KR101344788B1 - Hardmask composition and method of forming patterns and semiconductor integrated circuit device including the patterns - Google Patents

Abstract

[화학식 2]

상기 화학식 1 또는 2에서, A, B, R¹, R²　및 n 의 정의는 명세서에서 정의한 바와 같다.
또한 상기 하드마스크 조성물을　사용한 패턴 형성 방법 및 상기 방법으로 형성된 복수의 패턴을 포함하는 반도체 집적회로 디바이스　또한 제공한다.Provided is a hard mask composition including an aromatic ring-containing compound and a solvent including at least one of a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formula 2.
[Chemical Formula 1]

(2)

In Formula 1 or 2, the definitions of A, B, R ¹ , R ^2, and n are as defined in the specification.
The present invention also provides a method of pattern formation using the hard mask composition and a semiconductor integrated circuit device including a plurality of patterns formed by the method.

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. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

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

There is a need to reduce the size of patterns to provide larger amounts of circuitry for a given chip size, as well as in microelectronics as well as in the fabrication of microscopic structures (eg, micromachines, magnetoresist heads, etc.). .

Effective lithographic techniques are essential to achieving a reduction in pattern size. Lithographic influences the fabrication of microscopic structures not only in terms of directly imaging the pattern on a given substrate, but also in the manufacture of masks typically used for such imaging.

Typical lithographic processes include forming a patterned resist layer by patterning exposing the radiation-sensitive resist to imaging radiation. The exposed resist layer is then developed with a developer. The pattern is then transferred to the backing material by etching the material in the openings of the patterned resist layer. After the transfer is completed, the remaining resist layer is removed.

However, for some lithographic imaging processes, the resist used does not provide sufficient resistance to subsequent etching steps to such an extent that it can effectively transfer the desired pattern to the layer underlying the resist. Thus, for example, when an ultra thin resist layer is required, when the backing material to be etched is thick, when a considerable etching depth is required and / or when it is necessary to use a specific etchant for a given backing material, The hardmask layer is used as an intermediate layer between the resist layer and the backing material that can be patterned by transfer from the patterned resist.

The hard mask layer must be able to withstand the etching process necessary to receive the pattern from the patterned resist layer and transfer the pattern to the backing material.

The hard mask layer is desired to perform lithographic techniques using a hard mask composition that has high etch selectivity, is resistant to multiple etching, and minimizes the reflectivity between the resist and the backside layer. Patterns using such hardmask compositions may have improved optical properties.

One aspect of the present invention provides a hard mask composition that has high etch selectivity and can improve optical properties.

Another aspect of the present invention provides a method of forming a pattern using the hard mask composition.

Another aspect of the present invention provides a semiconductor integrated circuit device including a pattern formed by the above method.

According to an aspect of the present invention, a hard mask composition including an aromatic ring-containing compound and a solvent including at least one of a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formula 2 is provided.

[Formula 1]

(2)

In the above formula (1) or (2)

A is an aromatic ring group,

B is substituted or unsubstituted C1 to C30 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted Or an unsubstituted C7 to C30 arylalkylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or Unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, halogen group or a combination thereof,

R ¹ and R ² are each independently hydrogen, a hydroxy 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, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 hetero An aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, except where both R ¹ and R ² are hydrogen;

n is 1 to 190.

The A may be one selected from a substituted or unsubstituted aromatic ring group listed in Group 1 below.

[Group 1]

In the group 1,

Y ₁ to Y ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

B may be one selected from substituted or unsubstituted aromatic ring groups listed in Group 2 below.

[Group 2]

In group 2 above,

Z ₁ to Z ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

The aromatic ring-containing compound may have a weight average molecular weight of about 1000 to 10000.

The aromatic ring-containing compound and the solvent may be included in an amount of about 1 to 20 wt% and about 80 to 99 wt%, respectively, based on the total amount of the hard mask composition.

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

According to another aspect of the invention, the step of providing a material layer on the substrate, an aromatic ring containing compound and a solvent comprising at least one of a structural unit represented by the formula (1) and a structural unit represented by the formula (2) on the material layer Forming a hard mask layer by applying a hard mask composition comprising: forming a resist layer on the hard mask layer, exposing and developing the resist layer to form a resist pattern, using the resist pattern Selectively removing the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer.

[Formula 1]

(2)

In the above formula (1) or (2)

A is an aromatic ring group,

B is substituted or unsubstituted C1 to C30 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted Or an unsubstituted C7 to C30 arylalkylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or Unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, halogen group or a combination thereof,

R ¹ and R ² are each independently hydrogen, a hydroxy 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, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 hetero An aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, except where both R ¹ and R ² are hydrogen;

n is 1 to 190.

The A may be one selected from a substituted or unsubstituted aromatic ring group listed in Group 1 below.

[Group 1]

In the group 1,

Y ₁ to Y ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

B may be one selected from substituted or unsubstituted aromatic ring groups listed in Group 2 below.

[Group 2]

In group 2 above,

Z ₁ to Z ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

The aromatic ring-containing compound may have a weight average molecular weight of about 1000 to 10000.

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 step of forming the hard mask layer may be performed by a spin-on-coating method.

The manufacturing method may further include forming an auxiliary layer containing silicon on the material layer before forming the resist layer.

The manufacturing method may further include forming a bottom anti-reflective layer (BARC) before forming the hard mask layer.

According to still another aspect of the present invention, a semiconductor integrated circuit device including a plurality of patterns formed by the pattern forming method described above is provided.

The etching selectivity can be enhanced, resistance against multiple etching can be ensured, and optical characteristics can be improved.

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

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, alkyl group, C2 to C20 alkenyl group, C2 to C20 Alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, cycloalkyl group, C3 to C15 cycloalkenyl group, C6 To C15 is substituted with a substituent selected from a cycloalkynyl group, a heterocycloalkyl group, and a combination thereof.

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

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

The hard mask composition according to one embodiment comprises an aromatic ring-containing compound and a solvent.

The aromatic ring-containing compound may include at least one of a structural unit represented by the following Chemical Formula 1 and a structural unit represented by the following Chemical Formula 2.

[Formula 1]

(2)

In the above formula (1) or (2)

A is an aromatic ring group. The aromatic ring group herein refers to a ring group in which electrons are delocalized or resonated, and include an aryl group, heteroaryl group, or a combination thereof.

The A may be one selected from a substituted or unsubstituted aromatic ring group listed in Group 1 below.

[Group 1]

Y ₁ to Y ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

The aromatic ring groups listed in Group 1 may be linked to neighboring portions of Formula 1 or 2 in any carbon portion of the aromatic ring group, and the position thereof is not particularly limited.

B is substituted or unsubstituted C1 to C30 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted Or an unsubstituted C7 to C30 arylalkylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or Unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, halogen group or a combination thereof.

When B is an arylene group, it may be one selected from substituted or unsubstituted aromatic ring groups listed in Group 2 below.

[Group 2]

In group 2 above,

Z ₁ to Z ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

The aromatic ring groups listed in Group 2 may be connected to neighboring portions of Formula 1 or 2 in any carbon portion of the aromatic ring group, and the position thereof is not particularly limited.

R ¹ and R ² are each independently hydrogen, a hydroxy 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, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 hetero An aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, except where both R ¹ and R ² are hydrogen;

n is 1 to 190.

The aromatic ring group included in Formula 1 or Formula 2 may absorb light of a predetermined wavelength region, and the light of the predetermined wavelength region may be, for example, a short wavelength region of about 193 nm or 243 nm.

The aromatic ring-containing compound may include two or more structural units having different substituents or two or more aromatic ring-containing compounds having different substituents in the form of a mixture.

The weight average molecular weight of the aromatic ring-containing compound may be about 1000 to 10000. By having a weight average molecular weight in the above range, solubility can be ensured to achieve a desired coating thickness, and a good thin film can be formed.

The aromatic ring-containing compound may be included in an amount of about 1 to 20% by weight based on the total amount of the hard mask composition. It may be included in the range of about 3 to 15% by weight. By including the aromatic ring-containing compound within the above range, the optical characteristics can be improved while securing the coating properties.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility to the aromatic ring-containing compound, and examples thereof include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and ethyl lactate As shown in FIG.

The solvent may be included in an amount of about 80 to 99% by weight based on the total amount of the hard mask composition. By including the solvent within the above range, stable solubility can be ensured and coating properties can be improved.

The hard mask composition may further comprise additives such as surfactants, crosslinking agents, and the like.

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 crosslinking agent is an amino resin such as an etherified amino resin, which is used in order to cause self-crosslinking to occur more easily. Glycoluril compounds such as compounds represented by the following formula (A1) or (A2); A bis epoxy compound such as a compound represented by the following formula (B); A melamine resin such as an N-methoxymethyl melamine resin, an N-butoxymethyl melamine resin or a compound represented by the following formula (C); Or a mixture thereof.

(A1)

(A2)

[Formula B]

≪ RTI ID = 0.0 &

The surfactant and the crosslinking agent may be included in an amount of about 0.01 wt% to 5 wt% with respect to the hard mask composition. By including it in the above range, solubility and crosslinkability can be ensured 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 providing a layer of material on a substrate, applying a hard mask composition comprising an aromatic ring containing compound and a solvent on the layer of material to form a hard mask layer, Forming a resist layer, exposing and developing the resist layer to form a resist pattern, selectively removing the hard mask layer using the resist pattern and exposing a part of the material layer, And etching the exposed portions of the 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 sputtering or chemical vapor deposition method.

The hard mask layer may be formed by applying a hard mask composition.

The hard mask composition comprises an aromatic ring-containing compound and a solvent.

The aromatic ring-containing compound may include at least one of a structural unit represented by the following Chemical Formula 1 or a structural unit represented by the following Chemical Formula 2.

[Formula 1]

(2)

In the above formula (1) or (2)

A is an aromatic ring group. An aromatic ring group herein refers to a ring group in which an electron is delocalized or resonated, and includes an aryl group, heteroaryl group, or a combination thereof.

The A may be one selected from a substituted or unsubstituted aromatic ring group listed in Group 1 below.

[Group 1]

Y ₁ to Y ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

The aromatic ring groups listed in Group 1 may be linked to neighboring portions of Formula 1 or 2 in any carbon portion of the aromatic ring group, and the position thereof is not particularly limited.

B is substituted or unsubstituted C1 to C30 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted Or an unsubstituted C7 to C30 arylalkylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or Unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, halogen group or a combination thereof.

When B is an arylene group, it may be one selected from substituted or unsubstituted aromatic ring groups listed in Group 2 below.

[Group 2]

In group 2 above,

Z ₁ to Z ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.

The aromatic ring groups listed in Group 2 may be connected to neighboring portions of Formula 1 or 2 in any carbon portion of the aromatic ring group, and the position thereof is not particularly limited.

R ¹ and R ² are each independently hydrogen, a hydroxy 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, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 hetero An aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, except where both R ¹ and R ² are hydrogen;

n is 1 to 190.

The aromatic ring group included in Formula 1 or Formula 2 may absorb light of a predetermined wavelength region, and the light of the predetermined wavelength region may be, for example, a short wavelength region of about 193 nm or 243 nm.

The aromatic ring-containing compound may include two or more structural units having different substituents or two or more aromatic ring-containing compounds having different substituents in the form of a mixture.

The weight average molecular weight of the aromatic ring-containing compound may be about 1000 to 10000. By having a weight average molecular weight in the above range, solubility can be ensured to achieve a desired coating thickness, and a good thin film can be formed.

The aromatic ring-containing compound may be included in an amount of about 1 to 20% by weight based on the total amount of the hard mask composition. It may be included in the range of about 3 to 15% by weight. By including the aromatic ring-containing compound within the above range, the optical characteristics can be improved while securing the coating properties.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility to the aromatic ring-containing compound, and examples thereof include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and ethyl lactate As shown in FIG.

The solvent may be included in an amount of about 80 to 99% by weight based on the total amount of the hard mask composition. By including the solvent within the above range, stable solubility can be ensured and coating properties can be improved.

The hard mask composition may further comprise additives such as surfactants, crosslinking agents, and the like.

The hard mask composition may be prepared in the form of a solution and applied by a spin-on-coating method. The applied composition is then heat treated to form a hard mask layer.

At this time, the coating thickness and the heat treatment conditions of the hard mask composition are not particularly limited. For example, the hard mask composition may be applied in a thickness of about 500 to 7000 angstroms and heat-treated at about 100 to 500 DEG C for 10 seconds to 10 minutes.

Another auxiliary layer may be further formed before forming the hard mask layer. The auxiliary layer may be a silicon-containing thin film, for example, a thin film made of silicon nitride or silicon oxide.

Further, a bottom anti-reflective coating (BARC) may be further formed before forming the auxiliary layer.

A resist layer is then applied over the hardmask layer. The resist layer may be a radiation-sensitive imaging layer comprising a photosensitive material.

Then, the resist layer is exposed and developed to form a resist pattern.

Then, the hard mask layer is selectively removed using the resist pattern as a mask. At this time, if the auxiliary layer and / or the bottom anti-reflection layer are formed, they may be removed together. This may expose a portion of the underlying material layer.

The exposed portion of the material layer is then etched. Etching may be performed by dry etching using an etching gas. For example, CHF ₃ , CF ₄ , CH ₄ , Cl ₂ , BCl _3, or a mixed gas thereof may be used as the etching gas.

The hard mask layer, the resist layer, and the like are then removed using a conventional stripper to form a plurality of patterns formed from the material layer.

The plurality of patterns may vary from metal patterns, semiconductor patterns, insulating patterns, and the like, and may be various patterns in the semiconductor integrated circuit device. 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.

Synthesis of aromatic ring-containing compounds

Synthetic example  One

Into a 500 ml four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube, 2.02 g (0.01 mol) of pyrene and 19.1 g of naphthalene 2-carbonyl chloride were dissolved in 312 g of 1,2-dichloroethane. After making the solution, the solution was stirred. After 15 minutes, 14.6 g (0.109 mol) of aluminum trichloride was slowly added to the solution, and the reaction was performed at room temperature for 12 hours. After completion of the reaction, the salt was removed using water, and then concentrated by an evaporator. It was then diluted with cyclohexanone and adjusted to a solution of 15% by weight concentration. This solution was placed in a 1 L separatory funnel and n-heptane was added to precipitate to obtain a polymer represented by the following Chemical Formula 1a.

The polymer represented by the following Chemical Formula 1a has a weight average molecular weight of 2,300 and a degree of dispersion of 1.37.

[Formula 1a]

Synthetic example  2

Nitrogen gas was introduced into a 500 ml four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas introduction tube, and 1.62 g (0.008 mol) of pyrene and 21.2 g of pyrene 1-carbonyl chloride were dissolved in 311 g of 1,2-dichloroethane. After making the solution, the solution was stirred. After 15 minutes, 11.7 g (0.088 mol) of aluminum trichloride was slowly added to the solution, and the reaction was performed at room temperature for 12 hours. After completion of the reaction, the salt was removed using water, and then concentrated by an evaporator. It was then diluted with cyclohexanone and adjusted to a solution of 15% by weight concentration. This solution was placed in a 1 L separatory funnel and n-heptane was added to precipitate to obtain a polymer represented by the following Chemical Formula 1b.

The polymer represented by the following Chemical Formula 1b has a weight average molecular weight of 2,600 and a degree of dispersion of 1.31.

[Chemical Formula 1b]

Synthetic example  3

Nitrogen gas was introduced into a 500 ml four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube, and 2.42 g (0.0008 mol) of styrene and 15.3 g of naphthalene 2-carbonyl chloride were added to 264 g of 1,2-dichloroethane. After melting to form a solution, the solution was stirred. After 15 minutes, 11.7 g (0.109 mol) of aluminum trichloride was slowly added to the solution, and the reaction was performed at room temperature for 12 hours. After completion of the reaction, the salt was removed using water, and then concentrated by an evaporator. It was then diluted with cyclohexanone and adjusted to a solution of 15% by weight concentration. This solution was placed in a 1 L separatory funnel and n-heptane was added to precipitate to obtain a polymer represented by the following Chemical Formula 1c.

The polymer represented by the following Chemical Formula 1c has a weight average molecular weight of 3,100 and a degree of dispersion of 1.28.

[Chemical Formula 1c]

Synthetic example  4

Nitrogen gas was introduced into a 500 ml four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube, while 2.42 g (0.008 mol) of chlorine and 19.8 g of ethyl pyrene 1-carbonyl chloride were 284 g of 1,2-dichloroethane. After dissolving in to form a solution, the solution was stirred. After 15 minutes, 9.4 g (0.088 mol) of aluminum trichloride was slowly added to the solution, and the reaction was performed at room temperature for 12 hours. After completion of the reaction, the salt was removed using water, and then slowly added 3.63 g of sodium borohydride with methanol, and the reaction was performed at room temperature for 12 hours. After completion of the reaction, the salt was removed using water, and then concentrated by an evaporator. It was then diluted with cyclohexanone and adjusted to a solution of 15% by weight concentration. This solution was placed in a 1 L separatory funnel, and n-heptane was added to precipitate to obtain a polymer represented by the following Chemical Formula 2a.

The polymer represented by the following Chemical Formula 2a has a weight average molecular weight of 1,900 and a degree of dispersion of 1.42.

(2a)

Synthesis Example 5

Nitrogen gas was introduced into a 500 ml four-necked flask equipped with a mechanical stirrer, a cooling tube, and a nitrogen gas inlet tube, while 2.42 g (0.008 mol) of chlorine and 19.1 g of benzoperylene 5-carbonyl chloride were added to 1,2-dichloroethane. After dissolving in 26 g to form a solution, the solution was stirred. After 15 minutes, 8.2 g (0.061 mol) of aluminum trichloride was slowly added to the solution, and the reaction was performed at 70 ° C. for 12 hours. After completion of the reaction, the salt was removed using water, and then 3.18 g of sodium borohydride was slowly added with methanol, followed by reaction at 60 ° C. for 12 hours. After completion of the reaction, the salt was removed using water, and then concentrated by an evaporator. It was then diluted with cyclohexanone and adjusted to a solution of 15% by weight concentration. This solution was placed in a 1 L separatory funnel, and n-heptane was added to precipitate to obtain a polymer represented by the following Chemical Formula 2b.

The polymer represented by the following Chemical Formula 2b has a weight average molecular weight of 1,500 and a degree of dispersion of 1.44.

(2b)

Comparative Synthetic Example  One

8.75 g (0.05 mol) of α, α'-dichloro-p-xylene, 26.66 g of aluminum chloride, while introducing nitrogen gas into a 1 L four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel and a nitrogen gas introduction tube. 200 g of γ-butyrolactone was added and stirred.

After 10 minutes, a solution of 35.03 g (0.10 mol) of 4,4 '-(9-fluorenylidene) diphenol in 200 g of γ-butyrolactone was slowly added dropwise to the mixed solution for 30 minutes, followed by stirring for 12 hours. The polymerization was carried out.

After completion of the reaction, the acid was removed using water and then concentrated using an evaporator. Subsequently, the polymerization product was diluted with methyl amyl ketone and methanol, and the concentration was adjusted by adding a solution of methyl amyl ketone / methanol (4/1, weight ratio) at a concentration of 15% by weight again. The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight, to obtain a polymer represented by the following formula (3).

The polymer represented by the following formula (3) has a weight average molecular weight of 12,000 and a degree of dispersion of 2.0.

(3)

Hard mask  Preparation of the composition

Example  One

1.0 g of the aromatic ring-containing compound obtained in Synthesis Example 1, 0.1 g of a crosslinking agent (Powerlink 1174) represented by the following Chemical Formula A2, and 0.1 g of pyridinium p-toluene sulfonate were dissolved in 9 g of cyclohexanone and filtered to obtain a hard mask composition. Prepared.

(A2)

Example  2

A hardmask composition was prepared in the same manner as in Example 1, except that the aromatic ring-containing compound obtained in Synthesis Example 2 was used instead of the aromatic ring-containing compound obtained in Synthesis Example 1.

Example  3

A hardmask composition was prepared in the same manner as in Example 1, except that the aromatic ring-containing compound obtained in Synthesis Example 3 was used instead of the aromatic ring-containing compound obtained in Synthesis Example 1.

Example  4

A hardmask composition was prepared in the same manner as in Example 1, except that the aromatic ring-containing compound obtained in Synthesis Example 4 was used instead of the aromatic ring-containing compound obtained in Synthesis Example 1.

Example  5

A hardmask composition was prepared in the same manner as in Example 1, except that the aromatic ring-containing compound obtained in Synthesis Example 5 was used instead of the aromatic ring-containing compound obtained in Synthesis Example 1.

Comparative Example  One

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 1 was used instead of the aromatic ring-containing compound obtained in Synthesis Example 1.

Hard mask  Layer formation

After applying the hard mask composition according to Examples 1 to 5 and Comparative Example 1 by spin coating on a silicon wafer on which tetraethyl orthosilicate (TEOS) is formed, it was baked at 200 ° C. for 60 seconds to be baked at about 1500 kPa. A thick hardmask layer was formed.

Rating-1

The refractive index (n) and the extinction coefficient (k) of the hard mask layer formed from the hard mask composition according to Examples 1 to 5 were measured.

The refractive index and the extinction coefficient were measured using an Ellipsometer (manufactured by J.A. Woollam) while irradiating 193 nm light.

The results are shown in Table 1.

Optical Characteristic (193nm) Refractive index (n) Absorption coefficient (k) Example 1 1.38 0.42 Example 2 1.50 0.68 Example 3 1.22 0.59 Example 4 1.32 0.72 Example 5 1.32 0.65

Referring to Table 1, it can be seen that the hard mask layer formed of the hard mask compositions according to Examples 1 to 5 exhibits a refractive index (n) and an extinction coefficient (k) suitable for use as a hard mask layer for 193 nm light. .

Resist  Formation of patterns

After applying the hard mask composition according to Examples 1 to 5 and Comparative Example 1 on a silicon wafer on which tetraethyl allosilicate (TEOS) is formed by spin coating, baking at 200 ° C. for 60 seconds to harden a hard disk having a thickness of about 1500 μs. A mask layer was formed.

A KrF resist was applied on the hard mask layer and baked at 110 ° C. for 60 seconds, and then exposed using KrML exposure equipment ASML (XT: 1450G, NA0.93). It was then developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH).

Rating-2

The expose latitude (EL) margin and the depth of focus (DoF) margin due to the distance between the light source and the light source were investigated. In addition, FE-SEM was used to observe whether an undercut occurred in the patterned hard mask layer.

The results are shown in Table 2.

EL margin
(? CD / exposure energy, mJ) DoF margin (탆) Whether undercut occurred Example 1 0.2 0.15 X Example 2 0.2 0.15 X Example 3 0.2 0.15 X Example 4 0.2 0.15 X Example 5 0.2 0.15 X Comparative Example 1 0.1 0.10 ○

Referring to Table 2, it can be seen that the hard mask layer formed of the hard mask composition according to Examples 1 to 5 has a higher EL margin and a DoF margin than the hard mask layer formed of the hard mask composition according to Comparative Example 1. . In addition, it can be seen that the hard mask layer formed of the hard mask composition according to Examples 1 to 5 was formed with a good profile without an undercut observed.

Formation of patterns

Dry etching was performed using the CHF ₃ / CF ₄ mixed gas using the patterned hard mask layer as a mask, followed by dry etching again using the BCl ₃ / Cl ₃ mixed gas. All remaining organic matter was then removed using O ₂ gas.

Rating - 3

The tetraethyl allosilicate (TEOS) pattern was discussed using FE-SEM. The results are shown in Table 3.

Tetraethyl Allosilicate (TEOS) Pattern Example 1 Anisotropic Example 2 Anisotropic Example 3 Anisotropic Example 4 Anisotropic Example 5 Anisotropic Comparative Example 1 Tapered, rough surface

Referring to Table 3, the patterns formed using the hard mask compositions according to Examples 1 to 5 were all isotropically patterned in a vertical shape, whereas the patterns formed using the hard mask compositions according to Comparative Example 1 were not isotropically patterned. It can be seen that it shows a tapered shape and rough surface.

This is because when the hard mask composition according to Examples 1 to 5 is used, the etching is performed well because the resistance to the etching gas is sufficient, whereas when the hard mask composition according to Comparative Example 1 is used, the resistance to the etching gas is insufficient. It is judged that the etching selectivity for patterning to a shape is lacking.

Rating - 4

The etching resistance of the hard mask compositions according to Examples 1 to 5 and Comparative Example 1 was evaluated.

After applying the hard mask composition according to Examples 1 to 5 and Comparative Example 1 on a silicon wafer on which aluminum (Al) is formed by spin coating, baking at 300 ° C. for 60 seconds to form a hard mask layer having a thickness of about 3000 μm. Formed.

A KrF resist was applied on the hard mask layer and baked at 110 ° C. for 60 seconds, and then exposed using KrML exposure equipment ASML (XT: 1450G, NA0.93). It was then developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH).

Dry etching was performed using the CHF ₃ / CF ₄ mixed gas using the patterned hard mask layer as a mask, and the etching rate was calculated.

The results are shown in Table 4.

Etching Speed (Å / s) Example 1 28.9 Example 2 28.4 Example 3 28.1 Example 4 26.6 Example 5 25.1 Comparative Example 1 35

Referring to Table 4, it can be seen that the use of the hard mask compositions according to Examples 1 to 5 improves the etching resistance than the case of using 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 (15)

A hard mask composition comprising an aromatic ring-containing compound and a solvent comprising at least one of a structural unit represented by Formula 1 and a structural unit represented by Formula 2 below:
[Chemical Formula 1]

(2)

In the above formula (1) or (2)
A is an aromatic ring group,
B is substituted or unsubstituted C1 to C30 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted Or an unsubstituted C7 to C30 arylalkylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or Unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, halogen group or a combination thereof,
R ¹ and R ² are each independently hydrogen, a hydroxy 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, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 hetero An aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, except where both R ¹ and R ² are hydrogen;
n is 1 to 190.
In claim 1,
Wherein A is one selected from substituted or unsubstituted aromatic ring groups listed in Group 1 below:
[Group 1]

In the group 1,
Y ₁ to Y ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.
In claim 1,
Wherein B is one selected from substituted or unsubstituted aromatic ring groups listed in Group 2 below:
[Group 2]

In group 2 above,
Z ₁ to Z ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.
In claim 1,
The aromatic ring-containing compound has a weight average molecular weight of 1000 to 10000 hard mask composition.
In claim 1,
Wherein the aromatic ring-containing compound and the solvent are contained in an amount of 1 to 20 wt% and 80 to 99 wt%, respectively, based on the total content of the hard mask composition.
In 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.
Providing a layer of material over the substrate,
Forming a hardmask layer on the material layer by applying a hardmask composition including a solvent and an aromatic ring-containing compound including at least one of a structural unit represented by Formula 1 and a structural unit represented by Formula 2 below;
Forming a resist layer over the hardmask layer,
Exposing and developing the resist layer to form a resist pattern,
Selectively removing the hard mask layer using the resist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
: ≪ / RTI >
[Chemical Formula 1]

(2)

In the above formula (1) or (2)
A is an aromatic ring group,
B is substituted or unsubstituted C1 to C30 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted Or an unsubstituted C7 to C30 arylalkylene group, a substituted or unsubstituted C1 to C30 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, a substituted or Unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, halogen group or a combination thereof,
R ¹ and R ² are each independently hydrogen, a hydroxy 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, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 hetero An aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, except where both R ¹ and R ² are hydrogen;
n is 1 to 190.
In claim 7,
Wherein A is one selected from substituted or unsubstituted aromatic ring groups listed in Group 1 below:
[Group 1]

In the group 1,
Y ₁ to Y ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.
In claim 7,
Wherein B is one selected from substituted or unsubstituted aromatic ring groups listed in Group 2 below:
[Group 2]

In group 2 above,
Z ₁ to Z ₁₆ are each independently hydrogen or a C1 to C5 alkyl group.
In claim 7,
The aromatic ring-containing compound has a weight average molecular weight of 1000 to 10000 pattern formation method.
In claim 7,
Wherein the solvent comprises at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and ethyl lactate.
In claim 7,
Wherein the step of forming the hard mask layer is performed by a spin-on-coating method.
In claim 7,
Before the step of forming the resist layer
And forming an auxiliary layer containing silicon on the material layer.
The method of claim 13,
Before the step of forming the hard mask layer
And forming a bottom anti-reflective layer (BARC).
15. A semiconductor integrated circuit device comprising a plurality of patterns formed by a pattern forming method according to any one of claims 7 to 14.