy the solubility to the solvent, the gap-fill property and flatness property, and to be able to secure the chemical resistance, heat resistance and etch resistance. CONSTITUTION: A monomer for a hard mask composition is represented by Chemical formula 1. Herein, A is substituted or non-substituted benzene, substituted or non-substituted naphthalene, and substituted or non-substituted biphenyl or their combination, A' is substituted or non-substituted polycyclic aromatic, L is a single bond, or substituted or non-substituted C1-6 alkylene, and n is 1-5. The polycyclic aromatic includes pyrene, perylene, benzoperylene, coronene or their combination. Moreover, a hard mask composition comprises the monomer and a solvent.

Description

MONOMER FOR HARDMASK COMPOSITION AND HARDMASK COMPOSITION INCLUDING THE MONOMER AND METHOD OF FORMING PATTERNS USING THE HARDMASK COMPOSITION}

It relates to 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 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 requires properties such as chemical resistance, heat resistance, and etching resistance to withstand multiple etching processes.

On the other hand, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of a chemical vapor deposition method. Spin on coating method for solvent 　 A hard mask composition having solubility can be used.

However, the above-described properties and solubility required for the hard mask layer need a hard mask composition that can satisfy all of them in a mutually conflicting relationship. In addition, as the application range of the hard mask layer increases, a hard mask layer may be formed on a predetermined pattern by a spin-on coating method. In this case, the gap between the patterns may be filled with the hard mask composition. Fill and planarization properties are also required.

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

Another embodiment provides a hardmask composition comprising the monomer.

Another embodiment provides a method of forming a pattern using the hard mask composition.

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

[Formula 1]

In Formula 1,

A is a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted biphenyl group, or a combination thereof,

A 'is a substituted or unsubstituted polycyclic aromatic group,

L is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,

n is 1 to 5 ms.

The polycyclic aromatic group may be a pyrene group, a perylene group, a benzoperylene group, a coronene group, or a combination thereof.

The monomer for the hard mask composition may be represented by the formula (1a).

[Formula 1a]

In formula (1a)

L ¹ and L ² are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group.

The monomer for the hard mask composition may be represented by Formula 1aa or 1ab.

(1aa)

[Chemical Formula 1ab]

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

According to another embodiment, a hard mask composition including the monomer and the solvent is provided.

The monomer may be included in an amount of about 0.1 to 30 wt% based on the total content of the hard mask composition.

According to another embodiment, providing a material layer on a substrate, applying the hardmask composition described above on the material layer, heat treating the hardmask composition to form a hardmask layer, on the hardmask layer Forming a silicon-containing thin film layer, forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern, the silicon-containing thin film layer using the photoresist pattern, and Selectively removing the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer.

Applying the hard mask composition may be performed by a spin-on-coating method.

Forming the hard mask layer may be heat-treated at about 100 to 500 ℃.

It is also possible to secure chemical resistance, heat resistance and etching resistance while satisfying solubility in solvents, gap-fill characteristics 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 a hydrogen atom in a compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 It means substituted with a substituent selected from a cycloalkenyl group of, a cycloalkynyl group of C6 to C15, a C2 to C30 heterocycloalkyl group and a combination thereof.

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

Hereinafter, a monomer for a hard mask composition will be described.

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

[Formula 1]

In Formula 1, A, A ', L and n are defined as follows.

A is an aryl group having one or two rings, which may be substituted or unsubstituted, and may be a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted biphenyl group, or a combination thereof.

A ′ is a substituted or unsubstituted fused polycyclic aromatic group, wherein the polycyclic aromatic group may be, for example, a pyrene group, a perylene group, a benzoperylene group, a coronene group, or a combination thereof.

L may be a linking group and may be a single bond or a substituted or unsubstituted C1 to C6 alkylene group.

n is 1 to 5 ms.

The monomer may have rigid properties by having at least one polycyclic aromatic group in a substituent.

In particular, the monomer has a structure having a hydroxy group and a hydroxyalkylene group on both sides of the polycyclic aromatic group, and amplification crosslinking is possible based on the condensation reaction of the two functional groups can exhibit excellent crosslinking properties.

Therefore, the monomer may be crosslinked into a high molecular weight polymer in a short time even after heat treatment at a relatively low temperature, thereby exhibiting properties required in a hard mask layer such as excellent mechanical properties, heat resistance, chemical resistance, and etching resistance.

In addition, since the monomer includes a plurality of hydroxyl groups in the substituent, the solubility in the solvent is also high, so that the monomer may be prepared in a solution form and formed by a spin-on coating method.

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

The monomer may be represented by, for example, the following Formula 1a.

[Formula 1a]

In Formula 1a, L ¹ and L ² are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group.

The monomer may be, for example, represented by the formula 1aa or 1ab.

(1aa)

[Chemical Formula 1ab]

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

Hereinafter, a hard mask composition according to an embodiment will be described.

The hardmask composition according to one embodiment includes the monomer and the solvent described above.

The monomer is as described above, one monomer may be included alone or two or more monomers may be mixed and included.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the monomer, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) mono Methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, methylpyrrolidone, 　 Acetyl acetone, and ethyl 3-ethoxypropionate.

The monomer may be included in an amount of about 0.1 to 30 wt% based on the total content of the hard mask composition. By including the monomer in the above range it can be coated with a thin film of the 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 to 3 parts by weight based on 100 parts by weight of the hard mask composition. By including in the said range, solubility can be ensured without changing the optical characteristic of a hard mask composition.

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

According to one or more exemplary embodiments, a method of forming a pattern includes: providing a material layer on a substrate, applying a hardmask composition including the monomer and a solvent on the material layer, and heat treating the hardmask composition to form a hardmask layer. Forming a photoresist layer on the hard mask layer; forming a photoresist layer on the silicon mask layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the silicon-containing thin film layer and the hardmask layer and exposing 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, for example, a metal layer such as aluminum or copper, 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. have.

The hard mask composition may be prepared in the form of a solution and applied by a spin-on coating method. At this time, the coating thickness of the hard mask composition is not particularly limited, but may be applied, for example, to a thickness of about 100 to 10,000 kPa.

The heat treatment of the hard mask composition may be performed at, for example, about 10 seconds to 10 minutes at about 100 ° C to 500 ° C. 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.

In addition, 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. In addition, heat treatment 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: Friedel - Craft Acylation ( Friedel - Craft Acylation ) reaction

A solution was prepared by adding 20.6 g (0.101 mol) of terephthaloyl chloride, 47.0 g (0.203 mol) of 4-methoxypyrene and 221 g of 1,2-dichloroethane to the flask. Subsequently, 27 g (0.203 mol) of aluminum chloride was slowly added to the solution at room temperature, and then heated to 60 ° C. and stirred for 8 hours. When the reaction was completed, the precipitate formed by adding methanol to the solution was filtered to obtain bis (methoxypyrenylcarbonyl) benzene.

Step 2: Removal of methyl groups ( demethylation ) reaction

In the flask, 53.5 g (0.0900 mol) of bis (methoxypyrenylcarbonyl) benzene obtained in the first step, 91.1 g (0.450 mol) of 1-dodecanethiol, 30.3 g (0.540 mol) of potassium hydroxide and N, N- 262 g of dimethylformamide were added and then stirred at 120 ° C. for 8 hours. Subsequently, the mixture was cooled, neutralized with a 5% hydrogen chloride solution to pH 7, and the formed precipitate was filtered to obtain bis (hydroxypyrenylcarbonyl) benzene.

Step 3: Reduction ( reduction ) reaction

A solution was prepared by adding 24.0 g (0.0424 mol) of bis (hydroxypyrenylcarbonyl) benzene obtained in the second step and 160 g of tetrahydrofuran to the flask. 16.0 g (0.424 mol) of aqueous sodium borohydride solution was slowly added to the solution, followed by stirring at room temperature for 24 hours. Upon completion of the reaction, the mixture was neutralized with a 5% hydrogen chloride solution to pH 7 and extracted with ethyl acetate to obtain a monomer represented by the following Chemical Formula 1aa.

(1aa)

Synthetic example  2

Step 1: Friedel - Craft Acylation ( Friedel - Craft Acylation ) reaction

A solution was prepared by adding 20.0 g (0.0985 mol) of isophthaloyl chloride, 45.8 g (0.197 mol) of 4-methoxypyrene and 215 g of 1,2-dichloroethane to the flask. Subsequently, 26.3 g (0.197 mol) of aluminum chloride was slowly added to the solution at room temperature, and then heated to 60 ° C. and stirred for 8 hours. When the reaction was completed, the precipitate formed by adding methanol to the solution was filtered to obtain bis (methoxypyrenylcarbonyl) benzene.

Step 2: Removal of methyl groups ( demethylation ) reaction

In the flask, 50.0 g (0.0840 mol) of bis (methoxypyrenylcarbonyl) benzene obtained in the first step, 85.1 g (0.420 mol) of 1-dodecanethiol, 28.3 g (0.504 mol) of potassium hydroxide and N, N- 245 g of dimethylformamide was added and then stirred at 120 ° C. for 8 hours. Subsequently, the mixture was cooled, neutralized with a 5% hydrogen chloride solution to pH 7, and the formed precipitate was filtered to obtain bis (hydroxypyrenylcarbonyl) benzene.

Step 3: Reduction ( reduction ) reaction

A solution was prepared by adding 24.0 g (0.0424 mol) of bis (4-hydroxypyrenylcarbonyl) benzene obtained in the second step and 160 g of tetrahydrofuran to the flask. 16.0 g (0.424 mol) of aqueous sodium borohydride solution was slowly added to the solution, followed by stirring at room temperature for 24 hours. Upon completion of the reaction, the mixture was neutralized to pH 7 with 5% hydrogen chloride solution and extracted with ethyl acetate to obtain a monomer represented by the following Chemical Formula 1ab.

[Chemical Formula 1ab]

Comparative Synthetic Example  One

To the flask was added 8.75 g (0.05 mol) of α, α'-dichloro-p-xylene, 26.66 g of aluminum chloride and 200 g of γ-butyrolactone. A solution of 35.03 g (0.10 mol) of 4,4 '-(9-fluorenylidene) diphenol in 200 g of γ-butyrolactone was slowly added to the solution, followed by stirring at 120 ° C. for 12 hours. After polymerization, the acid was removed using water and then concentrated. Subsequently, the polymerization product was diluted with methylamylketone and methanol, and the concentration was adjusted by adding a solution of methylamylketone / methanol = 4/1 (weight ratio) at a concentration of 15% by weight again. The solution was placed in a separatory funnel, and n-heptane was added to remove the monomer and the low molecular weight to obtain a polymer represented by the following formula (2).

[Formula 2]

The weight average molecular weight of the polymer was 12,000, and the degree of dispersion was 2.04.

Comparative Synthetic Example  2

Step 1: Friedel - Craft Acylation ( Friedel - Craft Acylation ) reaction

To the flask was added 13.9 g (0.0989 mol) of benzoyl chloride, 10.0 g (0.0495 mol) of pyrene and 87 g of 1,2-dichloroethane. 13.2 g (0.0989 mol) of aluminum chloride was slowly added to the solution at room temperature, and then stirred at 8 ° C. for 8 hours. After the reaction was completed, methanol was added and the precipitate formed was filtered to obtain dibenzoylpyrene.

Step 2: Reduction ( reduction ) reaction

To the flask was added 5.00 g (0.0122 mol) of dibenzoylpyrene and 57 g of tetrahydrofuran. To this solution was slowly added an aqueous solution of 4.60 g (0.122 mol) of sodium borohydride and the mixture was stirred at room temperature for 24 hours. Upon completion of the reaction, neutralized with a 5% hydrogen chloride solution to pH 7 and extracted with ethyl acetate to obtain a compound represented by the following formula (3).

(3)

　　　　　　　

Hard mask  Preparation of the 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)), followed by filtration and hard mask composition. Was prepared.

Example 2

A hardmask 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.

Comparative example  One

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

Comparative example  2

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

Evaluation 1: Chemical Resistance

After applying the 10.0% by weight of the hard mask composition according to Examples 1, 2 and Comparative Example 2 on the silicon wafer by a spin-on coating method, the film was heat-treated at 240 ° C. for 1 minute on a hot plate to form a thin film. Initial thin film thickness was measured with a thin film thickness meter of K-MAC.

The thin film was then immersed in a mixed solvent of ethyl 3-ethoxypropionate (EEP) and ethyl lactate (EL) (7: 3v (v / v) for 1 minute. After immersion and removal, the thickness of the thin film was measured.

The results are shown in Table 1.

Initial Thin Film Thickness Thin film thickness after immersion Thin film thickness reduction rate (%) Example 1 2,663 2,660 -0.11 Example 2 2,996 2,972 -0.80 Comparative Example 2 2,490 123 -95.1

Referring to Table 1, it can be seen that the thin film formed from the hard mask composition according to Examples 1 and 2 has a smaller thickness reduction rate after immersion compared to the thin film formed from the hard mask composition according to Comparative Example 2.

From this, it can be seen that the hard mask compositions according to Examples 1 and 2 are sufficiently crosslinked even at heat treatment at a relatively low temperature of 240 ° C. as compared with the hard mask compositions according to Comparative Example 2, thereby forming a thin film having high chemical resistance. have.

Evaluation 2: Heat resistance

After applying the 10.0% by weight of the hard mask composition according to Examples 1, 2 and Comparative Example 2 on the silicon wafer by a spin-on coating method, the film was heat-treated at 240 ° C. for 1 minute on a hot plate to form a thin film. The thickness of the initial thin film was measured with a thin film thickness meter of K-MAC.

Subsequently, the thin film was heat-treated again at 400 ° C. for 2 minutes, and the thickness of the thin film was measured.

The results are shown in Table 2.

Initial Thin Film Thickness Thin film thickness after heat treatment at 400 ℃ Thin film thickness reduction rate (%) Example 1 2,713 2,408 -11.2 Example 2 3,053 2,767 -9.37 Comparative Example 2 2,479 310 -87.5

Referring to Table 2, it can be seen that the thin film formed from the hard mask composition according to Examples 1 and 2 has a smaller thickness reduction rate after heat treatment after 400 ° C. compared with 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 and 2 has a high crosslinking degree of thin film and high heat resistance even at a high temperature of 400 ° C. as compared with the hard mask composition according to Comparative Example 2.

Rating 3: Awareness of corrosion

After applying the 13.0% by weight of the hard mask composition according to Examples 1 and 2 and Comparative Examples 1 and 2 by the spin-on coating method on the silicon wafer, the film was heat-treated at 240 ° C. for 1 minute on a hot plate to form a thin film. The thickness of the thin film was measured by a thin film thickness gauge of K-MAC.

Subsequently, after dry etching for 60 seconds using N ₂ / O ₂ mixed gas in the thin film, the thickness of the thin film was measured. 　 In addition, after the dry etching for 100 seconds using a CFx mixed gas to the thin film, the thickness of the thin film was measured.

The results are shown in Table 3.

N ₂ / O ₂ CFx Initial thin film thickness Thin film thickness after etching Etching rate
(Å / s) Initial thin film thickness
(A) After etching
Thin film thickness
(A) Etching rate
(Å / s) Example 1 4,093 2,765 22.1 4,090 1,540 25.5 Example 2 4,048 2,704 22.4 4,056 1,496 25.6 Comparative Example 1 4,081 2,570 25.2 4,061 1,276 27.9 Comparative Example 2 3,503 1,673 30.5 3,518 418 31.0

* Bulk etch rate (BER)

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

Referring to Table 3, it can be seen that the thin film formed from the hard mask compositions according to Examples 1 and 2 has a lower etching rate than the thin film formed from the hard mask compositions according to Comparative Examples 1 and 2.

From this, it can be seen that the hard mask compositions according to Examples 1 and 2 have high etching resistance of the thin film as compared with the hard mask compositions according to Comparative Examples 1 and 2.

Evaluation 4: pattern formation

A silicon oxide (SiO ₂ ) layer having a thickness of 3,000 Pa was formed on the silicon wafer by chemical vapor deposition. Subsequently, the hard mask compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 were applied onto the silicon oxide layer by a spin-on coating method, followed by heat treatment at 240 ° C. on a hot plate for 1 minute to form a hard mask layer. Subsequently, a silicon nitride (SiN) layer was formed on the hard mask layer by chemical vapor deposition. Subsequently, a photoresist for KrF was coated and heat-treated at 110 ° C. for 60 seconds, and then exposed using an 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 CHF ₃ / CF ₄ mixed gas as a mask using the photoresist patterned by the above procedure. Subsequently, the hard mask layer was dry-etched using N ₂ / O ₂ mixed gas as a mask using the silicon nitride layer patterned by the above procedure. Subsequently, the silicon oxide layer was dry-etched using CHF ₃ / CF ₄ mixed gas as a mask using the hard mask layer patterned by the above process, and then all remaining organic substances were removed using O ₂ gas.

The cross section of the hard mask layer and the silicon oxide layer pattern was observed using an electron scanning microscope (SEM). The results are shown in Table 4.

Hard mask layer pattern shape Silicon Oxide Layer Pattern Shape Example 1 Vertical shape Vertical shape Example 2 Vertical shape Vertical shape Comparative Example 1 Tapered shape Tapered shape Comparative Example 2 Tapered shape Tapered shape

Referring to Table 4, the hard mask layer formed of the hard mask composition according to Examples 1 and 2 and the silicon oxide layer below are all patterned in a vertical shape, whereas the hard mask layer formed from the hard mask composition according to Comparative Examples 1 and 2 It can be seen that the mask layer was not patterned in a vertical shape and thus patterned in a tapered shape.

From this, when the hard mask composition according to Examples 1 and 2 is used, the material layer is formed in a good pattern due to better etching resistance than when using the hard mask compositions according to Comparative Examples 1 and 2, and is located below the hard mask layer. It can also be seen that it is formed in a good pattern.

Evaluation 5: gap-fill and planarization characteristics

After spin-on coating the hard mask composition according to Examples 1 and 2 and Comparative Examples 1 and 2 on the patterned silicon wafer and heat-treating at 240 ° C. for 60 seconds, the gap-fill characteristics and the FE-SEM equipment were used. The planarization characteristics were observed.

The gap-fill characteristics were determined by the presence of voids by observing the pattern cross section with an electron scanning microscope (SEM), and the planarization characteristics were quantified by Equation 1 below. The flattening characteristics are excellent as the difference between h ₁ and h ₂ is not large, and the smaller the number, the better the flattening characteristics.

[formula]

The results are shown in Table 5.

Planarization characteristics Gap-fill characteristic Example 1 10.3 No void Example 2 10.8 No void Comparative Example 1 128.0 No void Comparative Example 2 17.0 Void generation

Referring to Table 5, in the case of using the hard mask composition according to Examples 1 and 2, compared to the case of using the hard mask composition according to Comparative Examples 1 and 2, the degree of planarization was excellent and no voids were observed, thereby providing excellent gap-fill characteristics. It can be seen that represents.

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 (10)

Monomer for a hard mask composition represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
A is a substituted or unsubstituted benzene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted biphenyl group or a combination thereof,
A 'is a substituted or unsubstituted polycyclic aromatic group,
L is a single bond or a substituted or unsubstituted C1 to C6 alkylene group,
n is 1-5.
In claim 1,
The polycyclic aromatic group is a monomer for a hard mask composition comprising a pyrene group, a perylene group, a benzoperylene group, a coronene group or a combination thereof.
In claim 1,
The monomer is a monomer for a hard mask composition represented by the formula (1a).
[Formula 1a]

In formula (1a)
L ¹ and L ² are each independently a single bond or a substituted or unsubstituted C1 to C6 alkylene group.
4. The method of claim 3,
The monomer is a monomer for a hard mask composition represented by Formula 1aa or 1ab:
(1aa)

[Chemical Formula 1ab]

In claim 1,
The monomer is a monomer for a hard mask composition having a molecular weight of 500 to 3,000.
The monomer according to any one of claims 1 to 5, and
menstruum
Hard mask composition comprising a.
The method of claim 6,
The monomer is a hard mask composition containing 0.1 to 30% by weight based on the total content of the hard mask composition.
Providing a layer of material over the substrate,
Applying a hardmask composition according to claim 6 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 >
9. The method of claim 8,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method.
9. The method of claim 8,
Forming the hard mask layer is a pattern forming method which is heat-treated at 100 to 500 ℃.