KR102284581B1 - Compound, organic layer composition, and method of forming patterns - Google Patents

Abstract

상기 화학식 1에서,
X, Y 및 n의 정의는 명세서 내 기재한 바와 같다.It relates to a compound represented by the following Chemical Formula 1, an organic film composition including the compound, and a pattern forming method using the organic film composition.
[Formula 1]

In Formula 1,
The definitions of X, Y and n are as described in the specification.

Description

Compound, organic film composition and pattern formation method {COMPOUND, ORGANIC LAYER COMPOSITION, AND METHOD OF FORMING PATTERNS}

The present invention relates to a novel compound, an organic film composition including the compound, and a pattern forming method using the organic film composition.

Recently, the semiconductor industry has developed from a pattern of several hundreds of nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. An effective lithographic technique is essential to realize such ultra-fine technology.

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

Recently, as the size of a pattern to be formed is reduced, it is difficult to form a fine pattern having a good profile using only the above-described typical lithographic technique. Accordingly, a fine pattern may be formed by forming an organic layer called a hardmask layer between the material layer to be etched and the photoresist layer. The hard mask layer serves as an interlayer that transfers the micropattern of the photoresist to the material layer through a selective etching process. Therefore, the hardmask layer needs heat-resistance and etch-resistance properties to withstand multiple etching processes.

In addition, when there is a step difference in the substrate to be processed in the multi-patterning process, or when the pattern dense portion and the pattern-free region exist together on the wafer, the hard mask layer filled in the pattern has planarization characteristics that can minimize the step difference between the patterns This is especially important.

Therefore, there is a need for a material for a film structure that can satisfy the above-mentioned properties.

One embodiment provides a novel compound excellent in etch resistance, planarization properties, and gap-fill properties while ensuring solubility.

Another embodiment provides an organic film composition including the compound.

Another embodiment provides a pattern forming method using the organic film composition.

According to one embodiment, there is provided a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X and Y are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

n is an integer from 2 to 5;

In Formula 1, X and Y may have different structures.

In Formula 1, n may be 2 or 3.

In Formula 1, X may be a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, or a combination thereof.

In Formula 1, Y may be any one of substituted or unsubstituted moieties listed in Group 1 and Group 2 below.

[Group 1]

[Group 2]

In group 2,

Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,

Z ³ and Z ⁴ are N,

R ^d and R ^e are each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or an unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof:

However, in Groups 1 and 2, hydrogen in each moiety is each independently a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, Or substituted with a combination thereof, or unsubstituted.

The compound may have a molecular weight of 500 to 1,500.

According to another embodiment, there is provided an organic film composition comprising the above-described compound and a solvent.

According to another embodiment, forming a material layer on a substrate, applying the above-described organic film composition on the material layer, heat-treating the organic film composition to form a hardmask layer, on the hardmask layer forming a silicon-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; using the photoresist pattern the silicon-containing thin film layer; and selectively removing the hardmask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

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

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

The compound according to the present invention may form a polycyclic aromatic moiety through an electrocyclization reaction during a baking process after coating. Accordingly, it is possible to secure not only excellent etch resistance but also planarization characteristics. When the compound is used as an organic film material, a film having excellent film density can be formed. When the organic film material is applied to the resist underlayer, a fine pattern having a high aspect ratio may be realized.

1 is a flowchart for explaining a pattern forming method according to an embodiment;
2 is a reference diagram for explaining Equation 2 related to a planarization characteristic.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Unless otherwise defined herein, "substituted" means that a hydrogen atom in a compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, A hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol 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 C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alky Nyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 It means substituted with a substituent selected from a cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined in the present specification, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S and P.

In addition, unless otherwise defined herein, '*' indicates a connection point of a compound or a compound moiety.

Hereinafter, a compound according to an embodiment will be described.

A compound according to an embodiment is represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

X and Y are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

n is an integer from 2 to 5;

The compound has a cyclic group such as a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group located on the core, and 2 to 5 substituted or unsubstituted C6 to C30 aryl groups on both sides of the core. It has a structure in which a group or a substituent such as a substituted or unsubstituted C2 to C30 heteroaryl group is connected through an alkenylene having 4 carbon atoms.

The compound includes an aromatic/heteroaromatic ring group with strong heat resistance in its structure and is basically excellent in corrosion resistance. In addition, the compound may undergo an electron cycle (electrocyclization) reaction in the process of coating and baking, and accordingly, an aromatic/heteroaromatic ring group included in the compound structure may form a polycyclic aromatic/polycyclic heteroaromatic moiety. . Accordingly, the compound may have better corrosion resistance and heat resistance. In addition, since the compound can form a polycyclic aromatic/polycyclic heteroaromatic moiety in the subsequent baking process, the polycyclic aromatic/heteroaromatic ring group content in its structure itself may be relatively low, and thus it is advantageous to secure solubility .

In Formula 1, X and Y may be, for example, cyclic groups having different structures.

For example, in Formula 1, X may be a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, or a combination thereof, but is not limited thereto. it is not

For example, in Formula 1, Y may be any one of substituted or unsubstituted moieties listed in Group 1 and Group 2, but is not limited thereto.

[Group 1]

[Group 2]

In group 2,

Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,

Z ³ and Z ⁴ are N,

R ^d and R ^e are each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or an unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof:

However, in Groups 1 and 2, hydrogen in each moiety is each independently a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, Or substituted with a combination thereof, or unsubstituted.

Meanwhile, in Formula 1, n means the number of Y (substituent moieties) connected to X (core moiety) by alkenylene, and n may be, for example, 2 or 3, but is not limited thereto.

For example, the molecular weight of the above-described compound may be about 500 to 1,500, but is not limited thereto. The compound described above can be optimized by selecting a molecular weight within the above range to adjust the carbon content and solubility in a solvent of the organic film composition (eg, hard mask composition).

According to another embodiment, there is provided an organic film composition comprising the above-described compound and a solvent.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility for the compound, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) mono Methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone , may include at least one selected from methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate.

The compound may be included in an amount of about 0.1 to 50% by weight, about 0.1 to 30% by weight, or about 0.1 to 15% by weight based on the total content of the organic film composition. By including the compound in the above range, the thickness, surface roughness, and planarization degree of the organic layer can be adjusted.

The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

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

The crosslinking agent may be, for example, a melamine-based, substituted urea-based, or polymer-based agent. Preferably, crosslinking agents having at least two crosslinking substituents are, for example, methoxymethylated glycouryl, butoxymethylated glycouryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy A compound such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea may be used.

In addition, as the crosslinking agent, a crosslinking agent having high heat resistance may be used. As a crosslinking agent with high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (eg, a benzene ring, a naphthalene ring) in the molecule can be used.

The thermal acid generator is, for example, an acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and/or 2,4 ,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other organic sulfonic acid alkyl esters may be used, but the present invention is not limited thereto.

The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including in the above range, solubility can be improved without changing the optical properties of the organic film composition.

According to another embodiment, an organic film prepared by using the above-described organic film composition is provided. The organic film may be in a form that is cured through a heat treatment process after coating the above-described organic film composition on a substrate, for example, and may include, for example, an organic thin film used in electronic devices such as a hard mask layer, a planarization film, a sacrificial film, and a filler. there is.

Hereinafter, a method of forming a pattern using the above-described organic film composition will be described with reference to FIG. 1 .

1 is a flowchart illustrating a pattern forming method according to an exemplary embodiment.

A pattern forming method according to an embodiment includes forming a material layer on a substrate (S1), applying the above-described organic film composition on the material layer (S2), and heat-treating the organic film composition to form a hard mask layer (S3), forming a silicon-containing thin film layer on the hardmask layer (S4), forming a photoresist layer on the silicon-containing thin film layer (S5), exposing and developing the photoresist layer to form a photoresist pattern forming a (S6), selectively removing the silicon-containing thin film layer and the hardmask layer using the photoresist pattern and exposing a portion of the material layer (S7), and an exposed portion of the material layer and etching (S8).

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

The organic film composition is the same as described above, and may be prepared in a solution form and applied by a spin-on 　 coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but may be applied, for example, to a thickness of about 50 to 200,000 Å.

The heat treatment of the organic film composition may be performed, for example, at about 100 to 700° C. for about 10 seconds to 1 hour.

The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and/or SiN.

Also, before the step of forming the photoresist layer, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer.

The exposing of the photoresist layer may be performed using, for example, ArF, KrF, or EUV. In addition, a heat treatment process may be performed at about 100 to 700° C. after exposure.

The etching of 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 ,} or a mixture thereof.

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

The embodiments of the present invention described above will be described in more detail through the following examples. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

Synthesis example

Synthesis Example 1

In a flask, methoxypyrene ( 23.2 g, 0.1 mol) and N- bromosuccinimide (19.6 g, 0.1 mol) were _{dissolved in 150 mL of CH 3} CN and stirred at room temperature for 2 hours. After the reaction was completed, ethyl acetate (300 mL) was added to dilute the reactant, washed with DIW (200 mL), and the organic layer was removed. After removing the organic solvent under reduced pressure, the following compound 1a is obtained by column chromatography.

[Compound 1a]

The obtained compound 1a (24.9 g, 0.08 mol), acrolein (13.5 g, 0.24 mol), K2CO3 (16.6 g, 0.12 mol), KCl (6.0 g, 0.08 mol), tetrabutylammonium acetate (48.2 g, 0.16 mol) and palladium acetate (0.5g) was dissolved in dimethyl formamide (150ml) and stirred at 90℃ for 2 hours. After the reaction was completed, ethyl acetate (300 mL) was added to dilute the reactant, washed with DIW (200 mL), and the organic layer was removed. After removing the organic solvent under reduced pressure, the following compound 1b is obtained by column chromatography.

[Compound 1b]

J. Org . Chem . 2002, 67 , 3755-3763., the following compound A is obtained.

[Compound A]

After dissolving the compound A (6.2 g, 0.02 mol) and the compound 1b (14.3 g, 0.05 mol) in THF (200 mL) in a flask, the temperature was lowered to 0 °C. After that, potassium tert- butoxide (1.7g, 0.02mol) was slowly added over 30 minutes and stirred at 0° C. for 3 hours. After the reaction was completed, the reaction solution was slowly poured into DIW (200 mL), and the resulting solid was filtered and washed with diethyl ether (100 mL) to obtain the following compound 1c.

[Compound 1c]

After dissolving the compound 1c (4.6 g, 0.01 mol), 1-dodecanthiol (30.4 g, 0.02 mol) and potassium hydroxide (1.4 g, 0.03 mol) in NMP (100 mL) in a flask, the temperature was raised to 100° C. for 10 hours Stir. After completion of the reaction, the reaction solution is slowly poured into DIW (200 mL), the resulting solid is filtered, and the residual solvent is removed under reduced pressure, and then the compound represented by the following Chemical Formula 1-1 is obtained by column chromatography.

[Formula 1-1]

Synthesis Example 2

In Synthesis Example 1, a compound represented by the following Chemical Formula 1-2 was obtained in the same manner except that pyrene was used instead of methoxypyrene.

[Formula 1-2]

Synthesis Example 3

In Synthesis Example 1, except that indole was used instead of methoxypyrene, a compound represented by the following Chemical Formula 1-3 was obtained in the same manner.

[Formula 1-3]

Synthesis Example 4

The following compound 4a is obtained by using the method for preparing compound 1b using 2-bromo-7-methoxytriphenylene.

[Compound 4a]

In Synthesis Example 1, a compound represented by the following Chemical Formula 1-4 was obtained in the same manner except that the compound 4a was used instead of methoxypyrene.

[Formula 1-4]

Synthesis Example 5

Chem . Commun . 2003, 2618-2619., the following compound B is obtained.

[Compound B]

In Synthesis Example 1, a compound represented by the following Chemical Formula 1-5 was obtained by using the same method except that Compound B was used instead of Compound A.

[Formula 1-5]

Comparative Synthesis Example 1

28.83 g (0.2 mol) of 1-naphthol, 41.4 g (0.15 mol) of benzoperylene and 12.0 g (0.34 mol) of paraformaldehyde were added to the flask, and then 162 g of propylene glycol monomethyl ether acetate (PGMEA) was added. Next, after adding 0.19 g of p -toluene sulfonic acid monohydrate, the mixture is stirred at a temperature of 90 to 100° C. for 5 to 12 hours.

A sample is taken from the polymerization product at intervals of 1 hour, the weight average molecular weight of the sample is measured, and the reaction is completed when the weight average molecular weight is 1,800 to 2,500.

polymerization After the reaction is completed, the reactant is slowly cooled to room temperature, the reactant is added to 40 g of distilled water and 400 g of methanol, stirred vigorously, and then left to stand. After removing the supernatant and dissolving the precipitate in 80 g of propylene glycol monomethyl ether acetate (PGMEA), vigorously stirring using 320 g of methanol, and allowing to stand (1st). At this time, the obtained supernatant is removed again and the precipitate is dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (secondary). The first and second processes are referred to as a one-time purification process, and this purification process is performed three times in total. After the purified polymer is dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), methanol and distilled water remaining in the solution are removed under reduced pressure to obtain a compound represented by the following formula (X).

[Formula X]

Comparative Synthesis Example 2

In a flask, 50.0 g (0.143 mol) of 9,9'-bis(4-hydroxyphenyl)fluorene, 23.7 g (0.143 mol) of 1,4-bis(methoxymethyl)benzene, and 50 g of propylene glycol monomethyl ether acetate were added to the flask. added to prepare a solution. After adding 1.10 g (7.13 mmol) of diethyl sulfate to the solution, the mixture was stirred at 100° C. for 24 hours. When the polymerization is completed, it is precipitated in methanol to remove a monomer and a low molecular weight substance to obtain a compound represented by the following formula Y.

[Formula Y]

Comparative Synthesis Example 3

J. Am. Chem . Soc. 2014 , 136 , 17337-17342. to obtain the following compound C.

[Compound C]

In Synthesis Example 1, pyrene was used instead of methoxypyrene, and compound C was used instead of compound A to obtain a compound represented by the following formula (Z).

[Compound Z]

Preparation of hard mask composition

Example 1

After dissolving the compound obtained in Synthesis Example 1 in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3 (v/v)), a 0.1 μm Teflon filter Filtration to prepare a hard mask composition. According to the desired thickness, the weight of the compound was adjusted to 5 wt% to 20 wt% based on the total weight of the hardmask 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 instead of the compound obtained in Synthesis Example 1.

Comparative Example 1

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.

Evaluation 1: Corrosion resistance

After spin-coating the hard mask compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 on a silicon wafer, heat treatment at 400° C. for 2 minutes on a hot plate to form a 4000 Å thick thin film, The thin film thickness was measured with a thin film thickness meter.

Subsequently, the thin film formed _{was dry-etched for 100 seconds and 60 seconds using a CHF 3} /CF ₄ mixed gas and a N ₂ /O ₂ mixed gas, respectively, and then the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated by Equation 1 below from the thickness and etching time of the thin film before and after dry etching.

[Formula 1]

Bulk etch rate (BER) = (initial thin film thickness - thin film thickness after etching) / etch time (Å/sec)

The results are shown in Table 1.

CHF ₃ /CF ₄ bulk etch rate
(Å/sec) N ₂ /O ₂ bulk etch rate
(Å/sec) Example 1 23.2 21.4 Example 2 22.9 20.8 Example 3 21.2 24.9 Example 4 26.2 23.4 Example 5 24.7 22.3 Comparative Example 1 28.4 25.2 Comparative Example 2 30.0 27.5 Comparative Example 3 27.2 24.5

Referring to Table 1, the thin film formed from the hardmask composition according to Examples 1 to 5 has sufficient etch resistance to etching gas compared to the thin film formed from the hardmask composition according to Comparative Examples 1 to 3, so that the bulk etch characteristics are improved. can confirm.

Evaluation 2: Planarization Characteristics and Gap-Fill Characteristics

After applying the hardmask compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 to the patterned wafer and forming a thin film through a baking process using a hot plate, gap-fill characteristics and planarization performance were observed.

The gap-fill characteristic was determined by observing the cross section of the pattern with a scanning electron microscope (SEM) to determine the presence or absence of voids, and the flattening characteristic (step difference) was measured by measuring the thickness of the thin film around the pattern with a thin film thickness meter of K-MAC. Thus, it was quantified by the formula 2 shown in FIG. 2 .

[Formula 2]

Step (Å) = Thickness of the thin film measured at an arbitrary point where no pattern is formed on the substrate (h ₁ ) - Thickness of the thin film measured at the center of the portion where any one pattern is formed on the substrate (h ₂ )

In Equation 2, as _{the difference between h 1} and h ₂ , that is, the step is not large, the flattening characteristic is excellent.

The results are shown in Table 2.

planarization properties (h1-h2, Å) Gap Fill Characteristics
(with or without void) aspect ratio
(1:2) aspect ratio
(1:10) Example 1 51 121 no void Example 2 72 163 no void Example 3 75 135 no void Example 4 68 189 no void Example 5 95 206 no void Comparative Example 1 122 285 no void Comparative Example 2 106 310 void occurrence Comparative Example 3 90 198 void occurrence

Referring to Table 2, it can be seen that in Comparative Examples 1 to 3, the difference between h1 and h2 was large, so that the flatness was not very good. can

On the other hand, it can be seen that the hard masks according to Examples 1 to 5 have good gap-fill performance to the extent that voids are not observed, and also have excellent planarization characteristics because the difference between h1 and h2 is small compared to Comparative Examples.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also presented. It is within the scope of the invention.

Claims (15)

delete delete delete delete delete delete A compound represented by the following formula (1), and
menstruum
A hard mask composition comprising:
[Formula 1]

In Formula 1,
X is each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
Y is any one of the substituted or unsubstituted moieties listed in Group 1 and Group 2 below,
n is an integer from 2 to 5:
[Group 1]

[Group 2]

In group 2,
Z ¹ and Z ² are each independently NR ^d , O, S, Te or Se,
Z ³ and Z ⁴ are N,
R ^d and R ^e are each independently hydrogen, a hydroxyl group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or an unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof:
However, in Groups 1 and 2, hydrogen in each moiety is each independently a hydroxy group, a halogen group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, Or substituted with a combination thereof, or unsubstituted. In claim 7,
In Formula 1, X and Y are a hard mask composition having different structures. In claim 7,
In Formula 1, n is 2 or 3 of the hard mask composition. In claim 7,
In Formula 1, X is a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, or a combination thereof. delete In claim 7,
The compound is a hard mask composition having a molecular weight of 500 to 1,500. providing a layer of material over the substrate;
applying the hardmask composition according to any one of claims 7 to 10 and 12 over the material layer;
forming a hardmask layer by heat-treating the hardmask composition;
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 hardmask layer using the photoresist pattern and exposing a portion of the material layer; and
etching the exposed portion of the material layer;
containing
How to form a pattern. In claim 13,
The step of applying the hard mask composition is a pattern forming method performed by a spin-on coating method. In claim 13,
and forming a bottom anti-reflective layer (BARC) prior to forming the photoresist layer.

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