KR20160008929A - Monomer for hardmask composition and hardmask composition including the monomer and method of forming patterns using the hardmask composition - Google Patents

Abstract

The present invention relates to a monomer which is used in a hardmask composition and is represented by chemical formula 1. The present invention further relates to a hardmask composition comprising the monomer, and to a pattern formation method using the hardmask composition. In the chemical formula 1, A^0, A^1, A^2, A^3, A^4, X^1, X^2, Y^1, Y^2, M^1, M^2, k, l, m, n, p and q are the same as defined in the specification.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard mask composition comprising a monomer, a monomer, and the monomer, and a pattern forming method using the hard mask composition. BACKGROUND ART < RTI ID = 0.0 >

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

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

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

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

The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer is required to have properties such as chemical resistance and corrosion resistance so as to withstand the multiple etching process.

One embodiment provides a monomer for a hard mask composition that is excellent in chemical resistance and 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 ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

k and l are each independently 0 or 1, satisfying 1? k + 1? 2,

m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,

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

A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represent a substituted or unsubstituted cyclic group selected from the following group 1.

[Group 1]

In the group 1,

Z ¹ represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is ^a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,

Z ³ to Z ¹⁸ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein each of R ^a to R ^c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof.

At least one of A ⁰ , A ¹ , A ² , A ³ and A ⁴ may be a substituted or unsubstituted polycyclic aromatic ring group.

Wherein A ⁰ is a substituted or unsubstituted pyrene group, a sulfuryl group, a benzo sulfuryl group or nose nengi, A ^1, A ^2, A ³ and A ⁴ are each independently a substituted or unsubstituted benzene group, a naphthalene group, or by Phenyl group.

The monomer may be represented by the following general formula (2) or (3).

(2)

(3)

In the above Formulas 2 and 3,

A ⁰ , A ¹ , A ² , A ³ and A ⁴ are substituted or unsubstituted aromatic ring groups,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

m and n are integers satisfying 0? m? 3 and 0? n? 3.

The monomer may be represented by any one of the following formulas (4) to (9).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 4 to 9,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

m and n are integers satisfying 0? m? 3 and 0? n? 3.

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

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

[Chemical Formula 1]

In Formula 1,

A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

k and l are each independently 0 or 1, satisfying 1? k + 1? 2,

m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,

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

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

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

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

The step of forming the hard mask layer may be heat-treated 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 contain silicon oxynitride (SiON).

It is possible to secure the gap-fill characteristic and the planarization characteristic while enhancing the chemical resistance and corrosion-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, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a cyano group, A C3 to C30 cycloalkyl group, a C3 to C30 cycloalkyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C4 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, Substituted with a substituent selected from the group consisting of a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.

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

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

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

[Chemical Formula 1]

In Formula 1,

A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se- (selenium)

M ¹ and M ² are cyano groups,

k and l are each independently 0 or 1, satisfying 1? k + 1? 2,

m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,

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

The monomer is a compound having a structure having at least two or more substituents with an aromatic ring group having one or two rings as a core.

The substituent includes, similarly to the core, an aromatic ring group having one or two rings, and at least one of the aromatic ring groups is substituted with a cyano group (-CN).

Generally, the hard mask layer produced by the spin-on coating method tends to have a lower etch selectivity compared to the hard mask layer produced by physical or chemical vapor deposition methods. However, the monomer according to one embodiment contains a nitrile compound in which a cyano group (-CN) is introduced in a substituent, so that the selectivity to the etch gas is lower than that in the case where no cyano group (-CN) is introduced Can be further improved, and excellent chemical resistance and heat resistance can be secured.

When the monomer can include at least one cyano group (-CN), the number of cyano groups (-CN) substituted in the aromatic ring group is not limited in principle, and the maximum substituent And the like.

On the other hand, the above-mentioned monomers can be effectively formed by a spin-on coating method by further improving the solubility by a plurality of functional groups (X ¹ and X ² ) contained in each substituent, The gap-fill and planarization characteristics that can fill the gaps between the patterns when formed by the on-coating method are also excellent.

Also, it is possible to perform amplification crosslinking based on the condensation reaction of the plurality of functional groups, thereby exhibiting excellent crosslinking properties. 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.

As described above, the core and the substituent each independently include one or two or more rings or aromatic ring groups, and the range of the aromatic ring group is not limited in principle, but may be, for example, a substituted or unsubstituted Gt;

[Group 1]

In the group 1,

Z ¹ represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is ^a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,

Z ³ to Z ¹⁸ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein each of R ^a to R ^c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof.

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

For example, at least one of A ⁰ , A ¹ , A ² , A ³ and A ⁴ may be a substituted or unsubstituted polycyclic aromatic ring group and thus may have a rigid property.

For example, A ⁰ is a substituted or unsubstituted pyrene group, a perylene group, a benzopyrylene group or a coronene group, A ¹ , A ² , A ³ and A ⁴ each independently represent a substituted or unsubstituted benzene group, A naphthalene group or a biphenyl group, but is not limited thereto.

The monomer may include a plurality of aromatic ring groups in one substituent, and the plurality of aromatic ring groups may be connected by, for example, -O-, -S-, -NH-, or -Se-.

The monomer may be represented, for example, by the following formula (2) or (3).

(2)

(3)

In the above Formulas 2 and 3,

A ⁰ , A ¹ , A ² , A ³ and A ⁴ are substituted or unsubstituted aromatic ring groups,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

m and n satisfy 0? m? 3 and 0? n? 3.

The monomer may be represented, for example, by any one of formulas (4) to (9).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 4 to 9,

X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,

Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,

M ¹ and M ² are cyano groups,

m and n satisfy 0? m? 3 and 0? n? 3.

The monomer may have a molecular weight of about 800 to 5,000. By having a molecular weight in the above range, the monomer having a high carbon content has a good solubility in a solvent, and a good thin film by spin-on coating can be obtained.

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

The hard mask composition according to one embodiment comprises the above-mentioned monomers and a solvent.

The above-mentioned monomers are as described above, and one kind of monomers may be contained singly or two or more kinds of monomers may be mixed and contained.

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) Methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, methylpyrrolidone, 　 Acetyl acetone, and ethyl 3-ethoxypropionate.

The monomer may be included in an amount of about 0.1 to 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 secured without changing the optical properties of the hard mask composition.

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

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

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

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

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

The 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 or silicon oxide.

Further, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer.

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

The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof.

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

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

Monomeric  synthesis

Comparative Synthetic Example  One

20 g (0.1 mol) of pyrene, 34 g (0.2 mol) of methoxybenzoyl chloride and 312 g of 1,2-dichloroethane were added to a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube. After 15 minutes, 29.2 g (0.22 mol) of trichloro aluminum was slowly added, and the reaction was carried out at room temperature for 3 hours. After the completion of the reaction, the reaction product was added to methanol, and the precipitate was filtered to remove trichloroaluminum. The powder obtained through the above filtration was placed in a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube, and 91 g (0.45 mol) of 1-dodecan sulfate, 30 g (0.54 mol) of potassium hydroxide, 262 g of amide was added thereto, followed by stirring at 100 DEG C for 5 hours. After completion of the reaction, the reaction product was cooled, the pH was adjusted to pH < 5 using 7% hydrogen chloride solution, and the resulting precipitate was filtered. Thereafter, the obtained filtrate was dried in a vacuum oven to remove moisture.

160 g of tetrahydrofuran (THF) was further added to the powder thus obtained to prepare a solution state. An aqueous solution of 16 g (0.42 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 12 hours. The pH of the resulting solution was adjusted to pH <5 using a 7% hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was reduced under reduced pressure to obtain a compound represented by Formula 10a.

Comparative Synthetic Example  2

A compound represented by the following formula (10b) was obtained in the same manner as in Comparative Synthesis Example 1, except that perylene was used instead of pyrene.

[Chemical Formula 10b]

Comparative Synthetic Example  3

A compound represented by the following formula 10c was obtained in the same manner as in Comparative Synthesis Example 1, except that benzopyrilene was used instead of pyrene.

[Chemical Formula 10c]

Comparative Synthetic Example  4

20 g (0.1 mol) of pyrene, 17 g (0.1 mol) of methoxybenzoyl chloride and 150 g of 1,2-dichloroethane are added to a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube. After 15 minutes, 14.5 g (0.11 mol) of trichloroaluminum was slowly added and the reaction was carried out at room temperature for 1 hour. After confirming that the pyrene had been completely removed, 18 g (0.1 mol) of naphthoyl chloride and 14.5 g (0.11 mol) of trichloroaluminum were slowly added to the reaction mixture, and the reaction was further continued for 2 hours. After completion of the reaction, the reaction product was added to methanol, and the precipitate was filtered to remove trichloroaluminum. The powder obtained through the above filtration was placed in a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube, and 91 g (0.45 mol) of 1-dodecan sulfate, 30 g (0.54 mol) of potassium hydroxide, 262 g of amide was added thereto, followed by stirring at 100 DEG C for 5 hours. After completion of the reaction, the reaction product was cooled, the pH was adjusted to pH <5 with 7% hydrogen chloride solution, and the resulting precipitate was filtered. Thereafter, the obtained filtrate was dried in a vacuum oven to remove moisture.

To the powder thus obtained, 160 g of THF was added again to prepare a solution. An aqueous solution of 16 g (0.42 mol) of sodium borohydride was slowly added to the solution, followed by stirring at room temperature for 12 hours. The pH of the solution was adjusted to pH <5 with 7% hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was reduced to obtain the compound represented by Formula 10d.

Comparative Synthetic Example  5

In Comparative Synthesis Example 4, the compound represented by Formula 10e was obtained in the same manner except for using perylene instead of pyrene.

[Chemical Formula 10e]

Comparative Synthetic Example  6

In Comparative Synthesis Example 4, the compound represented by Formula 10f was obtained in the same manner except that benzopyrilene was used instead of pyrene.

[Formula 10f]

Synthetic example  One

15 g of acetonitrile / N-methyl-2-pyrrolidone (CH ₃ CN / NMP = 1/1) was added to 4.4 g (0.01 mol) of the intermediate compound after the methylation removal reaction of Comparative Synthesis Example 1 to prepare a solution Respectively. 3 g (0.022 mol) of potassium carbonate and 3.8 g (0.022 mol) of 4-nitropthalonitrile were added to the solution, followed by stirring at 85 ° C for 5 hours. The pH of the reaction solution was adjusted to pH <5 with 7% hydrogen chloride solution, and the precipitate was filtered. The powder obtained through the filtration process was dried in a vacuum oven to remove moisture. 16 g of THF was added again to the water-removed powder to obtain a solution state. An aqueous solution of 0.8 g (0.021 mol) of sodium borohydride was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the reaction mixture was adjusted to pH <5 with 7% hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was reduced to obtain the compound represented by Formula 11a.

Synthetic example  2

A compound represented by the following formula (11b) was obtained in the same manner as in Synthesis Example 1, except that an intermediate using perylene of Comparative Synthesis Example 2 was used in place of the intermediate using pyrene of Comparative Synthesis Example 1.

[Formula 11b]

Synthetic example  3

A compound represented by the following formula (11c) was obtained in the same manner as in Synthesis Example 1, except that an intermediate using benzopyrilene of Comparative Synthesis Example 3 was used in place of the intermediate using the pyrene of Comparative Synthesis Example 1.

[Chemical Formula 11c]

Synthetic example  4

15 g of acetonitrile / N-methyl-2-pyrrolidone (CH ₃ CN / NMP = 1/1) was added to 4.7 g (0.01 mol) of the intermediate obtained after the methylation removal of Comparative Synthesis Example 4 to prepare a solution . 1.5 g (0.011 mol) of potassium carbonate and 1.9 g (0.011 mol) of 4-nitropthalonitrile were added to the solution, and the mixture was stirred at 85 ° C for 5 hours. The pH of the reaction solution was adjusted to pH <5 with 7% hydrogen chloride solution, and the precipitate was filtered. The powder obtained through the filtration process was dried in a vacuum oven to remove moisture. The water-removed powder was further added with 16 g of THF to form a solution state. An aqueous solution of 0.8 g (0.021 mol) of sodium borohydride was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. The reaction solution was adjusted to pH <5 with 7% hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was reduced to obtain the compound represented by Formula 11d.

[Chemical Formula 11d]

Synthetic example  5

A compound represented by the following formula (11e) was obtained in the same manner as in Synthesis Example 4, except that an intermediate using perylene of Comparative Synthesis Example 5 was used in place of the intermediate using the pyrene of Comparative Synthesis Example 4.

[Chemical Formula 11e]

Synthetic example  6

A compound represented by the following formula (11f) was obtained in the same manner as in Synthesis Example 4, except that an intermediate using benzopyrilene of Comparative Synthesis Example 6 was used in place of the intermediate using the pyrene of Comparative Synthesis Example 1.

[Formula 11f]

Hard mask  Preparation of composition

Example  One

1.5 g of the compound obtained in Synthesis Example 1 was dissolved in 10 g of a mixed solvent of propylene glycol monoethylehter acetate (PGMEA) and ethyl lactate (EL) (7: 3 (v / v)) And filtered through a 0.1 um Teflon filter to produce a hard mask composition.

Example  2

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

Example  3

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

Example  4

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

Example  5

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 5 was used in place of the compound obtained in Synthesis Example 1.

Example  6

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 6 was used in place of the compound obtained in Synthesis Example 1.

Comparative Example  One

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

Comparative Example  2

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

Comparative Example  3

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

Comparative Example  4

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

Comparative Example  5

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 5 was used in place of the compound obtained in Synthesis Example 1.

Comparative Example  6

A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 6 was used instead of the compound obtained in Synthesis Example 1.

evaluation

Rating 1: Awareness of corrosion

The hard mask compositions according to Examples 2, 3 and 5 and Comparative Examples 2, 3 and 5 were spin-on coated on a silicon wafer and then heat-treated at 400 ° C for 2 minutes on a hot plate to form a thin film. The thickness of the thin film was then measured. Subsequently, the thin film was dry-etched for 100 seconds and 60 seconds using CF _x mixed gas and N ₂ / O ₂ gas, respectively, 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 1.

The etching rate (CF _x , Å / s) The etching rate (N ₂ / O ₂ , Å / s) Comparative Example 2 27.8 25.1 Comparative Example 3 25.6 21.9 Comparative Example 5 27.6 25.0 Example 2 23.6 22.1 Example 3 21.9 19.5 Example 5 25.0 23.2

Referring to Table 1, it can be seen that the thin films formed from the hard mask compositions according to Examples 2, 3 and 5, in which nitriles were introduced, exhibited a sufficient improvement in corrosion resistance in both CFx mixed gas and N ₂ / O ₂ gas have.

Evaluation 2: Chemical resistance

The hard mask compositions according to Examples 1, 2, 3 and 6 and Comparative Examples 1, 2, 3 and 6 were spin-on coated on a silicon wafer and then heat-treated at 240 DEG C for 1 minute on a hot plate to form a thin film. Then, the initial thin film thickness was measured by a thin film thickness meter of K-MAC. After the formed thin film was immersed in a KrF thinner for 1 minute, the thickness of the thin film was measured again and the presence or absence of mark formed on the thin film was confirmed.

The results are shown in Table 2.

Strip test (KrF thinner)
240 ℃ homeland Thickness reduction Comparative Example 1 △ 31% Comparative Example 2 △ 27% Comparative Example 3 △ 25% Comparative Example 6 O 100% Example 1 X 0.18% Example 2 X 0.12% Example 3 X 0.09% Example 6 △ 24%

Referring to Table 2, the thin films formed from the hard mask compositions according to Examples 1, 2, 3, and 6 had a thickness reduction rate after soaking compared to the thin films formed from the hard mask composition according to Comparative Examples 1, 2, You can see the less. From this, it can be seen that the thin film formed from the hard mask composition according to Examples 1, 2, 3 and 6 can form a thin film having high chemical resistance at a temperature of 240 ° C.

On the other hand, the hard mask compositions according to Examples 1 to 5 and Comparative Examples 1 to 5 were spin-on coated on a silicon wafer and then heat-treated at 400 ° C for 2 minutes on a hot plate to form a thin film. Then, the initial thin film thickness was measured by a thin film thickness meter of K-MAC. Subsequently, the formed thin film was immersed in a KrF thinner for 1 minute, and then the thickness of the thin film was measured again, and the presence or absence of mark formed on the thin film was confirmed.

The results are shown in Table 3.

Strip test (KrF thinner)
400 ° C homeland Thickness reduction Comparative Example 1 X 2.1% Comparative Example 2 X 1.8% Comparative Example 3 X 2.0% Comparative Example 4 X 2.6% Comparative Example 5 X 2.4% Example 1 X 0.09% Example 2 X 0.07% Example 3 X 0.12% Example 4 X 0.04% Example 5 X 0.06%

Referring to Table 3, it can be seen that the thin films formed from the hard mask compositions according to Examples 1 to 5 have a smaller thickness reduction rate after immersion than the thin films formed from the hard mask composition according to Comparative Examples 1 to 5. From this, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 5 can form a thin film having high chemical resistance at a temperature of 400 ° C.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (20)

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

In Formula 1,
A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,
X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,
M ¹ and M ² are cyano groups,
k and l are each independently 0 or 1, satisfying 1? k + 1? 2,
m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,
p and q are each independently an integer of 1 or more and satisfy 1? p + q? (the maximum number of substituents that A ⁰ can have). The method of claim 1,
Wherein A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represent a substituted or unsubstituted ring group selected from the following Group 1:
[Group 1]

In the group 1,
Z ¹ represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is ^a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z ³ to Z ¹⁸ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein each of R ^a to R ^c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof. The method of claim 1,
Wherein at least one of A ⁰ , A ¹ , A ² , A ³ and A ⁴ is a substituted or unsubstituted polycyclic aromatic ring group. 4. The method of claim 3,
A ⁰ is a substituted or unsubstituted pyrene group, a perylene group, a benzopyrylene group or a coronene group,
A ¹ , A ² , A ³ and A ⁴ each independently represent a substituted or unsubstituted benzene group, a naphthalene group or a biphenyl group
Monomer for a hard mask composition. The method of claim 1,
A monomer for a hard mask composition represented by the following formula (2) or (3):
(2)

(3)

In the above Formulas 2 and 3,
A ⁰ , A ¹ , A ² , A ³ and A ⁴ are substituted or unsubstituted aromatic ring groups,
X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,
M ¹ and M ² are cyano groups,
m and n are integers satisfying 0? m? 3 and 0? n? 3. The method of claim 5,
A monomer for a hard mask composition represented by any one of the following formulas (4) to (9):
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 4 to 9,
X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,
M ¹ and M ² are cyano groups,
m and n are integers satisfying 0? m? 3 and 0? n? 3. The method of claim 1,
Wherein the monomer has a molecular weight of from 800 to 5,000. A monomer represented by the following formula (1), and
menstruum
A hard mask composition comprising:
[Chemical Formula 1]

In Formula 1,
A ⁰ , A ¹ , A ² , A ³ and A ⁴ each independently represents a substituted or unsubstituted aromatic ring group,
X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,
M ¹ and M ² are cyano groups,
k and l are each independently 0 or 1, satisfying 1? k + 1? 2,
k and l are each independently 0 or 1, satisfying 1? k + 1? 2,
m and n are integers satisfying 0? m? 3 and 0? n? 3, and when k = 1, m is an integer of 1 or more, and when l = 1, n is an integer of 1 or more,
p and q are each independently an integer of 1 or more and satisfy 1? p + q? (the maximum number of substituents that A ⁰ can have). 9. The method of claim 8,
Wherein A ⁰ , A ¹ , A ² , A ³ and A ⁴ are each independently a substituted or unsubstituted ring group selected from the following group 1:
[Group 1]

In the group 1,
Z ¹ represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is ^a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, ^a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z ³ to Z ¹⁸ each independently represent C = O, NR ^a , oxygen (O), sulfur (S), CR ^b R ^c Or a combination thereof, wherein each of R ^a to R ^c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof. 9. The method of claim 8,
Wherein at least one of A ⁰ , A ¹ , A ² , A ³ and A ⁴ is a substituted or unsubstituted polycyclic aromatic ring group. 11. The method of claim 10,
A ⁰ is a substituted or unsubstituted pyrene group, a perylene group, a benzopyrylene group or a coronene group,
A ¹ , A ² , A ³ and A ⁴ each independently represent a substituted or unsubstituted benzene group, a naphthalene group or a biphenyl group
Hard mask composition. 9. The method of claim 8,
Wherein the monomer is represented by Formula 2 or 3:
(2)

(3)

In the above Formulas 2 and 3,
A ⁰ , A ¹ , A ² , A ³ and A ⁴ are substituted or unsubstituted aromatic ring groups,
X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,
M ¹ and M ² are cyano groups,
m and n are integers satisfying 0? m? 3 and 0? n? 3. The method of claim 12,
Wherein the monomer is a hard mask composition comprising a monomer for a hard mask composition represented by any one of the following formulas (4) to (9):
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

In the above Chemical Formulas 4 to 9,
X ¹ and X ² are each independently a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom or a halogen-containing group,
Y ¹ and Y ² are each independently -O-, -S-, -NH-, or -Se-,
M ¹ and M ² are cyano groups,
m and n are integers satisfying 0? m? 3 and 0? n? 3. 9. The method of claim 8,
Wherein the monomer has a molecular weight of 800 to 5000. &lt; Desc / Clms Page number 24 &gt; 9. The method of claim 8,
Wherein the monomer is included in an amount of 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 8 to 15 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 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
&Lt; / RTI &gt; 17. The method of claim 16,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method. 17. The method of claim 16,
Wherein the forming of the hard mask layer is performed at a temperature of 100 ° C to 500 ° C. 17. The method of claim 16,
And forming a bottom anti-reflective layer (BARC) on the silicon-containing thin film layer. 20. The method of claim 19,
Wherein the silicon-containing thin film layer contains silicon oxynitride (SiON).