KR101599958B1 - Hardmask composition and method of forming patterns using the hardmask composition - Google Patents

Abstract

A compound containing an aliphatic or aromatic ring connected to at least one of an amic acid group and an imide group, and a solvent, and a pattern forming method using the hard mask composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a hard mask composition and a pattern forming method using the hard mask composition. [0002]

Hardmask compositions and methods of forming patterns using the hardmask compositions.

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. However, the spin-on coating method should be presumed to have solubility in solvents.

However, the above-mentioned characteristics required for the hard mask layer are in conflict with each other, and a hard mask composition capable of satisfying all of them is needed.

One embodiment provides a hard mask composition capable of satisfying solubility, gap-fill characteristics, and planarization characteristics for a solvent while satisfying heat resistance and corrosion resistance.

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

According to one embodiment, there is provided a hard mask composition comprising a compound comprising an aliphatic or aromatic ring linked to at least one of an amic acid group and an imide group, and a solvent.

The compound may comprise at least two aliphatic or aromatic rings.

The compound may include at least one of the compounds represented by the following formulas (1) to (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 1 to 4,

X ¹ to X ⁴ and Y ¹ to Y ⁴ are each independently a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C6 to C60 arylene group, a substituted or unsubstituted C2 to C60 heterocycloalkylene group , A substituted or unsubstituted C2 to C60 heteroarylene group or a combination thereof,

n ₁ to n ₄ each independently represents an integer of 1 to 5;

X ¹ to X ⁴ and Y ¹ to Y ⁴ may each independently be a substituted or unsubstituted ring selected from the following group 1.

[Group 1]

In the group 1,

Z ¹ And Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, C = O, NR ^a , oxygen (O), sulfur (S) , 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, or a combination thereof.

At least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ is independently a C3 to C60 cycloalkylene group substituted with a hydroxy group, a C6 to C60 arylene group substituted with a hydroxy group, a C2 to C60 heterocycloalkyl A C2-C60 heteroarylene group substituted with a hydroxy group, or a combination thereof.

The compound may include at least one of the compounds represented by the following formulas (5) to (12).

[Chemical Formula 5]

[Chemical Formula 6]

 (7)

 [Chemical Formula 8]

 [Chemical Formula 9]

 [Chemical formula 10]

 (11)

 [Chemical Formula 12]

The compound may have a molecular weight of about 300 to 3,000.

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

According to another embodiment, there is provided a method of manufacturing a hard mask, comprising: providing a layer of material over a substrate; applying the hardmask composition over the material layer; heat treating the hardmask composition to form a hardmask layer; A step of forming a thin film layer, a step of forming a photoresist layer on the silicon-containing thin film layer, a step of exposing and developing the photoresist layer to form a photoresist pattern, Selectively removing the 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 about 100 < 0 > C to 500 < 0 > C.

The present invention provides a hard mask composition capable of securing heat resistance and corrosion resistance while satisfying solubility in a solvent, gap-fill property and planarization property.

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 defined otherwise herein, 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (F, Cl, Br 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 C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C 1 to C 30 arylalkyl group, a C 7 to C 30 arylalkyl group, a C 1 to C 30 alkoxy group, a C 1 to C 20 heteroalkyl group, a C 3 to C 20 heteroarylalkyl group, a C 3 to C 30 cycloalkyl group, a C 3 to C 15 cycloalkenyl group, C6 to C15 cycloalkynyl groups, C3 to C30 heterocycloalkyl groups, and combinations thereof.

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

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

A hardmask composition according to one embodiment comprises a compound comprising an aliphatic or aromatic ring linked to at least one of an amic acid group and an imide group, and a solvent.

The compound may comprise at least two aliphatic or aromatic rings, one of which may be connected to the nitrogen atom (N) of the amic group or the imide group and the other may be connected to the nitrogen atom (N) of the amic group or the imide group, Carbonyl (C = O) group.

The compound may include at least one of the compounds represented by the following formulas (1) to (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 1 to 4,

X ¹ to X ⁴ and Y ¹ to Y ⁴ are each independently a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C6 to C60 arylene group, a substituted or unsubstituted C2 to C60 heterocycloalkylene group , A substituted or unsubstituted C2 to C60 heteroarylene group or a combination thereof,

n ₁ to n ₄ each independently represents an integer of 1 to 5;

X ¹ to X ⁴ and Y ¹ to Y ⁴ may be, for example, each independently a substituted or unsubstituted ring selected from the following group 1.

[Group 1]

In the group 1,

Z ¹ And Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, C = O, NR ^a , oxygen (O), sulfur (S) , 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, 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 X ¹ to X ⁴ and Y ¹ to Y ⁴ is independently a C3 to C60 cycloalkylene group substituted with a hydroxy group, a C6 to C60 arylene group substituted with a hydroxy group, a C2 to C60 heterocycle substituted with a hydroxy group An alkylene group, a C2 to C60 heteroarylene group substituted with a hydroxy group, or a combination thereof. By including a cyclic group substituted with a hydroxy group in this manner, solubility in a solvent can be improved.

The amic acid compound represented by the above general formula (1) or (3) can be obtained, for example, from a cyclic compound having an amine group and a cyclic compound having an anhydride group. The imide compound represented by Formula 2 or Formula 4 can be obtained, for example, by heat-treating the amic acid compound represented by Formula 1 or 3.

[Reaction Scheme 1]

[Reaction Scheme 2]

In the above Reaction Formula 1 or 2, X is the same as defined above for X ¹ to X ⁴ , Y is the same as defined for Y ¹ to Y ⁴ described above, and n is the same as defined for n ₁ to n ₄ described above.

The compounds can control the solubility in solvents in the form of amic acid and imide according to their structural stiffness and can have good gap fill and planarization properties by spin-on coating method. The compounds may also have the desired thermal, mechanical stability and corrosion resistance required in hardmask compositions by including the aliphatic or aromatic rings.

The compound may include at least one of the compounds represented by the following formulas (5) to (12).

[Chemical Formula 5]

[Chemical Formula 6]

 (7)

 [Chemical Formula 8]

 [Chemical Formula 9]

 [Chemical formula 10]

 (11)

 [Chemical Formula 12]

The compound may have a molecular weight of about 300 to 3,000. By having a molecular weight in the above range, it is possible to optimize by adjusting the carbon content of the hard mask composition containing the compound and the solubility in the solvent.

The compound may contain one kind of compound alone or two or more kinds of compounds together.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the compound. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) But are not limited to, methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, , Methyl pyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate.

The compound may be included in an amount of about 0.1 to 30% by weight based on the total amount of the hard mask composition. By including the compound in the above range, the thickness, surface roughness and leveling of the hard mask layer can be controlled.

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.

The method of forming a pattern according to an embodiment includes the steps of providing a material layer on a substrate, applying a hard mask composition comprising the above-described compound 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 is as described above, and may be prepared in a solution form 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 50 to 10,000 A thick.

The step of heat-treating the hard mask composition may be performed at, for example, about 100 to 500 DEG C for about 10 seconds to 1 hour. By the heat treatment, the amic acid may be imidized and converted to an imide group, and the imidization ratio may be, for example, about 50 to 100%.

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.

Synthetic example

Synthetic example  One

In a flask, 5.0 g (0.0215 mol) of 1,6-diaminopyrene, 13.83 g (0.0646 mol) of 4-hydroxy-1,8-naphthalenedicarboxylic anhydride and 1-methyl- And the mixture was stirred for 12 hours. When the reaction was completed, methanol was added, and the precipitate was filtered and dried to obtain a compound represented by the following formula (13).

[Chemical Formula 13]

Synthetic example  2

The flask was charged with 6.09 g (0.0382 mol) of 5-amino-1-naphthol, 5.0 g (0.0127 mol) of perylene-3,4,9,10-tetracarboxylic dianhydride and 1-methyl- And the mixture was stirred for 12 hours. When the reaction was completed, methanol was added, and the precipitate was filtered and dried to obtain a compound represented by the following formula (14).

[Chemical Formula 14]

Synthetic example  3

The flask was charged with 6.89 g (0.0433 mol) of 5-amino-1-naphthol, 5.0 g (0.0144 mol) of 1,12-benzopyrilene-1 ', 2'- dicarboxylic anhydride, 48 g of pyrrolidinone was added and stirred for 12 hours. When the reaction is complete 　 After the addition of methanol, the precipitate was filtered and dried to obtain a compound represented by the following formula (15).

[Chemical Formula 15]

Synthetic example  4

The flask was charged with 9.33 g (0.0405 mol) of 4,4'-methylenebis (2-aminophenol), 5.00 g (0.0135 mol) of 1,2-coronenedicarboxylic anhydride and 1-methyl- 57 g of dinon were added and stirred for 12 hours. When the reaction was completed, methanol was added, and the precipitate was filtered and dried to obtain a compound represented by the following general formula (16).

[Chemical Formula 16]

Comparative Synthetic Example  One

Friedel-Craft Acylation: To the flask was added 10.0 g (0.0495 mol) of pyrene, 13.9 g (0.0989 mol) of benzoyl chloride and 87 g of 1,2-dichloroethane. 13.2 g (0.0989 mol) of aluminum chloride was slowly added to this solution at room temperature, then the temperature was raised to 60 ° C and the mixture was stirred for 8 hours. When the reaction was completed, methanol was added to the solution, and the resulting precipitate was filtered to obtain dibenzoyl pyrene.

Reduction: To the flask was added 5.00 g (0.0122 mol) of dibenzoyl pyrene and 57 g of tetrahydrofuran. To this solution was slowly added an aqueous solution of 4.60 g (0.122 mol) of sodium borohydride and the mixture was stirred 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 the following Chemical Formula 17.

[Chemical Formula 17]

Comparative Synthetic Example  2

To the flask was added 8.75 g (0.05 mol) of alpha, alpha '-dichloro-p-xylene, 26.66 g aluminum chloride and 200 g gamma -butyrolactone. To this solution was slowly added a solution prepared by dissolving 35.03 g (0.10 mol) of 4,4 '- (9-fluorenylidene) diphenol in 200 g of? -Butyrolactone, followed by stirring at 120 ° C for 12 hours. After the polymerization, the acid was removed using water and then concentrated. 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 wt%. This solution was placed in a separating funnel and n-heptane was added to remove the monomer and low molecular weight to obtain a polymer represented by the following formula (18).

[Chemical Formula 18]

The weight average molecular weight of the polymer was 12,000 and the degree of dispersion was 2.04.

Hard mask  Preparation of composition

Example  One

The compound obtained in Synthesis Example 1 was dissolved in 1-methyl-2-pyrrolidinone to 10% by weight and 13% by weight, respectively, followed by filtration to prepare a hard mask composition.

Example  2

The compound obtained in Synthesis Example 2 was added to 1-methyl-2-pyrrolidinone in an amount of 10% by weight and 13% by weight, respectively Dissolved and filtered to prepare a hard mask composition.

Example  3

The compound obtained in Synthesis Example 3 was dissolved in 1-methyl-2-pyrrolidinone to 10% by weight and 13% by weight, respectively, followed by filtration to prepare a hard mask composition.

Example  4

The compound obtained in Synthesis Example 4 was dissolved in 1-methyl-2-pyrrolidinone in an amount of 10% by weight and 13% by weight, respectively, and filtered to prepare a hard mask composition.

Comparative Example  One

The compound obtained in Comparative Synthesis Example 1 was dissolved in 1-methyl-2-pyrrolidinone to 10% by weight and 13% by weight, respectively, followed by filtration to prepare a hard mask composition.

Comparative Example  2

The compound obtained in Comparative Synthesis Example 2 was dissolved in 1-methyl-2-pyrrolidinone to 10% by weight and 13% by weight, respectively, followed by filtration to prepare a hard mask composition.

evaluation

Rating 1: Gapfil  And planarization characteristics

A 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 having a pattern formed thereon and heat-treated at 400 ° C for 120 seconds to form a thin film, The cross-section was observed using a Field Emission Scanning Electron Microscope (FE-SEM) instrument.

The gap-fill characteristics were determined by observing the cross-section of the pattern to determine whether or not a void was generated, and the planarization characteristic was measured by measuring the thickness of the thin film from the cross-sectional image. The planarization property is h1 And h2 are not so large, the better the planarization characteristic, the smaller the value is.

[Equation 1]

The results are shown in Table 1.

Gap-fill characteristic Planarization characteristics Example 1 No voids 8.3 Example 2 No voids 7.5 Example 3 No voids 8.8 Example 4 No voids 9.3 Comparative Example 1 Void generation 14.0 Comparative Example 2 No voids 88.2

Referring to Table 1, the thin films formed from the hard mask compositions according to Examples 1 to 4 exhibited excellent gap-fill characteristics as well as excellent flatness compared to the thin films formed from the hard mask composition according to Comparative Examples 1 and 2 Able to know.

Evaluation 2: Heat resistance

The hard mask composition (compound content: 13 wt%) according to Examples 1 to 4 and Comparative Example 1 was 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. Subsequently, the thin film was collected and heated to 800 ° C at a rate of 10 ° C / minute using a thermogravimetric analysis (TGA) to measure the pyrolysis temperature. The temperature (T _{d, 10} ) when 10% of the total weight of the film was reduced is shown in Table 2.

Pyrolysis temperature (T _{d , 10,} ° C) Example 1 562 Example 2 584 Example 3 614 Example 4 630 Comparative Example 1 390

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 higher heat resistance than the thin film formed from the hard mask composition according to Comparative Example 1.

Rating 3: Awareness of corrosion

The hard mask composition (compound content: 13 wt.%) According to Examples 1 to 4 and Comparative Example 2 was spin-on coated on a silicon wafer and then heat-treated at 400 占 폚 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 60 seconds and 100 seconds using N ₂ / O ₂ mixed gas or CF _x gas, and then the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated from the thickness of the thin film before and after the dry etching and the etching time according to the following equation (2).

[Equation 2]

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

The results are shown in Table 3.

The etching rate (N ₂ / O ₂ , Å / s) The etching rate (CF _x , Å / s) Example 1 22.5 27.9 Example 2 22.3 27.4 Example 3 22.8 26.5 Example 4 23.5 26.3 Comparative Example 1 29.4 33.2 Comparative Example 2 26.7 32.0

Referring to Table 3, the thin films formed from the hard mask compositions according to Examples 1 to 4 exhibited a low etch rate due to the sufficient etch resistance to the etching gas as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 and 2 .

Evaluation 4: Pattern formation

A silicon oxide (SiO ₂₎ layer of thickness 3000Å was formed by chemical vapor deposition on a silicon wafer. Next, the hard mask composition according to Examples 1 to 4 and Comparative Examples 1 and 2 was spin-on coated on the silicon oxide layer, and then heat-treated at 400 ° C for 2 minutes on a hot plate to form a hard mask layer having a thickness of 3,000 Å. Subsequently, a silicon nitride (SiN) layer was formed on the hard mask layer by chemical vapor deposition. Subsequently, a KrF photoresist was coated on the silicon nitride layer, and then heat-treated at 110 ° C. for 60 seconds. Then, the resist pattern was exposed using an ASML (XT: 1400, NA 0.93) exposure apparatus and an aqueous 2.38 wt% tetramethylammonium hydroxide (TMAH) Respectively. Subsequently, using the patterned photoresist as a mask, a silicon nitride layer was dry-etched using a CHF ₃ / CF ₄ mixed gas. Then a silicon oxide layer using a CHF ₃ / CF ₄ gas mixture by the the patterned silicon nitride layer using N ₂ / O ₂ gas mixture as a mask dry etching the hard mask layer, patterning the hard mask layer as a mask. Dry etching. The remaining organic material was then removed using O ₂ gas.

A section of the pattern of the hard mask layer and the silicon oxide layer was observed using a scanning electron microscope (SEM).

The results are shown in Table 4.

Hard mask layer pattern shape Silicon oxide layer pattern shape Example 1 Vertical shape Vertical shape Example 2 Vertical shape Vertical shape Example 3 Vertical shape Vertical shape Example 4 Vertical shape Vertical shape Comparative Example 1 Tapered shape Tapered shape Comparative Example 2 Tapered shape Tapered shape

Referring to Table 4, the hard mask layer formed from the hard mask composition according to Examples 1 to 4 and the underlying silicon oxide layer were all patterned in a vertical shape, whereas the hard mask layer formed from the hard mask composition according to Comparative Examples 1 and 2 It can be seen that the mask layer is patterned in a tapered shape. From the results, it was found that when the hard mask composition according to Examples 1 to 4 was used, it was formed in a good pattern with superior corrosion resistance and a good pattern as compared with the hard mask composition according to Comparative Examples 1 and 2, It can also be seen that a good pattern is formed.

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 (11)

delete delete A hard mask composition comprising at least one of the compounds represented by the following formulas (1) to (4), and a solvent:
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 1 to 4,
X ¹ to X ⁴ and Y ¹ to Y ⁴ are each independently a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C6 to C60 arylene group, a substituted or unsubstituted C2 to C60 heterocycloalkylene group , A substituted or unsubstituted C2 to C60 heteroarylene group or a combination thereof,
At least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ is independently a C3 to C60 cycloalkylene group substituted with a hydroxy group, a C6 to C60 arylene group substituted with a hydroxy group, a C2 to C60 heterocycloalkylene group substituted with a hydroxy group , A C2 to C60 heteroarylene group substituted with a hydroxy group, or a combination thereof,
n ₁ to n ₄ each independently represents an integer of 1 to 5;
4. The method of claim 3,
Each of X ¹ to X ⁴ and Y ¹ to Y ⁴ is independently a substituted or unsubstituted ring selected from the following group 1,
Wherein at least one of X ¹ to X ⁴ and Y ¹ to Y ⁴ is independently a ring selected from the following Group 1 substituted with a hydroxy group:
[Group 1]

In the group 1,
Z ¹ and Z ² are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted 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 are each independently 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, An unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof.
delete 4. The method of claim 3,
Wherein said compound comprises at least one of the compounds represented by the following formulas (5) to (12).
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

4. The method of claim 3,
Wherein the compound has a molecular weight of 300 to 3,000.
4. The method of claim 3,
Wherein the compound is contained in an amount of 0.1 to 30% by weight based on the total amount of the hard mask composition.
Providing a layer of material over the substrate,
Applying a hard mask composition according to any one of claims 3, 4 and 6 to 8 on said material layer,
Heat treating the hard mask composition to form a hard mask layer,
Forming a silicon-containing thin film layer on the hard mask layer,
Forming a photoresist layer on the silicon-containing thin film layer,
Exposing and developing the photoresist layer to form a photoresist pattern
Selectively removing said silicon-containing thin film layer and said hard mask layer using said photoresist pattern and exposing a portion of said material layer; and
Etching the exposed portion of the material layer
≪ / RTI >
The method of claim 9,
Wherein the step of applying the hard mask composition is performed by a spin-on coating method.
The method of claim 9,
Wherein the forming of the hard mask layer is performed at a temperature of 100 ° C to 500 ° C.