KR101757809B1 - Monomer for hardmask composition and hardmask composition including the monomer and method of forming patterns using the hardmask composition - Google Patents

Abstract

상기 화학식 1에서,
T, R¹, R² 및 R³의 정의는 명세서에 기재된 바와 같다.A hard mask composition comprising the monomer, and a pattern forming method using the hard mask composition.
[Chemical Formula 1]

In Formula 1,
T, R ¹ , R ² and R ³ are 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, a monomer, and the monomer, and a pattern forming method using the hard mask composition. BACKGROUND ART < RTI ID = 0.0 >

A monomer, 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 exhibit erosion-awareness so as to withstand the multiple etching process.

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.

However, the hard mask layer, which is generally applied by a spin-coating technique, tends to have poor etch selectivity as compared to a hard mask layer formed by a chemical or physical deposition method.

One embodiment provides a monomer for a hard mask composition that is excellent in etch selectivity.

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,

T is a triazine or triazine derivative,

R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is one or two or more.

Provided that at least one of R ¹ , R ² and R ³ includes a substituted or unsubstituted aryl group.

At least one of R ¹ , R ² and R ³ may include at least two substituted or unsubstituted aryl groups.

The two substituted or unsubstituted aryl groups may be connected to each other by a C1 to C6 hydroxyalkylene, a C1 to C6 substituted or unsubstituted aminoalkylene, a C1 to C6 halogenated alkylene, or a combination thereof.

At least one of R ¹ , R ² and R ³ of the monomer may be represented by the following formula (2).

(2)

In Formula 2,

X and Y are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cyclo A substituted or unsubstituted C2 to C20 heteroaryl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a combination thereof,

M is a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, or a combination thereof,

O is an oxygen atom,

n is 0 or 1;

Provided that at least one of X and Y is a substituted or unsubstituted C6 to C30 aryl.

And at least one of X and Y may be any one selected from the following Group 1.

[Group 1]

The substituted or unsubstituted heteroaryl group may include triazine.

The monomer may be represented by any one of the following formulas (3) to (5).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,

T is a triazine or triazine derivative,

A ¹ to A ¹⁸ each independently represent a substituted or unsubstituted C6 to C30 aryl group,

M ¹ to M ⁷ each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,

O is an oxygen atom.

The monomer may have a molecular weight of 800 to 5000.

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

[Chemical Formula 1]

In Formula 1,

T is a triazine or triazine derivative,

R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is one or two or more.

Provided that at least one of R ¹ , R ² and R ³ includes a substituted or unsubstituted aryl group.

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

It is possible to secure the gap-fill property and the planarization property while being excellent in corrosion resistance and awakening.

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

[Chemical Formula 1]

In Formula 1,

T is a triazine or triazine derivative,

R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is one or two or more.

Provided that at least one of R ¹ , R ² and R ³ includes a substituted or unsubstituted aryl group.

The monomer has a structure in which triazine is used as a core and three substituents are connected to the core. The three substituents (R ¹ , R ^2, and R ³ ) include at least one substituted or unsubstituted aryl group, thereby ensuring corrosion resistance and heat resistance.

The number of carbon atoms of the substituted or unsubstituted aryl group is not limited in principle, and may be, for example, C6 to C50, C6 to C40, or C6 to C30, but is not limited thereto. For example, the substituted or unsubstituted aryl group may be a substituted or unsubstituted polycyclic aromatic ring group.

For example three substituents (R ^1, R ² and R ³⁾ is May be a combination of a substituted or unsubstituted aryl group and a hydroxy group, and may be, for example, a combination of benzene, pyrene, and a hydroxy group.

The three substituents (R ^1, R ² and R ³⁾ is And may include at least two substituted or unsubstituted aryl groups, one of which may be a substituted or unsubstituted polycyclic aromatic ring group.

The two substituted or unsubstituted aryl groups may be connected to each other by a C1 to C6 hydroxyalkylene, C1 to C6 substituted or unsubstituted aminoalkylene, C1 to C6 halogenated alkylene, or a combination thereof . As a result, the solubility can be further improved to effectively form a spin-on coating method, and a gap-fill characteristic capable of filling a gap between patterns when formed by a spin-on coating method on a lower film having a predetermined pattern And the planarizing property are also excellent.

As described above, the monomer has a triazine structure in the core, and thus the etching selectivity can be further improved. The position where the three substituents (R ¹ , R ² and R ³ ) are connected to the triazine is not limited, and may be, for example, 1,3,5-triazine.

At least one of R ¹ , R ² and R ³ may be represented, for example, by the following formula (2).

(2)

In Formula 2,

X and Y are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cyclo A substituted or unsubstituted C2 to C20 heteroaryl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a combination thereof,

M is a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, or a combination thereof,

O is an oxygen atom,

n is 0 or 1;

Provided that at least one of X and Y is a substituted or unsubstituted C6 to C30 aryl group such as, but not limited to, the following group 1.

[Group 1]

Any one of the substituents (R ¹ , R ^2, and R ³ ) may include a substituted or unsubstituted heteroaryl group, and may include, for example, triazine.

Meanwhile, the monomer may be represented by any one of the following formulas (3) to (5), but is not limited thereto.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,

T is a triazine or triazine derivative,

A ¹ to A ¹⁸ each independently represent a substituted or unsubstituted C6 to C30 aryl group,

M ¹ to M ⁷ each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,

O is an oxygen atom.

The monomer may have a molecular weight of about 800 to 5,000. 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.

On the other hand, the solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the monomer. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, ) Monomethyl 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% by weight based on the total content 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 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 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 100 to 10,000 A thick.

The step of heat-treating the hard mask composition may be performed at, for example, about 100 to 500 ° C for about 60 seconds to 20 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 before the step of forming the photoresist layer.

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

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

Synthesis of intermediate A

In a 500-ml two-necked flask equipped with a mechanical stirrer and a condenser, 10.1 g (0.05 mol) of pyrene, 9.2 g (0.05 mol) of cyanuric chloride and 1, 2-dichloroethane 2-Dichloroethane) was added and stirred sufficiently. After 15 minutes, 7.3 g (0.06 mol) of trichloroaluminum was slowly added to the flask, and the reaction was carried out at room temperature for 12 hours. After completion of the reaction, water was used to remove the trichloroaluminum and then concentrated using an evaporator to obtain Intermediate A shown below.

[Intermediate A]

Synthesis of intermediate B

14.4 g (0.1 mole) of 2-naphthol, 9.2 g (0.05 mole) of cyanuric chloride and 100 g of acetone were dissolved in a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube. 70 ml of a 2M NaOH solution was slowly added thereto, and the reaction was carried out at room temperature for 12 hours. After completion of the reaction, 500 ml of water was added and then filtered to obtain the following intermediate B:

[Intermediate B]

Synthesis of intermediate C

The following intermediate C was obtained using the same method except that 1,3,5-trichlorobenzene was used instead of cyanuric chloride in the synthesis of intermediate B:

[Intermediate C]

Synthetic example  One

In a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube, 20.1 g (0.1 mol) of pyrene and 17.0 g (0.1 mol) of methoxybenzoyl chloride were placed in 200 g of 1,2-dichloroethane and stirred . After 15 minutes, 14.6 g (0.11 mol) of trichloroaluminum was slowly added and the reaction was carried out at room temperature for 12 hours. After completion of the reaction, trichloroaluminum was removed using water and then concentrated using an evaporator.

The resulting compound was placed in a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube, and 45.5 g (0.22 mol) of 1-dodecan sulfate, 16.8 g (0.3 mol) of potassium hydroxide, And the mixture was stirred at 130 DEG C for 5 hours. After completion of the reaction, the reaction product was cooled, and the reaction product was neutralized to pH 5 with 7% hydrogen chloride solution. The precipitate formed was dissolved in 300 g of methylene chloride, and the organic layer was separated. The separated organic solvent layer was concentrated by an evaporator to obtain a methyl-removed compound.

The methyl-removed compound was dissolved using 150 g of dioxane and the solution was cooled to 0 < 0 > C. To the cooled solution, 50 g (0.5 mol) of triethylamine was added, and then 6.1 g (0.033 mol) of cyanuric chloride was slowly added dropwise. The reaction mixture was stirred at room temperature for 2 hours, then heated to 100 DEG C and reacted for 8 hours. After completion of the reaction, the reaction product was extracted with ammonium chloride solution and ethyl acetate. The extracted solution was reduced in pressure to remove the solvent, and 160 g of tetrahydrofuran was added to the obtained compound to obtain a solution. An aqueous solution of 16 g (0.42 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 12 hours. After the reaction was completed, the reaction mixture was acidified to a pH of less than 5 with a 7% hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was reduced to obtain a compound represented by the following formula (1a).

[Formula 1a]

Synthetic example  2

In the same manner as in Synthesis Example 1 except that benzopyrilene was used in place of pyrene and cyanuric chloride was used instead of the intermediate A, a compound represented by the following Formula 1b was obtained.

[Chemical Formula 1b]

　

Synthetic example  3

20.6 g (0.1 mol) of terephthaloyl chloride, 47 g (0.2 mol) of 4-methoxypyrene and 221 g of 1,2-dichloroethane were added to a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube, Prepared. 27 g (0.2 mol) of trichloroaluminum was added slowly to the solution at room temperature, then the temperature was raised to 60 ° C and the mixture was stirred for 8 hours. When the reaction was completed, the reaction solution was dropped into methanol to form a precipitate. The precipitate was filtered to obtain bis (methoxypyrylcarbonyl) benzene.

91 g (0.45 mol) of 1-dodecan sulfate, 30.3 g (0.55 mol) of potassium hydroxide and 250 g of N, N-dimethylformamide were added to the compound obtained above, followed by stirring at 120 ° C for 8 hours. After the reaction was terminated, the reaction was cooled and acidified to pH less than 5 with 7% H 2 O. The precipitate formed was filtered off to give the methylated compound.

The methyl-removed compound was dissolved in 150 g of dioxane, Lt; 0 > C. 50 g (0.5 mol) of triethylamine was added to the cooled solution, and then 79.9 g (0.2 mol) of the intermediate B was slowly added dropwise. The reaction was heated to 100 DEG C and reacted for 8 hours. After termination of the reaction, the reaction was extracted with ammonium chloride solution and ethyl acetate. The extracted solution was then depressurized to remove the solvent. To the compound thus obtained, 160 g of tetrahydrofuran was added to obtain a solution. An aqueous solution of 16 g (0.42 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 12 hours. After the reaction was completed, the reaction mixture was acidified with a 7% hydrogen chloride solution to a pH of less than 5, extracted with ethyl acetate, and the organic solvent was reduced to obtain a compound represented by the following formula 1c.

[Chemical Formula 1c]

Comparative Synthetic Example  One

A compound represented by the following formula (6) was obtained in the same manner as in Synthesis Example 1, except that 1,3,5-trichlorobenzene was used instead of cyanuric chloride.

[Chemical Formula 6]

Comparative Synthetic Example  2

27.6 g (0.1 mol) of benzoperylene, 17 g (0.1 mol) of methoxybenzoyl chloride and 312 g of 1,2-dichloroethane were placed in a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube. After 15 minutes, 15 g (0.11 mol) of trichloroaluminum was slowly added, and the reaction solution was reacted at room temperature for 5 hours. After completion of the reaction, trichloroaluminum was removed using water and then concentrated using an evaporator. The resulting compound was placed in a 500-ml two-necked flask equipped with a mechanical stirrer and a cooling tube, and 45 g (0.23 mol) of 1-dodecan sulfate, 18 g (0.3 mol) of potassium hydroxide and 250 g of N, N- Followed by stirring at 130 DEG C for 5 hours. After completion of the reaction, the reaction product was cooled and the reaction product was acidified with a 7% hydrogen chloride solution to a pH of less than 5. The resulting precipitate was dissolved in 300 g of methylene chloride and the organic layer was separated. The separated organic solvent layer was concentrated by an evaporator to obtain a methyl-removed compound. (0.1 mole) and 10.9 g (0.05 mole) of hydroxypyrane were dissolved in 150 g of dioxane, and the solution was treated with 0 Lt; 0 > C. 50 g (0.5 mol) of triethylamine was added to the cooled solution, and then 9.1 g (0.05 mol) of 1,3,5-trichlorobenzene was slowly dropped thereinto. The reaction was stirred at room temperature for 2 hours, then heated to 100 DEG C and reacted for 8 hours. The reaction was terminated by extraction with ammonium chloride solution and ethyl acetate. The extracted solution was then depressurized to remove the solvent.

To the compound thus obtained, 160 g of tetrahydrofuran was added to obtain a solution. An aqueous solution of 16 g (0.42 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 12 hours. After the reaction was completed, the reaction mixture was acidified to pH 5 with 7% hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was reduced to obtain a compound represented by the following formula (7).

(7)

Comparative Synthetic Example  3

A compound represented by the following formula (8) was obtained in the same manner as in Synthesis Example 3, except that Intermediate C was used instead of Intermediate B.

[Chemical Formula 8]

Hard mask  Preparation of composition

Example  One

The compound obtained in Synthesis Example 1 was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), A composition was prepared. The content of the compound was adjusted to 4.0 wt.% Or 13.0 wt.% Based on the total weight of the hard mask composition, depending on the intended thickness.

Example  2

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

Example  3

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 instead of the compound 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 compound obtained in Comparative Synthesis Example 1 was used instead of the compound 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 compound obtained in Comparative Synthesis Example 2 was used instead of the compound obtained in Synthesis Example 1.

Comparative Example  3

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

Awareness of corrosion  evaluation

The hard mask composition according to Examples 1 to 3 and Comparative Examples 1 to 3 was spin-on coated on a silicon wafer and then heat-treated at 400 DEG C for 90 seconds on a hot plate to form a thin film having a thickness of 4,000 ANGSTROM.

Subsequently, the thin film was dry-etched for 60 seconds and 100 seconds using N ₂ / O ₂ mixed gas and CF _x gas, and then the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated from the thickness and etch time of the thin film before and after dry etching according to the following equation. The thickness of the thin film was measured using a thin film thickness meter of K-MAC.

[Equation 1]

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

The results are shown in Table 1.

The etching rate (CF _x , Å / s) The etching rate (N ₂ / O ₂ , Å / s) Comparative Example 1 27.21 23.5 Example 1 25.42 18.12 Comparative Example 2 26.02 22.46 Example 2 23.35 16.74 Comparative Example 3 26.54 24.23 Example 3 22.86 14.46

Referring to Table 1, the thin films formed from the hard mask compositions according to Examples 1 to 3 had a sufficient etch resistance to the etching gas as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 3, .

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 (20)

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

In Formula 1,
T is a group containing a triazine or triazine structure,
R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is a group having one or two or more combinations of
At least one of R ¹ , R ² and R ³ includes at least two substituted or unsubstituted aryl groups,
The two substituted or unsubstituted aryl groups are connected by C1 to C6 hydroxyalkylene, C1 to C6 substituted or unsubstituted aminoalkylene, C1 to C6 halogenated alkylene, or a combination thereof. delete delete The method of claim 1,
At least one of R < ¹ >, R < ² > and R < ³ >
(2)

In Formula 2,
X is independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cyclo A substituted or unsubstituted C2 to C20 heteroarylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, or a combination thereof,
Y is independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group , A substituted or unsubstituted C2 to C20 heteroaryl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a combination thereof,
M is a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, or a combination thereof,
O is an oxygen atom,
n is 0 or 1;
Provided that X and Y satisfy at least one of the following (i) and (ii):
(i) X is a substituted or unsubstituted C6 to C30 arylene group;
(ii) Y is a substituted or unsubstituted C6 to C30 aryl group. 5. The method of claim 4,
Wherein at least one of X and Y is any one selected from the following Group 1:
[Group 1]

The method of claim 1,
Wherein the substituted or unsubstituted heteroaryl group comprises triazine. The method of claim 1,
A monomer for a hard mask composition represented by any one of the following formulas (3) to (5):
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,
T is a group containing a triazine or triazine structure,
A ¹ , A ² , A ³ , A ⁸ , A ⁹ and A ¹⁴ to A ¹⁶ are each independently a substituted or unsubstituted C6 to C30 arylene group,
A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹² , A ¹³ , A ¹⁷ and A ¹⁸ are each independently a substituted or unsubstituted C6 to C30 aryl group,
M ¹ to M ⁷ each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,
O is an oxygen atom. The method of claim 1,
Wherein the monomer has a molecular weight of from 800 to 5,000. A monomer represented by the following formula (1), and
menstruum
A hard mask composition comprising:
[Chemical Formula 1]

In Formula 1,
T is a group containing a triazine or triazine structure,
R ¹ , R ² and R ³ are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, an oxygen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, Is a group having one or two or more combinations of
At least one of R ¹ , R ² and R ³ includes at least two substituted or unsubstituted aryl groups,
The two substituted or unsubstituted aryl groups are connected by C1 to C6 hydroxyalkylene, C1 to C6 substituted or unsubstituted aminoalkylene, C1 to C6 halogenated alkylene, or a combination thereof. delete delete The method of claim 9,
Wherein at least one of R < ¹ >, R < ² > and R < ³ >
(2)

In Formula 2,
X is independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cyclo A substituted or unsubstituted C2 to C20 heteroarylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, or a combination thereof,
Y is independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group , A substituted or unsubstituted C2 to C20 heteroaryl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, or a combination thereof,
M is a hydroxy group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, or a combination thereof,
O is an oxygen atom,
n is 0 or 1;
Provided that X and Y satisfy at least one of the following (i) and (ii):
(i) X is a substituted or unsubstituted C6 to C30 arylene group;
(ii) Y is a substituted or unsubstituted C6 to C30 aryl group. The method of claim 12,
Wherein at least one of X and Y is any one selected from the following Group 1:
[Group 1]

The method of claim 9,
Wherein said substituted or unsubstituted heteroaryl group comprises triazine. The method of claim 9,
Wherein the monomer is represented by any one of the following formulas (3) to (5):
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas 3 to 5,
T is a group containing a triazine or triazine structure,
A ¹ , A ² , A ³ , A ⁸ , A ⁹ and A ¹⁴ to A ¹⁶ are each independently a substituted or unsubstituted C6 to C30 arylene group,
A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹² , A ¹³ , A ¹⁷ and A ¹⁸ are each independently a substituted or unsubstituted C6 to C30 aryl group,
M ¹ to M ⁷ each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted aryl group, or a combination thereof,
O is an oxygen atom. The method of claim 9,
Wherein the monomer has a molecular weight of 800 to 5000. < Desc / Clms Page number 24 > The method of claim 9,
Wherein the monomer is included in an amount of 0.1 to 30% by weight based on the total amount of the hard mask composition. Providing a layer of material over the substrate,
Applying a hard mask composition according to any one of claims 9 to 17 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 > The method of claim 18,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method. The method of claim 18,
Wherein the step of forming the hard mask layer comprises a heat treatment at 100 ° C to 500 ° C.