KR101666484B1 - 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, A, A', A″, L, L', X, X′, m 및 n은 명세서에서 정의한 바와 같다.A hard mask composition comprising the monomer, and a pattern forming method using the same.
[Chemical Formula 1]

In Formula 1, A, A ', A ", L, L', X, X ', m and n 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 for a hard mask composition, a hard mask composition comprising the monomer, and a pattern forming method using the hard mask composition. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

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

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

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

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

The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer is required to 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, there is a need for a hard mask composition capable of satisfying all of these requirements because the corrosion resistance required for the hard mask layer is generally in conflict with the gap-fill and planarization characteristics.

One embodiment provides a monomer for a hard mask composition that is capable of satisfying the gap-fill and planarization characteristics while also satisfying corrosion resistance.

Another embodiment provides a hardmask composition comprising the monomer.

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

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

[Chemical Formula 1]

In Formula 1,

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

X and X 'each independently represents a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group , A substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkyl ether, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Lt; / RTI &

L and L 'are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group or a combination thereof,

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

Provided that at least one of A, A 'and A "is an aromatic ring group selected from the 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 C 2 to C 20 alkynylene groups, C = O, NR, oxygen (O), sulfur (S), or a substituted or unsubstituted C 2 to C 20 heteroarylene group, It is a combination,

Z ³ is nitrogen (N), CR, or a combination thereof,

R is 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 aromatic ring group selected from the following group 2.

[Group 2]

At least one of A, A 'and A' 'may be a substituted or unsubstituted polycyclic aromatic group.

Wherein A, A 'or A "is a group selected from the group consisting of 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 by any one selected from the following formulas (1a) to (1d).

[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 each independently represent a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 aryl A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkyl ether , A substituted or unsubstituted C7 to C20 arylalkylene ether, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C1 to C20 alkylboranyl group, a substituted or unsubstituted C6 to C30 arylborane group, Lt; / RTI >

Z ^c , Z ^d , Z ^e and Z ^g 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 aryl Substituted or unsubstituted C 2 to C 20 heteroarylene groups, substituted or unsubstituted C 2 to C 20 alkenylene groups, substituted or unsubstituted C 2 to C 20 alkynylene groups, C = O, NR, oxygen (O), sulfur (S) or a combination thereof,

Z ^a , Z ^b and Z ^f are each independently nitrogen (N), CR or a combination thereof,

Wherein R is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

OR ₁ and OR ₂ each independently represent a C1 to C30 alkoxy group.

The monomer may have a molecular weight of from 200 to 5,000.

According to another embodiment, there is provided a hard mask composition comprising a monomer represented by Formula 1 and a solvent.

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

Comprising the steps of: providing a layer of material over a substrate; applying the hardmask composition described above on the layer of material; heat treating the hardmask composition to form a hardmask layer; forming a thin layer of silicon- , Forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively etching 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.

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).

A monomer for a hard mask composition is provided which can satisfy gap-fill and planarization characteristics while satisfying heat resistance.

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.

Also, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from B, 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,

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

X and X 'each independently represents a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group , A substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkyl ether, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Lt; / RTI &

L and L 'are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group or a combination thereof,

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

Thus, the monomer may have a rigid property by containing an aromatic ring group in the core and the substituent, respectively. Here, the range of the aromatic ring group is not limited in principle, but at least one of A, A 'and A "should be an aromatic ring group selected from the following group 1.

[Group 1]

In the group 1,

Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C 2 to C 20 alkynylene groups, C = O, NR, oxygen (O), sulfur (S), or a substituted or unsubstituted C 2 to C 20 heteroarylene group, It is a combination,

Z ³ is nitrogen (N), CR, or a combination thereof,

R is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.

The connection positions of the respective rings in the group 1 are not particularly limited.

Thus, the monomer has a structure containing at least one heteroaromatic ring group. Thus, not only the adhesion between the hard mask layer and the wafer layer can be ensured, but also the gap-fill characteristic can be improved.

At least one of A, A 'and A "may be a substituted or unsubstituted aromatic ring group selected from the following group 2.

[Group 2]

In the group 2, 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.

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

Further, as described above, since the monomer has at least one heteroaromatic ring group, it is possible to secure the erosion arousal and increase the affinity between the hard mask layer and the wafer layer, thereby satisfying the gap-fill property.

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, 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, A, A 'or A "in the above formula (1) is a substituent selected from the group consisting of a hydrogen atom, a thioyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, To C30 alkoxy groups or combinations thereof.

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

[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 each independently represent a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 aryl A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkyl ether , A substituted or unsubstituted C7 to C20 arylalkylene ether, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C1 to C20 alkylboranyl group, a substituted or unsubstituted C6 to C30 arylborane group, Lt; / RTI >

Z ^c , Z ^d , Z ^e and Z ^g 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 aryl Substituted or unsubstituted C 2 to C 20 heteroarylene groups, substituted or unsubstituted C 2 to C 20 alkenylene groups, substituted or unsubstituted C 2 to C 20 alkynylene groups, C = O, NR, oxygen (O), sulfur (S) or a combination thereof,

Z ^a , Z ^b and Z ^f are each independently nitrogen (N), CR or a combination thereof,

Wherein R is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,

OR ₁ and OR ₂ each independently represent a C1 to C30 alkoxy group.

The monomer may have a molecular weight of from 200 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.

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

The monomer may be included in an amount of about 0.1 to 50% 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 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, 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 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.

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

30.2 g (0.1 mol) of benzoperylene and 95.9 g (0.5 mol) of 3-quinolinecarbonyl chloride were added to a flask together with 500 g of a chloroform / dichloromethane mixture to prepare a solution Respectively. The solution was then stirred using a stirring bar, and 122.33 g (0.5 mol) of aluminum chloride was added portionwise and allowed to react at room temperature.

After completion of the reaction, water was used to remove reaction by-products and unreacted aluminum chloride. Then 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 After the addition, the mixture was stirred at 120 ° C for 8 hours. The mixture was then cooled and neutralized to pH 7 with 10% hydrogen chloride solution.

The mixture was then extracted with ethyl acetate and the powder obtained by rotary evaporation was dissolved in 200 mL of tetrahydrofuran and 18.98 g (0.5 mol) of lithium aluminum hydride was added thereto. Was added to the reaction mixture in small amounts. 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

50.0 g (0.166 mol) of coronene and 97.3 g (0.499 mol) of 2H-chromene-3-carbonyl chloride were added to the flask together with 700 g of a chloroform / dichloromethane mixture To prepare a solution. Subsequently, the solution was stirred using a stirring bar, 66.6 g (0.499 mol) of aluminum chloride was added in small portions, and the mixture was heated to 60 DEG C and stirred 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. 300 ml of the dried reaction product (61.8 g, 0.095 mol), K ₄ Fe (CN) ₆ (0.054 mol), PS-Pd (II) -anthra catalyst (1.0 mol% Pd) and triethylamine Was dissolved in N, N-dimethylformamide and stirred at 100 ° C for 24 hours.

After the reaction was completed, the mixture was slowly cooled to room temperature and filtered to remove the PS-Pd (II) -anthra catalyst, and the filtrate was purified by flash column chromatography using silica gel. The obtained powder was dissolved in 300 mL of tetrahydrofuran, and 38 g (1.0 mol) of lithium aluminum hydride (LiAlH ₄ ) 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

21.8 g (0.105 mol) of phenanthro [4,5-bcd] thiophene and 48.5 g (0.22 mol) of methoxy naphthoyl chloride were added together with 500 g of a chloroform / dichloromethane mixture To prepare a solution. The solution was stirred using a stirring bar and reacted with a small amount of 61.2 g (0.35 mol) of aluminum chloride.

After completion of the reaction, water was used to remove reaction by-products and unreacted aluminum chloride. The reactants obtained with the powder were heated (reflux) with 40 ml of formamide and 5 ml of 85% formic acid for 3 hours at 190 ° C. The reaction product was cooled to a temperature of 100 ° C or lower and then added to 250 ml of normal temperature water. The resulting precipitate was filtered and washed with a water / methanol mixture to remove the side reaction product to obtain a compound represented by the following formula 1cc.

[Formula 1cc]

Synthetic example  4

26.4 g (0.105 mol) of benzopyrene and 58.4 g (0.3 mol) of 2H-chromene-3-carbonyl chloride were added to 500 g of a chloroform / dichloromethane mixture The solution was put together. The solution was stirred using a stirring bar, and 40.0 g (0.3 mol) of aluminum chloride was gradually added thereto.

After completion of the reaction, water was used to remove reaction by-products and unreacted aluminum chloride, and the reaction product obtained by the powder was filtered and dried. 95.9 g (0.5 mol) of the dried powder and 3-quinolinecarbonyl chloride were added to 500 g of chloroform / dichloromethane mixed solution, stirred using a stirring bar, and aluminum chloride 122.33 g (0.5 mol) was added in small portions, and the mixture was heated to 60 DEG C and reacted for 12 hours.

After completion of the reaction, reaction by-products and unreacted aluminum chloride were removed using water, extracted with ethyl acetate, and dried under reduced pressure. After the resulting compound into a 1 L flask, a dimethylformamide 270 g of sodium borohydride _{(NaBH 4, Sodium Borohydride) 37.83g} (1 mol) was added little by little. Upon completion of the addition, the mixture was reacted at 50 DEG C with stirring for 18 hours. After completion of the reaction, the reaction mixture was neutralized with a 7% hydrogen chloride solution to a pH of about 6, extracted with ethyl acetate, and dried by rotary evaporation to obtain a compound represented by the following Chemical Formula 1dd.

[Chemical Formula 1dd]

Comparative Synthetic Example  One

42 g (0.166 mol) of perylene and 95.3 g (0.499 mol) of naphthoyl chloride were placed in a mixture of 700 g of chlroform / dichlromethane to prepare a solution. The solution was stirred using a stirring bar and 66.6 g (0.499 mol) of aluminum chloride (AlCl ₃ , Aluminum Chloride) was added little by little, and then the temperature was raised to 60 ° C and the mixture was reacted for 8 hours with stirring.

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. 57.6 g (0.105 mol) of the dried reaction product and 200 g of Raney Nickel were stirred with 600 ml of 2-propanol for 1 hour while refluxing. After completion of the reaction, the mixture was cooled to room temperature, and then the organic layer was removed. The mixture was rotary evaporated to obtain a compound represented by the following formula (2).

(2)

Hard mask  Preparation of composition

Example  One

The compound obtained in Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), .

Example  2

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

Example  3

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

Example  4

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

Comparative Example  One

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

Rating 1: Awareness of corrosion

On the silicon wafer, the hard mask composition (monomer content: 10.0% by weight based on the total composition) according to Examples 1 to 4 and Comparative Example 1 was applied by spin-on coating method and then heat-treated on a hot plate at 240 캜 for 1 minute, . The thickness of the thin film was measured by a thin film thickness gauge of K-MAC.

Subsequently, the thin film was dry-etched for 100 seconds using a CF _x mixed gas, and the thickness of the thin film was measured. The bulk etch rate (BER) was calculated according to the following equation 1.

[Equation 1]

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

The results are shown in Table 1.

Initial thin film thickness (Å) Thickness after etching (Å) The etching rate (Å / sec) Comparative Example 1 4853 3630 25.2 Example 1 4763 3585 24.7 Example 2 4586 3447 24.8 Example 3 4618 3482 24.5 Example 4 4693 3542 24.5

Referring to Table 1, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 4 has a lower etching rate than the thin film formed from the hard mask composition according to Comparative Example 1. [

From the results, it can be seen that the hard mask composition according to Examples 1 to 4 has higher corrosion resistance due to the high degree of crosslinking of the thin film as compared with the hard mask composition according to Comparative Example 1.

Evaluation 2: Contact angle  characteristic

The hard mask composition (monomer content: 10.0 wt% based on the total composition) according to Examples 1 to 4 and Comparative Example 1 was applied onto a silicon wafer using a spinner, respectively. Subsequently, the film was baked on a hot plate at 400 DEG C for 120 seconds to form a thin film. Then, the contact angle of the thin film was measured with a contact angle meter, and the coating property of the thin film was confirmed by a thin film thickness meter of K-MAC.

The results are shown in Table 2.

Contact angle Coating property Comparative Example 1 64 Poor - pinhole occurrence Example 1 47 Good Example 2 50 Good Example 3 51 Good Example 4 49 Good

Referring to Table 2, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 4 has a smaller contact angle value as compared with the thin film formed from the hard mask composition according to Comparative Example 1. [ This means that the hard mask composition according to Examples 1 to 4 has high hydrophilicity compared to the hard mask composition according to the comparative example. Accordingly, the hard mask composition according to Examples 1 to 4 has high affinity with silicon wafers It can be confirmed that it has good thin film coating properties.

Evaluation 3: Gap-fill and planarization characteristics

The hard mask composition (monomer content: 10.0 wt.% Based on the total composition) according to Examples 1 to 4 and Comparative Example 1 was spin-coated on a patterned silicon wafer and heat-treated at 400 ° C for 120 seconds on a hot plate, 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 voids were 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 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 2]

The results are shown in Table 3.

Gap fill characteristics (with or without void) Planarization characteristics
main coating (1500 rpm) aspect ratio
(1: 1.5) aspect ratio
(1:10) Comparative Example 1 void None Has void 24.55 Example 1 void None void None 21.57 Example 2 void None void None 22.62 Example 3 void None void None 23.83 Example 4 void None void None 21.95

Referring to Table 3, the thin film formed from the hard mask composition according to Examples 1 to 4 has a superior leveling property and voids as compared with the thin film formed from the hard mask composition according to Comparative Example 1, .

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 (18)

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

In Formula 1,
A, A 'and A "are each independently a substituted or unsubstituted aromatic ring group,
X and X 'each independently represents a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group , A substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkyl ether, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Lt; / RTI &
L and L 'are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group or a combination thereof,
m and n each independently represent an integer of 0 or more and satisfy 1? m + n? (the maximum number of substituents A can have).
Provided that at least one of A, A 'and A "is an aromatic ring group selected from the following group 1, and when m is 0, at least one of A and A" is an aromatic ring group selected from the following group 1 When n is 0, at least one of A and A 'is an aromatic ring group selected from the following Group 1, and A does not contain a coronene moiety:
[Group 1]

In the group 1,
Z ¹ and Z ² are each independently C═O, NR, oxygen (O), sulfur (S), or a combination thereof wherein R is hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, A halogen-containing group,
Z ³ is nitrogen (N). The method of claim 1,
Wherein at least one of A, A 'and A " is a substituted or unsubstituted aromatic ring group selected from the following Group 2:
However, A does not include a coronene moiety.
[Group 2]

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,
Wherein A, A 'or A "is a group selected from the group consisting of 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 ≪ / RTI > or a combination thereof. The method of claim 1,
Wherein the monomer is represented by any one of the following formulas (1a), (1c) and (1d):
[Formula 1a]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above formulas (1a), (1c) and (1d)
X ^a , X ^b and X ^e to X ^h each independently represent a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group , A substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, A substituted or unsubstituted C1 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkenyl group A substituted or unsubstituted C7 to C20 arylalkylene ether, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C1 to C20 alkylboranyl group, a substituted or unsubstituted C6 to C30 arylborane group, A combination thereof,
Z ^e and Z ^g are each independently C═O, NR, oxygen (O), sulfur (S), or a combination thereof wherein R is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, A halogen-containing group,
Z ^a , Z ^b and Z ^f are respectively nitrogen (N)
OR ₁ and OR ₂ each independently represent a C1 to C30 alkoxy group. The method of claim 1,
Wherein the monomer has a molecular weight of from 200 to 5,000. A monomer represented by the following formula (1), and
menstruum
A hard mask composition comprising:
[Chemical Formula 1]

In Formula 1,
A, A 'and A "are each independently a substituted or unsubstituted aromatic ring group,
X and X 'each independently represents a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group , A substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkyl ether, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Lt; / RTI &
L and L 'are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group or a combination thereof,
m and n each independently represent an integer of 0 or more and satisfy 1? m + n? (the maximum number of substituents A can have).
Provided that at least one of A, A 'and A "is an aromatic ring group selected from the following group 1, and when m is 0, at least one of A and A" is an aromatic ring group selected from the following group 1 When n is 0, at least one of A and A 'is an aromatic ring group selected from the following Group 1, and A does not contain a coronene moiety:
[Group 1]

In the group 1,
Z ¹ and Z ² are each independently C═O, NR, oxygen (O), sulfur (S), or a combination thereof wherein R is hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, A halogen-containing group,
Z ³ is nitrogen (N). 8. The method of claim 7,
Wherein at least one of A, A 'and A " is a substituted or unsubstituted aromatic ring group selected from the following group 2:
However, A does not include a coronene moiety.
[Group 2]

9. The method of claim 8,
Wherein at least one of A, A 'and A " is a substituted or unsubstituted polycyclic aromatic group. The method of claim 9,
Wherein A, A 'or A "is a group selected from the group consisting of 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. 8. The method of claim 7,
Wherein the monomer is represented by any one of the following formulas (1a), (1c), and (1d):
[Formula 1a]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above formulas (1a), (1c) and (1d)
X ^a , X ^b and X ^e to X ^h each independently represent a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group , A substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, A substituted or unsubstituted C1 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkenyl group A substituted or unsubstituted C7 to C20 arylalkylene ether, a substituted or unsubstituted C1 to C30 haloalkyl group, a substituted or unsubstituted C1 to C20 alkylboranyl group, a substituted or unsubstituted C6 to C30 arylborane group, A combination thereof,
Z ^e and Z ^g are each independently C═O, NR, oxygen (O), sulfur (S), or a combination thereof wherein R is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, A halogen-containing group,
Z ^a , Z ^b and Z ^f are respectively nitrogen (N)
OR ₁ and OR ₂ each independently represent a C1 to C30 alkoxy group. 8. The method of claim 7,
Wherein the monomer has a molecular weight of from 200 to 5,000. 8. The method of claim 7,
Wherein the monomer is included in an amount of from 0.1% to 50% 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 7 to 13 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 said silicon-containing thin film layer and said hard mask layer using said photoresist pattern and exposing a portion of said material layer; and
Etching the exposed portion of the material layer
≪ / RTI > The method of claim 14,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method. The method of claim 14,
Wherein the forming of the hard mask layer is performed at a temperature of 100 ° C to 500 ° C. The method of claim 14,
And forming a bottom anti-reflective layer (BARC) on the silicon-containing thin film layer. The method of claim 17,
Wherein the silicon-containing thin film layer contains silicon oxynitride (SiON).