KR101684978B1 - Hardmask composition, method of forming patterns using the hardmask composition and semiconductor integrated circuit device including the patterns including the patterns - Google Patents

Abstract

[화학식 2]

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

(2)

In Formula 1 and 2, A, A ', A ", L, L', X, X ', m, n, Ar and B are as defined in the specification.

Description

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

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

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

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

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

The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer is required to have properties such as heat resistance and corrosion resistance 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. The spin-on coating method can use a hard mask composition having solubility in solvents.

However, there is a need for a hard mask composition capable of satisfying both of the above-mentioned properties and solubility required for a hard mask layer in a trade-off relationship with each other.

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

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

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

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

[Chemical Formula 1]

In Formula 1,

A represents any one selected from the group consisting of a substituted or unsubstituted cyclic group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group and a substituted or unsubstituted C2 to C20 alkynylene group ego,

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

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

L and L 'are each independently a single bond, a substituted or unsubstituted C1 to 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 1 to 6, and m + n? (the maximum number of substituents that A may have).

(2)

In Formula 2,

Ar is a substituted or unsubstituted aromatic group selected from the following Group 1,

B is any one or a combination of two or more members selected from the following Group 2.

[Group 1]

[Group 2]

In the group 2, M ¹ and M ² each independently represents a hydrogen atom, 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 C 1 to C 30 alkoxy Or a combination thereof.

Each of A, A 'and A "may independently be a substituted or unsubstituted cyclic group selected from the following Group 3.

[Group 3]

In the group 3,

Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR ^a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom or a combination thereof,

Z ³ to Z ¹⁷ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.

At least one of A, A 'and A " may be a 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.

Wherein Ar is substituted with at least one hydrogen atom 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, .

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 And Y ^a to Y ^h each independently represents 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, to be.

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

The polymer may have a weight average molecular weight of 1,000 to 10,000.

The weight ratio of the monomer to the polymer may be monomer: polymer = 5: 5 to 1: 9.

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 monomer and the polymer may be contained in an amount of 0.1% by weight to 50% by weight based on 100% by weight of the solvent.

According to another embodiment, there is provided a method of manufacturing a hard mask, comprising the steps of providing a material layer on a substrate, applying the hard mask composition described above on the material layer, heat treating the hard mask composition to form a hard mask layer, Containing thin film layer; forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

The step of applying the hard mask composition may be performed by a spin-on coating method.

The step of forming the hard mask layer may include a heat treatment at 100 ° C to 500 ° C.

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

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

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

It is possible to improve the properties required in the hard mask layer such as heat resistance, corrosion resistance, planarization characteristics and gap-fill characteristics.

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

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a cyano group, A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a C1 to C4 alkoxy group, a substituted or unsubstituted C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, A C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, It means substituted with a substituent selected.

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

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

The hard mask composition according to one embodiment comprises a monomer represented by the following formula (1), a polymer having a moiety represented by the following formula (2), and a solvent.

[Chemical Formula 1]

In Formula 1,

A represents any one selected from the group consisting of a substituted or unsubstituted cyclic group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group and a substituted or unsubstituted C2 to C20 alkynylene group ego,

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

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

L and L 'are each independently a single bond, a substituted or unsubstituted C1 to 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 1 to 6, and m + n? (the maximum number of substituents that A may have).

(2)

In Formula 2,

Ar is a substituted or unsubstituted aromatic group selected from the following Group 1,

B is any one or a combination of two or more members selected from the following Group 2.

[Group 1]

[Group 2]

In the group 2, M ¹ and M ² each independently represents a hydrogen atom, 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 C 1 to C 30 alkoxy Or a combination thereof.

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

First, the monomers contained in the hard mask composition will be described.

Wherein the core represented by A in Formula 1 is a substituted or unsubstituted cyclic group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 alkylene group, A substituted or unsubstituted C2 to C20 alkenylene group, and a substituted or unsubstituted C2 to C20 alkynylene group.

The monomer includes a ring group substituted or unsubstituted in a substituent group.

For example, the monomer may comprise a substituted or unsubstituted cyclic group selected from the following Group 3 independently of the core and the substituent.

[Group 3]

In the group 3,

Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR ^a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom or a combination thereof,

Z ³ to Z ¹⁷ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.

In the group 3, the connecting position of each ring is not particularly limited, and each ring may be substituted or unsubstituted. When the ring in the group 3 is a substituted ring, it may be substituted with, for example, a C1 to C20 alkyl group, a halogen atom, a hydroxy group, etc., but the substituent is not limited.

In Formula 1, at least one of A, A 'and A "may be, for example, a polycyclic aromatic group in the group 1.

Meanwhile, m and n, which are the numbers of substituents in the above formula (1), are each independently an integer of 1 to 6, and the sum thereof can be appropriately selected within a range not exceeding the maximum number of substituents that A can have.

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

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

For example, A 'and A "in the above formula (1) are those wherein at least one hydrogen atom is replaced by a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, An alkoxy group, or a combination 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 And Y ^a to Y ^h each independently represents 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, to be.

The monomer may be an alkylene group, for example, as shown in Formula 1c above.

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 monomer may be contained in the hard mask composition alone or in a mixture of two or more kinds of monomers.

Next, the polymer contained in the hard mask composition will be described.

The polymer includes aromatic moieties that are substituted or unsubstituted in the repeating unit. This is represented by Ar in the above formula (2). Ar is selected from Group 1 and may be, for example, a polycyclic aromatic group.

Wherein Ar is a group selected from the group consisting of a hydrogen atom, 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, Lt; / RTI >

In Formula 2, B is any one or two or more of the groups selected from Group 2 above. The combination may be selected by a person skilled in the art according to the desired properties, for example, two or three different combinations selected from the group 2, but is not limited thereto. In addition, the position of the combination objects in the combination can be appropriately selected by a person skilled in the art.

The polymer may include, for example, a moiety represented by any one selected from the following formulas (2a) to (2c).

(2a)

(2b)

[Chemical Formula 2c]

In the above general formulas (2a) to (2d)

Y ¹ To Y ⁴ each independently represent a hydroxyl group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkoxy group or a combination thereof.

The polymer may have, for example, a weight average molecular weight of 1,000 to 10,000, but is not limited thereto.

The polymer may be contained in the hard mask composition alone or in a mixture of two or more polymers.

On the other hand, the solvent included in the hard mask composition is not particularly limited as long as it has sufficient solubility or dispersibility in the monomer and the polymer, and examples thereof include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene (Ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, methylpyrrolidone and acetyl acetone. And may include at least one.

The monomer and the polymer may be included in an amount of about 0.1 to 50% by weight based on 100% by weight of the solvent. The monomer and the polymer may be coated with a thin film having a desired thickness by being included in the above range.

The monomer and the polymer may be in a weight ratio of monomer: polymer of, for example, 5: 5 to 1: 9.

The hard mask composition may further comprise a surfactant.

The surfactant may be, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

The surfactant may be included in an amount of about 0.001 to 3 parts by weight based on 100 parts by weight of the hard mask composition. By including it in the above range, the solubility can be improved without changing the optical properties of the hard mask composition.

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

A patterning method according to one embodiment includes the steps of providing a layer of material on a substrate, applying a hard mask composition comprising the above-mentioned monomers and a solvent on the material layer, heat treating the hard mask composition to form a hard mask layer Containing thin film layer on the hard mask layer; forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the silicon-containing thin film layer and the hard mask layer using a mask to expose a portion of the material layer, and etching the exposed portion of the material layer.

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be finally patterned and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer may be formed by, for example, a chemical vapor deposition method.

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

The heat treatment of the hard mask composition may be performed at a temperature of, for example, about 100 캜 to 500 캜 for about 10 seconds to about 10 minutes. In the heat treatment step, the monomer may cause self-crosslinking and / or cross-linking reaction.

The silicon-containing thin film layer may be made of, for example, silicon nitride, silicon oxide or silicon oxynitride (SiON).

The method may further include forming a bottom anti-reflective coating (BARC) on the silicon-containing thin film layer. For example, a thin film layer containing silicon oxynitride may be formed on the hard mask layer, then a bottom antireflection layer may be formed thereon, and then a photoresist layer may be formed on the bottom antireflection layer.

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

The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may include, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof. It is not.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied to various patterns in a semiconductor integrated circuit device, for example.

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

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Monomeric  synthesis

Synthetic example  One

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

To the flask, 29.6 g (0.105 mol) of methoxyperylene, 11.06 g (0.05 mol) of isophthaloyl chloride and 223 g of dichloroethane were added to prepare a solution. Then, 14.68 g (0.105 mol) of aluminum chloride was added little by little to the solution and stirred for 2 hours. After completion of the reaction, the reaction product obtained by the powder was filtered and dried.

Step 2: Removal of methyl groups ( demethylation ) reaction

39.62 g (0.2 mol) of 1-dodecanethiol, 13.73 g (0.24 mol) of potassium hydroxide and 350 g of N, N-dimethylformamide were added to the flask, followed by stirring at 120 ° C for 3 hours . The mixture was then cooled, neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate and dried.

Step 3: Reduction ( reduction ) reaction

The compound thus obtained was dissolved in 100 mL of tetrahydrofuran, and 25.56 g (0.67 mol) of sodium borohydride was added little by little to the flask, followed by stirring at 50 DEG C for 12 hours. After completion of the reaction, the reaction mixture was neutralized with a 7% hydrogen chloride solution to a pH of about 7, and extracted with ethyl acetate to obtain a compound represented by the following formula (1aa).

(1aa)

Synthetic example  2

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

To the flask, 15.85 g (0.05 mol) of benzopyrene, 23.13 g (0.105 mol) of methoxynaphthoyl chloride and 214 g of dichloroethane were added to prepare a solution. 14.68 g (0.11 mol) of aluminum chloride was slowly added to the solution, and the mixture was stirred at room temperature for 1 hour. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 2: Removal of methyl groups ( demethylation ) reaction

36.21 g (0.18 mol) of 1-dodecanethiol, 12.55 g (0.22 mol) of potassium hydroxide and 315 g of N, N-dimethylformamide were added to the flask, followed by stirring at 120 ° C for 8 hours . The mixture was then cooled, neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate and dried.

Step 3: Reduction ( reduction ) reaction

To the flask, the compound obtained above was dissolved in 100 mL of tetrahydrofuran, and 22.98 g (0.60 mol) of lithium aluminum hydride was gradually added thereto. 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

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

To the flask, a solution was prepared by adding dimethyl malonyl chloride (22.6 g, 0.1345 mol), methoxy pyrene (62.4 g, 0.269 mol) and 556 g of 1,2-dichloroethane. Subsequently, aluminum chloride (17.9 g, 0.1345 mol) was slowly added to the solution, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.

Step 2: Removal of methyl groups ( demethylation ) reaction

To the flask was added the above-obtained compound (5.60 g, 0.01001 mol), 1-dodecan sulfate (10.13 g, 0.05005 mol), potassium hydroxide (3.37 g, 0.06006 mol) and N, N- dimethylformamide Followed by stirring at 120 ° C for 8 hours. The mixture was cooled and neutralized to about pH 6-7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried.

Step 3: Reduction ( reduction ) reaction

To the flask was added the compound obtained above (2.19 g, 0.004120 mol) and 28.5 g of tetrahydrofuran to prepare a solution. Then, an aqueous solution of sodium borohydride (3.12 g, 0.08240 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction solution was neutralized to pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by the following formula 1cc.

[Formula 1cc]

Synthetic example  4

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

27.6 g (0.1 mol) of benzoperrylene and 48.5 g (0.22 mol) of methoxynaphthoyl chloride were placed in a 500 g of chloroform / dichloromethane mixture and stirred using a stirring bar. Subsequently, 61.2 g (0.35 mol) of aluminum chloride was added to the mixture in small increments. When the reaction was completed, methanol was added to the mixture, and the resulting precipitate was filtered and dried.

Step 2: Removal of methyl groups ( demethylation ) reaction

To the flask was added the above obtained compound (6.50 g, 0.01001 mol), 1-dodecan sulfate (10.13 g, 0.05005 mol), potassium hydroxide (3.37 g, 0.06006 mol) and N, N- dimethylformamide Followed by stirring at 120 ° C for 8 hours. Subsequently, the reaction product was cooled and neutralized to about pH 6-7 with 5% hydrogen chloride solution, and the precipitate formed was filtered and dried.

Step 3: Reduction ( reduction ) reaction

To the flask was added the compound obtained above (5.60 g, 0.01001 mol), 40 ml of formamide and 5 ml of 85% formic acid, and the mixture was refluxed at 190 ° C for 3 hours. Subsequently, 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 Chemical Formula 1dd.

[Chemical Formula 1dd]

Synthesis of polymer

Polymerization Example  One

28.33 g (0.2 mol) of 1-naphthol, 28.32 g (0.14 mol) of pyrene and 12.0 g (0.34 mol) of paraformaldehyde were added to the flask. Subsequently, 0.19 g (0.34 mol) of p-toluenesulfonic acid monohydrate was dissolved in 162 g of propylene glycol monomethyl ether acetate (PGMEA), and the solution was poured into a flask and stirred at 90 to 100 ° C for 5 to 12 hours. Samples were taken from the polymerization reactants at intervals of 1 hour. When the weight average molecular weight of the sample was 3500 to 4000, the reaction was completed and then cooled to room temperature. The reaction product was poured into 40 g of distilled water and 400 g of methanol, stirred vigorously and allowed to stand (primary). The supernatant was removed and the precipitate was dissolved in 80 g of PGMEA (second order) of floroprene glycol monomethyl ether acetate (PGMEA). The primary and secondary processes were referred to as a one-time purification process, and this purification process was performed three times in total. After the purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a compound represented by the following formula (2aa).

[Formula 2aa]

Polymerization Example  2

10 g (0.055 mol) of 1-hydroxypyrylene and 9.14 (mol) of 4,4-methoxymethylbenzene were sequentially added to the flask and dissolved in 43 g of propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution. Subsequently, 0.12 g (0.025 mol) of diethylsulfite was added to the solution, followed by stirring at 90 to 120 ° C for about 5 to 10 hours. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 4,200 to 5,000.

The purification process was then purified by the same procedure as Polymerization Example 1 to obtain a compound represented by the following Formula 2bb.

(2bb)

Polymerization Example  3

16.52 g (0.055 mol) of 1-hydroxy perylene and 9.9 g (0.068 mol) of 1-naphthol were sequentially added to the flask and dissolved in 32 g of propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution. Then, 22 g (0.11 mol) of 1,4-bismethoxymethylbenzene and 0.8 g (0.009 mol) of diethylsulfite were added to the solution, followed by stirring at 90 to 120 ° C for about 8 to 15 hours. Samples were taken from the polymerization reactants at intervals of 1 hour and the reaction was completed when the weight average molecular weight of the sample was 4,600 to 5,500.

Thereafter, the purification process was repeated seven times in the same manner as in Polymerization Example 1 to obtain a compound represented by the following formula (2cc).

[Formula 2cc]

Comparative Synthetic Example  One

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

To the flask, a solution was prepared by adding 50.0 g (0.166 mol) of coronene, 46.8 g (0.333 mol) of benzoyl chloride and 330 g of 1,2-dichloroethane. Subsequently, 44.4 g (0.333 mol) of aluminum chloride was added slowly to the solution at room temperature, and the temperature was raised to 60 ° C and the mixture was stirred for 8 hours. When the reaction was completed, methanol was added to the solution, and the resulting precipitate was filtered and dried.

Step 2: Reduction ( reduction ) reaction

To the flask was added 25.0 g (0.0492 mol) of the coupling compound and 174 g of tetrahydrofuran. 18.6 g (0.492 mol) of sodium borohydride aqueous solution was slowly added to the solution, followed by stirring at room temperature for 24 hours. After the reaction was completed, the reaction solution was neutralized to about pH 7 with 5% hydrogen chloride solution, extracted with ethyl acetate, and dried to obtain a compound represented by Formula 3 below.

(3)

Comparative Polymerization Example  One

Benzomethacrylate (10 g, 0.057 mol) and cyclohexyl methacrylate (10.6 g, 0.057 mol) were mixed in a flask under a nitrogen atmosphere in 41 g of methyl ethyl ketone. Then, 2.6 g of dimethyl-2,2'-azobis (2-methylpropiolate) as a polymerization initiator was added to the mixture at 80 DEG C for 4 hours by syringe, and further stirred for 2 hours. After completion of the polymerization, the resulting polymer was slowly precipitated in an excess amount of hexane solvent. The resulting precipitate was filtered, and the precipitate was dissolved again in an appropriate amount of a mixed solvent of hexane / isopropanol and stirred. Subsequently, the resulting precipitate was dried in a vacuum oven maintained at 50 캜 for about 24 hours to obtain a compound represented by the formula (4).

The weight-average molecular weight (Mw) of the obtained polymer was 6200 and the degree of dispersion (Mw / Mn) was 1.45.

[Chemical Formula 4]

(A: b = 1: 1 in the above formula (4)

Hard mask  Preparation of composition

Example  One

Propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3) were mixed at a ratio of 3: 7 (weight ratio) to the monomer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 1 (v / v)) to prepare a solution. The solution was then filtered to produce a hard mask composition. The amount of the compound was adjusted according to the desired thickness.

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 and the polymer obtained in Polymerization Example 2 were used in a ratio of 5: 5 (weight ratio).

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 and the polymer obtained in Synthesis Example 3 were used in a ratio of 7: 3 (weight ratio).

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 and the polymer obtained in Polymerization Example 3 were used in a ratio of 3: 7 (weight ratio).

Comparative Example  One

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

Comparative Example  2

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

evaluation

Evaluation 1: Heat resistance

The hard mask composition (compound content: 10% by weight) according to Examples 1 to 4 and Comparative Examples 1 and 2 was spin-on coated on a silicon wafer and then an outgas generated upon heat treatment at 300 캜 for 5 minutes at a thickness of about 2000 Å QCM (Quartz Crystal Microbalance).

The results are shown in Table 1.

sublimate (ng) Example 1 57 Example 2 61 Example 3 45 Example 4 42 Comparative Example 1 180 Comparative Example 2 125

Referring to Table 1, it can be seen that the thin films formed from the hard mask compositions according to Examples 1 to 4 have a low outgassing as compared to the thin films formed from the hard mask composition according to Comparative Examples 1 and 2. That is, the hard mask compositions according to Examples 1 to 4 are excellent in heat resistance and can be applied to a high-temperature process.

Evaluation 2: Awareness of corrosion

The hard mask composition (compound content: 13.0% by weight) according to Examples 1 to 4 and Comparative Example 2 was coated on a silicon wafer by a spin-on coating method and then heat-treated at 300 캜 for 5 minutes to a thickness of about 4000 Å. 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 the dry etching 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 2.

Bulk etch rate (Å / sec) N2O2 etch CFx etch Example 1 24.87 27.21 Example 2 23.75 26.32 Example 3 23.11 24.75 Example 4 22.52 24.3 Comparative Example 2 29.7 32.4

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 lower etching rate than the thin film formed from the hard mask composition according to Comparative Example 2. [

From the results, it can be seen that the hard mask composition according to Examples 1 to 4 has higher corrosion resistance than the hard mask composition according to Comparative Example 2 because of its high degree of crosslinking.

Evaluation 3: Gap-fill and planarization characteristics

The hard mask composition (compound content: 13 wt%) according to Examples 1 to 4 and Comparative Examples 1 and 2 was spin-coated on a patterned silicon wafer to a thickness of about 1700 Å. Next, after heat treatment at 300 ° C for 120 seconds on a hot plate, gap-fill characteristics and planarization characteristics were observed using a V-SEM apparatus.

The gap-fill characteristics were determined by observing the cross section of the pattern with a scanning electron microscope (SEM) to determine whether or not a void was generated, and the planarization characteristic was numerically expressed by the following equation (2). The planarization characteristic is better as the difference between h1 and h2 is smaller, and the smaller the value is, the better the planarization characteristic is.

[Equation 2]

The results are shown in Table 3.

Planarization characteristics Gap Fill Character
(with or without void) aspect ratio
(1: 2) aspect ratio
(1: 5) Example 1 4.52 70.23 void None Example 2 3.61 73.10 void None Example 3 4.38 79.42 void None Example 4 5.49 68.15 void None Comparative Example 1 13.21 93.48 void occurrence Comparative Example 2 15.83 99.43 void None

Referring to Table 3, the thin films formed from the hard mask compositions according to Examples 1 to 4 had a superior degree of planarization and voids as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 and 2, Quot ;. < / RTI >

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 (17)

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

In Formula 1,
A represents any one selected from the group consisting of a substituted or unsubstituted cyclic group, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group and a substituted or unsubstituted C2 to C20 alkynylene group ego,
A ' and A " are each independently a substituted or unsubstituted ring group,
X and X 'are each independently a hydroxyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkoxy group,
L and L 'are each independently a single bond, a substituted or unsubstituted C1 to 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 1 to 6, and m + n? (the maximum number of substituents that A may have).
(2)

In Formula 2,
Ar is a substituted or unsubstituted aromatic group selected from the following group 1 '
B is any one or a combination of two or more members selected from the following Group 2.
[Group 1 ']

[Group 2]

In the group 2, M ¹ and M ² each independently represents a hydrogen atom, 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 C 1 to C 30 alkoxy Or a combination thereof. The method of claim 1,
Wherein A, A 'and A " are each independently a substituted or unsubstituted ring group selected from the following Group 3:
[Group 3]

In the group 3,
Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR ^a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom or a combination thereof,
Z ³ to Z ¹⁷ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein R ^a to R ^c are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof. 3. The method of claim 2,
Wherein at least one of A, A 'and A " is a 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 Or a combination thereof. The method of claim 1,
Wherein Ar is substituted with at least one hydrogen atom 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 > The method of claim 1,
Wherein the monomer is 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 And Y ^a to Y ^h each independently represents 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, to be. The method of claim 1,
Wherein the monomer has a molecular weight of from 200 to 5,000. The method of claim 1,
Wherein the polymer has a weight average molecular weight of from 1,000 to 10,000. The method of claim 1,
Wherein the weight ratio of the monomer to the polymer is monomer: polymer = 5: 5 to 1: 9. The method of claim 1,
Wherein the solvent comprises at least one selected from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and ethyl lactate. The method of claim 1,
Wherein the monomer and the polymer are contained in an amount of 0.1 wt% to 50 wt% based on 100 wt% of the solvent. Providing a layer of material over the substrate,
Applying a hard mask composition according to any one of claims 1 to 11 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 12,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method. The method of claim 12,
Wherein the forming of the hard mask layer is performed at a temperature of 100 ° C to 500 ° C. The method of claim 12,
And forming a bottom anti-reflective layer (BARC) on the silicon-containing thin film layer. 16. The method of claim 15,
Wherein the silicon-containing thin film layer contains silicon oxynitride (SiON). A semiconductor integrated circuit device comprising a plurality of patterns formed by the pattern forming method according to claim 12.