KR101684977B1 - Hardmask composition, method of forming patterns using the hardmask composition and semiconductor integrated circuit device including the patterns including the patterns - Google Patents

Abstract

[화학식 2]

상기 화학식 1 및 2에서, A, A', A″, L, L′, X, X′, m, n, B, Y, R¹ 및 R²은 명세서에서 정의한 바와 같다.There is provided a hard mask composition comprising a monomer represented by the following formula (1), a monomer represented by the following formula (2), and a solvent.
[Chemical Formula 1]

(2)

Wherein A, A ', A ", L, L', X, X ', m, n, B, Y, R ¹ and R ² are as defined in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to a hard mask composition, a pattern forming method using the same, and a semiconductor integrated circuit device including the pattern. [0002]

A hard mask composition, a pattern formation method using the same, and a semiconductor integrated circuit device including the pattern.

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. Such a hard mask layer must ensure corrosion resistance in order to withstand the multiple etching process, and it should satisfy a predetermined level of optical characteristics so that it can be used as an antireflection film.

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 is not only easy to process but also can improve gap-fill and planarization properties. The spin-on coating method can use a hard mask composition having solubility in solvents.

However, the above-mentioned characteristics required for the hard mask layer are in conflict with each other, and a hard mask composition capable of satisfying all of them is needed.

One embodiment provides a hardmask composition that is capable of satisfying solubility, gap-fill, and planarization properties for a solvent while also satisfying corrosion resistance and optical properties.

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

Another embodiment provides a semiconductor integrated circuit device comprising a pattern formed by the above method.

According to one embodiment, there is provided a hard mask composition comprising a monomer represented by the following formula (1), a monomer represented by the following formula (2), and a solvent.

[Chemical Formula 1]

In Formula 1,

A, A 'and A "are each independently a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,

X and X 'are each independently a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkoxy group,

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

m and n are each independently an integer of 0 or more and satisfy 1? m + n? (the maximum number of substituents A can have).

(2)

In Formula 2,

B is a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,

Y is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted aliphatic cyclic group, a substituted or unsubstituted multichannel alkyl group, a substituted or unsubstituted aromatic cyclic group, or a combination thereof,

R ¹ and R ² are each independently a hydrogen atom, a glycidyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted C2 to C6 alkenyl group, An unsubstituted C2 to C6 acyl group, a substituted or unsubstituted C2 to C6 acetal group or a combination thereof.

A, A ', A "and B each independently represent a substituted or unsubstituted cyclic group selected from the groups listed in Group 1 below.

[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 substituted or unsubstituted polycyclic aromatic group.

At least one of A, A 'and A "is a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkoxy group May be included in at least one combination.

The monomer represented by Formula 2 may be represented by the following Formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)

Y is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted aliphatic cyclic group, a substituted or unsubstituted multichannel alkyl group, a substituted or unsubstituted aromatic cyclic group, or a combination thereof,

R1 and R2 each independently represent a hydrogen atom, a glycidyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted C2 to C6 alkenyl group, Substituted C2 to C6 acyl groups, substituted or unsubstituted C2 to C6 acetal groups, or combinations thereof.

The Y may have a cyclic structure and may be, for example, a substituted or unsubstituted aliphatic cyclic group, a substituted or unsubstituted multicyclic alkyl group, a substituted or unsubstituted aromatic cyclic group, or a combination thereof.

The monomer represented by the formula (2) may be represented by any one of the following formulas (2a) to (2e).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

The monomer represented by the formula (2) may be contained in an amount of 5 to 50% by weight based on the monomer represented by the formula (1).

The monomers represented by the formulas (1) and (2) may independently have a molecular weight of 150 to 6,000.

The solvent may comprise at least one selected from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and ethyl lactate.

The total amount of the monomers represented by the formulas (1) and (2) may be 0.1 to 50% by weight based on 100% by weight of the solvent.

According to another embodiment, there is provided a method of manufacturing a hard mask, comprising the steps of providing a material layer on a substrate, applying the hard mask composition described above on the material layer, heat treating the hard mask composition to form a hard mask layer, 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; 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 100 ° C to 500 ° C.

And forming a bottom anti-reflection layer (BARC) on the silicon-containing thin film layer.

The silicon-containing thin film layer may be one containing silicon oxynitride (SiON).

According to another embodiment, there is provided a semiconductor integrated circuit device including a plurality of patterns formed by the above-described pattern forming method.

It is possible to improve the properties required in the hard mask layer such as corrosion resistance, optical characteristics, planarization characteristics and gap-fill 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, an amino 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 substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a C1 to C4 alkoxy group, a substituted or unsubstituted C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, A C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, It means substituted with a substituent selected.

Unless otherwise stated, "multi-ring alkyl group" means a fused ring in which two or more rings share at least one carbon-carbon bond.

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

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

The hardmask composition according to one embodiment comprises two or more different monomers, and a solvent.

The hard mask composition comprises a monomer represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

A, A 'and A "are each independently a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,

X and X 'are each independently a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkoxy group,

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

m and n are each independently an integer of 0 or more and satisfy 1? m + n? (the maximum number of substituents A can have).

(2)

In Formula 2,

B is a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,

Y is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted aliphatic cyclic group, a substituted or unsubstituted multichannel alkyl group, a substituted or unsubstituted aromatic cyclic group, or a combination thereof,

R ¹ and R ² are each independently a hydrogen atom, a glycidyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted C2 to C6 alkenyl group, An unsubstituted C2 to C6 acyl group, a substituted or unsubstituted C2 to C6 acetal group or a combination thereof.

First, the monomer represented by Formula 1 will be described.

The monomer is a structure having a core and at least one substituent, and containing an aliphatic cyclic group or an aromatic cyclic group, each of which is substituted or unsubstituted in the core and the substituent. The monomers may thus have rigid properties by including a plurality of cyclic groups.

M and n, which represent the number of substituents in Formula 1, are each independently an integer of 0 or more, and the sum thereof can be appropriately selected within a range that does not exceed the maximum number of substituents that A may have.

The monomers each contain a predetermined functional group (X and X ') in the substituent group. By including such functional groups, the solubility of the monomer can be improved, and the monomer can be effectively formed by a spin-on coating method. In addition, the gap-fill characteristic and the planarization characteristic that can fill the gaps between the patterns when formed by the spin-on coating method on the lower film having a predetermined pattern are also excellent.

In addition, amplification crosslinking is possible based on the condensation reaction of the functional groups, and thus excellent crosslinking properties can be exhibited. Accordingly, even when the monomer is heat-treated at a relatively low temperature, the monomer can be crosslinked in a high molecular weight polymer in a short time, thereby exhibiting properties required in a hard mask layer such as excellent mechanical properties, heat resistance characteristics and corrosion resistance.

For example, A, A 'and A "may each independently be a substituted or unsubstituted cyclic group selected from the groups listed in Group 1 below.

[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.

In the group 1, the linking position of each ring is not particularly limited, and each ring may be substituted or unsubstituted. When the ring shown in the group 1 is a substituted ring, it may be substituted with, for example, a C1 to C20 alkyl group, a halogen atom, a hydroxy group and the like, but the substituent is not limited.

For example, at least one of A, A 'and A' 'may be a substituted or unsubstituted polycyclic aromatic group. By including at least one polycyclic aromatic group in this manner, corrosion-resistance can be further improved.

For example, at least one of A, A 'and A "is a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkoxy Group, or a combination thereof.

The monomer may be represented, for example, by any one of the following formulas (1a) to (1g).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above general formulas (1a) to (1d)

X ^a to X ^h and M ¹ to M ⁸ each independently represent a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 An alkoxy group or a combination thereof.

Meanwhile, as described above, the hard mask composition includes a monomer represented by the following formula (2).

Hereinafter, the monomer represented by the following general formula (2) will be described.

(2)

In Formula 2,

B is a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,

Y is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted aliphatic cyclic group, a substituted or unsubstituted multichannel alkyl group, a substituted or unsubstituted aromatic cyclic group, or a combination thereof,

R ¹ and R ² are each independently a hydrogen atom, a glycidyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted C2 to C6 alkenyl group, An unsubstituted C2 to C6 acyl group, a substituted or unsubstituted C2 to C6 acetal group or a combination thereof.

O represents an oxygen atom.

The monomer is a structure represented by Y, and an aliphatic cyclic group or aromatic cyclic group is connected to both sides of the core.

By including the monomer having such a structure, the hard mask composition can further improve the optical characteristics.

B may be, for example, a substituted or unsubstituted cyclic group selected from the groups listed in Group 1 above.

For example, the monomer represented by the formula (2) may be represented by the following formula (2-1) or (2-2).

[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)

Y is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted multibranched alkyl group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted aromatic ring group, or a combination thereof,

R1 and R2 each independently represent a hydrogen atom, a glycidyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted C2 to C6 alkenyl group, Substituted C2 to C6 acyl groups, substituted or unsubstituted C2 to C6 acetal groups, or combinations thereof.

The monomer represented by the formula (2) may be represented by any one of the following formulas (2a) to (2e).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

The hard mask composition can satisfy the characteristics required in the hard mask layer such as corrosion resistance, optical characteristics, gap-fill and planarization characteristics by blending the monomers represented by the above formulas (1) and (2).

In relation to the blending ratio, the monomer represented by Formula 2 may be included in an amount of about 5 to 50% by weight, more preferably about 5 to 20% by weight, based on the monomer represented by Formula 1, But the present invention is not limited thereto.

For example, the monomers represented by the formulas (1) and (2) may independently have a molecular weight of 150 to 6,000.

On the other hand, the solvent included in the hard mask composition is not particularly limited as long as it has sufficient solubility or dispersibility in the monomers, and examples thereof include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol At least one member selected from the group consisting of butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, methylpyrrolidone and acetyl acetone One can be included.

The monomers represented by the general formulas (1) and (2) may be contained in an amount of about 0.1 to 50% by weight based on the total content of the hard mask composition. By incorporating the monomers within 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 to 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 improved 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. At this time, the coating thickness of the hard mask composition is not particularly limited, but may be applied to a thickness of, for example, about 100 Å to 10,000 Å.

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, silicon oxide or silicon oxynitride (SiON).

The method may further include forming a bottom anti-reflective coating (BARC) on the silicon-containing thin film layer. For example, a thin film layer containing silicon oxynitride may be formed on the hard mask layer, then a bottom antireflection layer may be formed thereon, and then a photoresist layer may be formed on the bottom antireflection 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 include, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof. It is not.

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.

When the pattern is included in a semiconductor integrated circuit device, for example, a metal wiring; Semiconductor pattern; A contact hole, a bias hole, a damascene trench, or the like.

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

The flask was charged with 50.0 g (0.166 mol) of coronene and 93 g (0.499 mol) of 4-methylthio-benzoyl Chloride with 700 g of a mixture of chloroform / dichloromethane To prepare a solution. The solution was stirred using a stirring bar, and 66.6 g (0.499 mol) of aluminum chloride was gradually added thereto, followed by heating to 60 DEG C and stirring for 8 hours.

After completion of the reaction, methanol was added to precipitate the precipitate, which was then filtered and washed with a water / methanol mixture to remove reaction by-products and unreacted aluminum chloride. 183.6 g (0.908 mol) of 1-dodecanethiol, 61.0 g (1.09 mol) of potassium hydroxide and 500 g of N, N-dimethylformamide were added to the dried reaction product, followed by stirring at 120 DEG C for 8 hours. Next, the mixture was cooled, neutralized to pH 7 with 10% hydrochloric acid solution, extracted with ethyl acetate, and the powder obtained by rotary evaporation was dissolved in 300 mL of tetrahydrofuran , And 32.3 g (0.85 mol) of lithium aluminum hydride were added little by little and reacted. After completion of the reaction, the reaction side product was removed using a water / methanol mixture to obtain a compound represented by the following formula (1aa).

(1aa)

Synthetic example  2

28.2 g (0.1 mol) of methoxybenzopyrene and 23.5 g (0.11 mol) of methoxynaphthoyl chloride were placed in a 500 g of chloroform / dichloromethane mixed solution to prepare a solution. The solution was stirred using a stirring bar, and 36.7 g (0.15 mol) of aluminum chloride was added little by little and reacted at room temperature.

After 1 hour, 21 g (0.11 mol) of naphthoyl chloride was added, and 36.7 g (0.15 mol) of aluminum chloride was further added thereto. After completion of the reaction, water was used to remove reaction by-products and unreacted aluminum chloride. 108.0 g (0.534 mol) of 1-dodecanethiol, 35.9 g (0.640 mol) of potassium hydroxide (KOH) and 300 g of N, N-dimethylformamide were added to the reaction product obtained by the powder Then, the mixture was stirred at 120 ° C for 8 hours. The mixture was then cooled and neutralized to pH 7 using 10% hydrogen chloride solution. Thereafter, the mixture was extracted with ethyl acetate and the powder obtained by rotary evaporation was dissolved in 200 mL of tetrahydrofuran. 18.98 g (0.5 mol) of lithium aluminum hydride was added little by little . After completion of the reaction, the reaction side product was removed using a water / methanol mixture to obtain a compound represented by the following formula (1bb).

≪ RTI ID = 0.0 &

Synthetic example  3

A solution was prepared by adding 1.4-cyclohexanedicarbonyl chloride (28.0 g, 0.1345 mol), methoxypyrene (62.4 g, 0.269 mol) and 496 g of 1,2-dichloroethane to the flask. Subsequently, aluminum chloride (17.9 g, 0.1345 mol) 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.

To the flask was added the compound obtained above (6.00 g, 0.01001 mol), 1-dodecan sulfate (10.13 g, 0.05005 mol), potassium hydroxide (3.37 g, 0.06006 mol) and 30.3 g of N, N-dimethylformamide Followed by stirring at 120 ° C for 8 hours. The mixture was then cooled, neutralized to pH 6-7 with 5% hydrochloric acid solution, and the precipitate formed was filtered and dried.

To the flask was added the compound obtained above (4.00 g, 0.00699 mol) and 28.5 g of tetrahydrofuran to prepare a solution. An aqueous solution of sodium borohydride (5.29 g, 0.1398 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 24 hours. When the reaction was completed, the reaction mixture was neutralized to pH 7 with 5% hydrochloric acid solution, extracted with ethyl acetate, and dried to obtain a compound represented by the formula 1cc.

[Formula 1cc]

Synthetic example  4

39.44 g of cyclohexanecarbonyl chloride, 62.4 g of pyrene and 523 g of 1,2-dichloroethane were added to the flask to prepare a solution. 35.8 g of aluminum chloride was slowly added to the solution, and the mixture was reacted at room temperature for 12 hours with stirring. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

To the flask, a solution was prepared by adding 45 g of the compound obtained above, 24.6 g of p-methoxybenzoyl chloride and 467 g of 1,2-dichloroethane. To the solution was slowly added 19.2 g of aluminum chloride 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.

8.93 g of the compound obtained above, 20.26 g of 1-dodecan sulfate, 6.74 g of potassium hydroxide and 30.3 g of N, N-dimethylformamide were added to the flask and reacted at 120 DEG C for 8 hours with stirring. The reaction mixture was cooled, neutralized to about pH 6-7 with 5% hydrochloric acid solution, and the precipitate formed was filtered and dried.

6.05 g of the compound obtained on the flask and 37.4 g of tetrahydrofuran were added to prepare a solution. To the solution was slowly added an aqueous solution of 10 g of sodium borohydride and the mixture was reacted for 24 hours at room temperature with stirring. When the reaction was completed, the reaction solution was neutralized to pH 7 with 5% hydrochloric acid solution, extracted with ethyl acetate, and dried to obtain a compound represented by the formula 1dd.

[Chemical Formula 1dd]

Synthetic example  5

280 g of 12H-dibenzo [b, h] fluorene-12-one, 100 g of phenol, 0.17 g of 2-mercaptopropionate and 6.11 g of sulfuric acid were placed and 500 ml of toluene was added thereto and stirred for 1 hour. Then, the temperature inside the flask was raised to 55 캜 and stirred for 12 hours. When the concentration of 12H-dibenzo [b, h] fluorene-12-one became 0.1% or less, the flask temperature was lowered to 25 ° C, and 300 g of toluene and 80 g of water The flask was charged with 32% aqueous NaOH solution until the pH reached 7. After standing for 1 hour, the water layer was removed, and the temperature was raised to 80 캜 while stirring with leaving only the organic layer. When the inside temperature of the flask reached 80 DEG C, 80 g of water was added thereto, stirred, and the water layer was removed. Then, only the organic layer was recovered and the pressure was reduced at 80 캜 for 3 hours to remove toluene and phenol. The residue was recrystallized from 500 g of isopropyl ether to obtain 4,4 '- (12H-dibenzo [b, h] fluorene- (12H-dibenzo [b, h] fluorene-12,12-diyl) diphenol.

Synthetic example  6

280 g of 12H-dibenzo [b, h] fluorene-12-one, 150 g of 2-naphthol, 0.17 g of 2-mercaptopropionate and 6.11 g of sulfuric acid were placed and then 700 ml of toluene was added thereto and stirred for 1 hour. Then, the temperature inside the flask was raised to 55 캜 and stirred for 12 hours. When the content of 12H-dibenzo [b, h] fluorene-12-one became less than 0.1% by gas chromatography (6890N, manufactured by agilent technology), the flask temperature was lowered to 25 ° C, and 400 g of toluene and 120 g of water The flask was charged with 32% aqueous NaOH solution until the pH reached 7. After standing for 1 hour, the water layer was removed, and the temperature was raised to 80 캜 while stirring with leaving only the organic layer. When the inside temperature of the flask reached 80 캜, 120 g of water was added thereto, stirred, and the water layer was removed. Then, only the organic layer was recovered and the pressure was reduced at 80 캜 for 3 hours to remove toluene and 2-naphthol, and recrystallized from 800 g of isopropyl ether to obtain 6,6 '- (12H-dibenzo [b, h] fluorene- 12,12-diyl) dinaphthalen-2-ol (6,6 '- (12H-dibenzo [b, h] fluorene-12,12-diyl) dinaphthalen-2-ol.

Comparative Synthetic Example  One

In a 500 ml four-necked flask equipped with a mechanical stirrer, a cooling tube and a nitrogen gas inlet tube, while introducing nitrogen gas, 109.2 g of 1-hydroxypyrrole and 18.2 g of paraformaldehyde were added to 308 g of propyleneglycolmonomethyletheracetate (PGMEA ) And stir well. After 15 minutes, 4.76 g of pyridinium p-toluene sulfonate was slowly added and the reaction was carried out at 100 ° C for 12 hours. After completion of the reaction, the acid was removed using water and then concentrated using an evaporator. Then diluted with methanol and adjusted to a concentration of 15% by weight. The solution was poured into a 1-liter separatory funnel, and n-heptane was added thereto to remove low-molecular weight compounds containing monomers to obtain a compound represented by Formula (3).

(3)

(n = 8.0)

The polymer had a weight average molecular weight (Mw) of 2,100 and a polydispersity of 1.22.

Comparative Synthetic Example  2

To the flask, a solution was prepared by adding 50.0 g (0.166 mol) of coronene, 46.8 g (0.333 mol) of benzoyl chloride and 330 g of 1,2-dichloroethane. Subsequently, 44.4 g (0.333 mol) of aluminum chloride was added slowly to the solution 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.

Then 25.0 g (0.0492 mol) of the compound obtained above and 174 g of tetrahydrofuran were added to the flask. 18.6 g (0.492 mol) of sodium borohydride aqueous solution was slowly added to the solution, followed by stirring at room temperature for 24 hours. After 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 Formula 4 below.

[Chemical Formula 4]

Hard mask  Preparation of composition

Example  One

90 weight% of the compound obtained in Synthesis Example 2 and 10 weight% of 4,4 '- (9-Fluorenylidene) diphenol (manufactured by Aldrich) represented by the following Formula 2aa % Was dissolved in a mixed solution of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)) and filtered to prepare a hard mask composition. The total content of the two kinds of monomers was adjusted to 13.0% by weight based on the total weight of the hard mask composition, depending on the desired thickness.

[Formula 2aa]

Example  2

(4,4'- (9-Fluorenylidene) diphenol) (manufactured by Aldrich) represented by the general formula (2aa) instead of 4,4'- A hard mask composition was prepared in the same manner as in Example 1, except that (1,3-adamantanediyl) diphenol (4,4 '- (1,3-Adamantanediyl) diphenol) .

(2bb)

Example  3

(4,4 '- (9-Fluorenylidene) diphenol) (manufactured by Aldrich) represented by the formula (2aa) instead of the compound represented by the formula Hardmask composition was prepared in the same manner as in Example 1 except that the compound was used.

[Formula 2cc]

Example  4

(9,4-bis (4-fluorenylidene) diphenol) represented by the following formula (2dd) instead of 4,4 '- Except that 9,9-bis (6-hydroxy-2-naphthyl) fluorine (manufactured by Aldrich) was used instead of 9,9-bis (6-hydroxy-2-naphthyl) fluorene .

[Chemical Formula 2dd]

Example  5

(9) was obtained in the same manner as in Synthesis Example 6, except that 4,4 '- (9-fluorenylidene) diphenol (manufactured by Aldrich) Hardmask composition was prepared in the same manner as in Example 1 except that the compound was used.

≪ EMI ID =

Example  6

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

Example  7

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 3 was used in place of the compound obtained in Synthesis Example 2.

Example  8

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 4 was used instead of the compound obtained in Synthesis Example 2.

Comparative Example  One

The compound obtained in Comparative Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)) to prepare a solution. The solution was then filtered to produce a hard mask composition. The amount of the compound was adjusted according to the desired thickness.

Comparative Example  2

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

Comparative Example  3

Except that 4,4 '- (9-fluorenylidene) diphenol (manufactured by Aldrich) represented by Formula 2aa was used instead of the compound obtained in Comparative Synthesis Example 1 The hard mask composition was prepared in the same manner as in Comparative Example 1.

evaluation

Evaluation 1: Gap-fill and planarization characteristics

The hard mask composition (monomer content: 13 wt% based on the total composition) according to Examples 1 to 8 and Comparative Example 1 was spin-coated on a patterned silicon wafer and heat-treated on a hot plate at 350 DEG C for 120 seconds, Gap-fill and planarization characteristics were observed using an emission scanning microscope (FE-SEM) equipment.

The gap-fill characteristics were determined by observing the pattern section with an FE-SEM to determine whether a void was generated, and the planarization characteristic was measured by measuring the thickness of the hard mask layer from the image of the pattern section observed with the FE-SEM, Respectively. 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 1.

Planarization characteristics Gap-fill characteristic Example 1 8% or less void None Example 2 8% or less void None Example 3 8% or less void None Example 4 8% or less void None Example 5 8% or less void None Example 6 8% or less void None Example 7 8% or less void None Example 8 8% or less void None Comparative Example 1 25% void occurrence

Referring to Table 1, when the hard mask composition according to Examples 1 to 8 was used, the degree of planarization was excellent and the void was not observed as compared with the case of using the hard mask composition according to Comparative Example 1, . ≪ / RTI >

Evaluation 2: Awareness of corrosion

The hard mask composition (monomer content: 13.0 wt% based on the total composition) according to Examples 1 to 8 and Comparative Examples 1 and 3 was applied on a silicon wafer by a spin-on coating method, The thin film was formed by heat treatment. The thickness of the thin film was then measured. Was then proceeding to dry etching for 60 seconds each using N ₂ / O ₂ mixed gas _{(50mT / 300W / 10 O 2} /50 N 2) to the thin film was further measured the thickness of the thin film. The bulk etch rate (BER) was calculated from the thin film thickness before and after the dry etching and the dry time using the following equation (2).

[Equation 2]

(Initial thin film thickness - thin film thickness after etching) / etching time (Å / s)

The results are shown in Table 2.

N ₂ / O ₂ The etching rate (Å / sec) CF _x The etching rate (Å / sec) Example 1 23.4 27.5 Example 2 23.7 27.9 Example 3 23.1 27.4 Example 4 23.1 27.5 Example 5 23.1 27.9 Example 6 22.9 25.0 Example 7 24.1 28.4 Example 8 24.3 28.3 Comparative Example 1 26.2 30.9 Comparative Example 3 48.8 56.1

Referring to Table 2, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 8 has a lower etching rate than the thin film formed from the hard mask composition according to Comparative Examples 1 and 3.

Evaluation 3: Optical characteristics

The hard mask composition (monomer content: 5.0% by weight based on the total composition) according to Examples 1 to 5 and Comparative Example 2 was coated on a silicon wafer by spin-on coating method and baked at 350 캜 for 120 seconds to form a film having a thickness of about 800 Å Of the hard mask layer.

The refractive index (n) and the extinction coefficient (k) of the hard mask layer were measured. The refractive index and the extinction coefficient were measured using an Ellipsometer (manufactured by J.A. Woollam) while irradiating light having a wavelength of 193 nm to 633 nm.

Optical properties (193 nm) Optical properties (633 nm) Refractive index (n) Absorption coefficient (k) Refractive index (n) Absorption coefficient (k) Example 1 1.431 0.433 1.821 0.048 Example 2 1.427 0.411 1.813 0.045 Example 3 1.441 0.481 1.832 0.052 Example 4 1.433 0.476 1.816 0.050 Example 5 1.428 0.498 1.822 0.056 Comparative Example 2 1.495 0.755 1.946 0.108

Referring to Table 3, the hard mask thin film formed from the hard mask composition according to Examples 1 to 5 has a refractive index (refractive index) that can be used as a hard mask and an antireflection film as compared with the hard mask thin film formed with the hard mask composition according to Comparative Example 2 n) and an extinction coefficient (k).

It can be seen that the hard mask thin film formed from the hard mask composition according to Examples 1 to 5 is applicable as a hard mask layer even in a pattern process using a light source with a low wavelength such as 193 nm and has an extinction coefficient k at 633 nm 0.1 or less, it can be applied to a thick hard mask having a thickness of about 10,000 to 50,000 angstroms.

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 (16)

A monomer represented by the following general formula (1)
A monomer represented by the following formula (2), and
menstruum
A hard mask composition comprising:
[Chemical Formula 1]

In Formula 1,
A, A 'and A "are each independently a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,
X and X 'are each independently a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkoxy group,
L and L 'are each independently a single bond, a substituted or unsubstituted C1 to C6 alkylene group or a combination thereof,
m and n are each independently an integer of 0 or more and satisfy 1? m + n? (the maximum number of substituents A can have)
Provided that when A, A 'and A " are both aromatic ring groups, A' and A " are each independently at least one hydrogen atom thereof is a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, ≪ / RTI > atoms: < RTI ID = 0.0 >
(2)

In Formula 2,
B is a substituted or unsubstituted aliphatic cyclic group or aromatic cyclic group,
Y is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted aliphatic cyclic group, a substituted or unsubstituted multichannel alkyl group, a substituted or unsubstituted aromatic cyclic group, or a combination thereof,
R ¹ and R ² are each independently a hydrogen atom, a glycidyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted C2 to C6 alkenyl group, An unsubstituted C2 to C6 acyl group, a substituted or unsubstituted C2 to C6 acetal group or a combination thereof.
The method of claim 1,
Wherein A, A ', A " and B are each independently a substituted or unsubstituted ring group selected from the groups listed in 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. 3. The method of claim 2,
Wherein at least one of A, A 'and A " is a substituted or unsubstituted polycyclic aromatic group. The method of claim 1,
At least one of A, A 'and A "is a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkoxy group Of at least one of < RTI ID = 0.0 > a < / RTI > The method of claim 1,
The monomer represented by Formula 2 is represented by Formula 2-1 or 2-2.
[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)
Y is a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted aliphatic cyclic group, a substituted or unsubstituted multichannel alkyl group, a substituted or unsubstituted aromatic cyclic group, or a combination thereof,
R ¹ and R ² are each independently a hydrogen atom, a glycidyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted C2 to C6 alkenyl group, An unsubstituted C2 to C6 acyl group, a substituted or unsubstituted C2 to C6 acetal group or a combination thereof. The method of claim 1,
Wherein the monomer represented by the formula (2) is represented by any one of the following formulas (2a) to (2e):
(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

The method of claim 1,
Wherein the monomer represented by Formula 2 is contained in an amount of 5 to 50 wt% based on the monomer represented by Formula 1. [ The method of claim 1,
Wherein the monomers represented by Formulas 1 and 2 each independently have a molecular weight of 150 to 6,000. The method of claim 1,
Wherein the solvent comprises at least one selected from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and ethyl lactate. The method of claim 1,
Wherein the total amount of the monomers represented by the formulas (1) and (2) is 0.1 wt% to 50 wt% with respect to 100 wt% of the solvent. Providing a layer of material over the substrate,
Applying a hard mask composition according to any one of claims 1 to 10 on the 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 > 12. The method of claim 11,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method. 12. The method of claim 11,
Wherein the forming of the hard mask layer is performed at a temperature of 100 ° C to 500 ° C. 12. The method of claim 11,
And forming a bottom anti-reflective layer (BARC) on the silicon-containing thin film layer. The method of claim 14,
Wherein the silicon-containing thin film layer contains silicon oxynitride (SiON). A semiconductor integrated circuit device comprising a plurality of patterns formed by the pattern forming method according to claim 11.