KR102359989B1 - Compound and hardmask composition, hardmask layer and method of forming patterns - Google Patents

Abstract

상기 화학식 1에서, A 내지 E의 정의는 명세서에 기재된 바와 같다.The present invention relates to a compound represented by the following Chemical Formula 1, a hard mask composition including the compound, a hard mask layer including a cured product of the hard mask composition, and a pattern forming method using the hard mask composition.
[Formula 1]

In Formula 1, the definitions of A to E are as described in the specification.

Description

COMPOUND AND HARDMASK COMPOSITION, HARDMASK LAYER AND METHOD OF FORMING PATTERNS

The present invention relates to a compound, a hardmask composition including the compound, a hardmask layer including a cured product of the hardmask composition, and a pattern forming method using the hardmask composition.

Recently, the semiconductor industry is developing 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 auxiliary layer called a hardmask layer between the material layer to be etched and the photoresist layer.

One embodiment provides a compound that can be effectively applied to a hardmask layer.

Another embodiment provides a hard mask composition comprising the compound.

Another embodiment provides a hardmask layer including a cured product of the hardmask composition.

Another embodiment provides a pattern forming method using the hardmask composition.

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

[Formula 1]

In Formula 1,

A is a substituted or unsubstituted C6 to C30 aromatic ring,

B to E are each independently hydrogen, deuterium, a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their is a combination,

A to E each independently exist, or at least two of A to E are linked to each other to form a ring.

A may be any one of substituted or unsubstituted selected from the following group 1.

[Group 1]

B and D are each independently hydrogen or a substituted or unsubstituted C6 to C30 aryl group, and C and E are each independently a hydroxyl group; amine group; a substituted or unsubstituted C1 to C30 alkoxy group; Alternatively, it may be a C6 to C30 aryl group substituted with a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof.

At least one of B and C may include a condensed ring, and at least one of D and E may include a condensed ring.

At least one of B and C may include a C6 to C30 condensed ring substituted with a hydroxyl group, and at least one of D and E may include a C6 to C30 condensed ring substituted with a hydroxyl group.

The substituted or unsubstituted C6 to C30 aryl group may each independently include any one substituted or unsubstituted selected from Group 2 below.

[Group 2]

Any one selected from Group 2 may be substituted with at least one hydroxyl group

A may be connected with B to form a ring, may be connected with D to form a ring, or may be connected with B and D to form a ring.

The compound represented by Formula 1 may be represented by Formulas 2 to 7 below.

[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

[Formula 6] [Formula 7]

In Formulas 2 to 7,

A is a substituted or unsubstituted C6 to C30 aromatic ring,

B ¹ to B ⁴ and D ¹ to D ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,

C ¹ to C ³ and E ¹ to E ³ are each independently a C6 to C30 aryl group substituted with a hydroxyl group.

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

According to another embodiment, a hardmask layer including a cured product of the hardmask composition is provided.

According to another embodiment, applying the above-described hardmask composition on the material layer and heat-treating to form a hardmask layer, forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer A pattern comprising forming a photoresist pattern, selectively removing the hardmask layer using the photoresist pattern and exposing a portion of the material layer, and etching the exposed portion of the material layer A method of forming is provided.

It is possible to secure excellent film density and etch resistance of the hardmask layer.

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

Hereinafter, unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is deuterium, a halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group group, hydrazino group, hydrazono group, carbonyl group, carbayl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl 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 cycloalkynyl group, C2 to C30 heterocyclic group, and combinations thereof mean substituted with a substituent.

In addition, the substituted 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 , ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to two adjacent substituents of a C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, and a C2 to C30 heterocyclic group They can also be fused to form rings. For example, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

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

As used herein, the term "aryl group" refers to a group having one or more hydrocarbon aromatic moieties, and broadly includes non-condensed aromatic moieties, condensed aromatic moieties, and hydrocarbon aromatic moieties. A form connected by a single bond, a form in which hydrocarbon aromatic moieties are connected by an alkylene group, a form in which each ring is fused to two non-parallel sides on a benzene ring, and a form in which two non-parallel sides on a benzene ring are connected to each other It also includes a form in which each ring condensed to is connected by a single bond or a double bond. Aryl groups include monocyclic, polycyclic, or fused polycyclic (ie, rings bearing adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a concept including a heteroaryl group, in addition to carbon (C) in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof It means containing at least one hetero atom selected from N, O, S, P and Si. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may include one or more heteroatoms.

More specifically, a substituted or unsubstituted aryl group and/or a substituted or unsubstituted heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted A substituted or unsubstituted chrysenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted pycenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, A substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group , substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridinyl group, substituted or Unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimi Dazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or Unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazinyl group, substituted or unsubstituted A phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group Group, pyridoindolyl group, benzopyridooxazinyl group, benzopyridothiazinyl group, 9,9-dimethyl 9,10 dihydroacridinyl group, A combination of these or a combination thereof may be in a fused form, but is not limited thereto. In one embodiment of the present invention, the heterocyclic group or the heteroaryl group may be a pyridyl group, a carbazolyl group or a pyridoindolyl group.

As used herein, the term “aromatic ring” refers to a non-condensed aromatic ring, a condensed aromatic ring, a form in which aromatic rings are connected by a single bond, a form in which each ring condensed to two non-parallel sides on a benzene ring is fused, a benzene ring Each ring condensed on the two non-parallel sides of the above includes a form connected by a single bond or a double bond, or a combination thereof.

In the present specification, the ethynyl group refers to a functional group in which a carbon-carbon triple bond (-C≡CH) is located at the end of the compound.

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

The compound may include a core (A) having an aromatic ring, and the core (A) may be substituted with a plurality of substituents (X) including an ethynyl group at the terminal. When the compound has a plurality of substituents (X) including an ethynyl group at the terminal, the carbon content of the compound can be increased and a hard layer can be formed, so that high film density and corrosion resistance can be imparted.

As an example, the number of substituents (X) substituted in the aforementioned core (A) may be two, and the compound may be represented by Formula 1 below.

[Formula 1]

In Formula 1,

A is a substituted or unsubstituted C6 to C30 aromatic ring,

B to E are each independently hydrogen, deuterium, a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their is a combination,

A to E each independently exist, or at least two of A to E are linked to each other to form a ring.

the aromatic ring is a single ring; is a fused ring in which two or more aromatic rings are fused; It may be an unfused ring in which two or more aromatic rings are connected by a single bond, a C1 to C5 alkylene group, or O.

When the compound includes the core (A) having an aromatic ring, the carbon content of the compound can be increased to form a hard layer, and thus high corrosion resistance can be imparted.

For example, A may be a monocyclic or polycyclic ring, and may be a condensed ring or a non-condensed ring.

For example, A may be any one of substituted or unsubstituted selected from the following group 1.

[Group 1]

The plurality of substituents (X) substituted for the above-mentioned core (A) have an ethynyl group, and thus, by crosslinking of the ethynyl group at the terminal during curing of the composition including the compound, high film strength of the layer prepared therefrom , film density and high etch resistance to etching gas.

Due to the intermolecular π-π stacking interaction of the carbon of the ethynyl group, the layer made of the compound may exhibit higher film strength and film density.

For example, at least one of B and C is a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof may be, and at least one of D and E is a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or their It can be a combination.

For example, B to E are each independently a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof can be

For example, at least one of B to E is a hydroxyl group; amine group; a substituted or unsubstituted C1 to C30 alkoxy group; Alternatively, it may be a C6 to C30 aryl group substituted with a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof.

For example, at least two of B to E are a hydroxyl group; amine group; a substituted or unsubstituted C1 to C30 alkoxy group; Alternatively, it may be a C6 to C30 aryl group substituted with a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof.

For example, at least one of B and C is a hydroxyl group; amine group; a substituted or unsubstituted C1 to C30 alkoxy group; or a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof may be a C6 to C30 aryl group, and at least one of D and E is a hydroxyl group; amine group; a substituted or unsubstituted C1 to C30 alkoxy group; Alternatively, it may be a C6 to C30 aryl group substituted with a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof.

For example, B and D are each independently hydrogen or a substituted or unsubstituted C6 to C30 aryl group, and C and E are each independently a hydroxyl group; amine group; a substituted or unsubstituted C1 to C30 alkoxy group; Alternatively, it may be a C6 to C30 aryl group substituted with a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof. In B and D, a substituted or unsubstituted C6 to C30 aryl group is a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof, a C6 to C30 aryl group, or an unsubstituted C6 to C30 It may be an aryl group.

For example, B to E may be a single ring or a polycyclic ring, and may be a condensed ring or a non-condensed ring.

For example, at least one of B to E may include a condensed ring, for example, at least two of B to E may include a condensed ring, for example, at least one of B and C may include a condensed ring and D And at least one of E may include a condensed ring, for example, B to E may each independently include a condensed ring. As described above, when the compound includes the condensed ring, higher corrosion resistance to the etching gas of the layer made of the compound can be imparted.

For example, at least one of B to E may include a C6 to C30 condensed ring substituted with a hydroxyl group, for example, at least two of B to E may include a C6 to C30 condensed ring substituted with a hydroxyl group, such as , at least one of B and C may include a C6 to C30 condensed ring substituted with a hydroxyl group, and at least one of D and E may include a C6 to C30 condensed ring substituted with a hydroxyl group, for example, B to E are each independently It may include a C6 to C30 condensed ring substituted with a hydroxyl group.

For example, in B to E, the substituted or unsubstituted C6 to C30 aryl groups may each independently include any one substituted or unsubstituted selected from Group 2 below.

[Group 2]

For example, any one selected from Group 2 may be substituted with at least one hydroxyl group.

For example, at least one of B to E may include pyrene, for example, at least two of B to E may include pyrene, for example, at least one of B and C may include pyrene, and D And at least one of E may include pyrene, for example, B to E may each independently include pyrene.

For example, at least one of B to E may include hydroxypyrene, for example, at least two of B to E may include hydroxypyrene, for example, at least one of B and C may include hydroxypyrene. It includes pyrene and at least one of D and E may include hydroxypyrene, for example, B to E may each independently include hydroxypyrene.

For example, A may be connected with B to form a ring, may be connected with D to form a ring, or may be connected with B and D to form a ring. Accordingly, since the carbon content of the compound can be increased, a harder layer can be formed, and thus higher etch resistance can be provided.

For example, when A and B are connected to form a ring, B may be a non-condensed ring, when A and D are connected to form a ring, D may be a non-condensed ring, and A, B and D are connected to form a ring, B and D may be a non-condensed ring, wherein the non-condensed ring may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, specifically a hydroxyphenyl group or an unsubstituted phenyl group can be

For example, the compound represented by Formula 1 may be represented by Formulas 2 to 7 below.

[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

[Formula 6] [Formula 7]

In Formulas 2 to 7,

A is as described above,

B ¹ to B ⁴ and D ¹ to D ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,

C ¹ to C ³ and E ¹ to E ³ are each independently a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a C6 to C30 aryl group substituted with a combination thereof.

For example, B ¹ to B ⁴ , C ¹ to C ³ , D ¹ to D ⁴ and E ¹ to E ³ may each independently be a monocyclic or polycyclic ring, and may be a condensed ring or a non-condensed ring.

For example, B ¹ , B ³ , D ¹ and D ³ may each independently include a condensed ring, for example, B ¹ , B ³ , D ¹ and D ³ are each independently a substitution selected from Group 2 Or it may be any one of unsubstituted, for example, may be a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyrenyl group, specifically, a hydroxynaphthyl group, an unsubstituted naphthyl group, a hydroxypyrenyl group Or it may be an unsubstituted pyrenyl group.

For example, B ² , B ⁴ , D ² and D ⁴ may each independently include a non-condensed ring, for example, may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, specifically, It may be a hydroxyphenyl group or an unsubstituted phenyl group.

For example, C ¹ to C ³ and E ¹ to E ³ may each independently be a C6 to C30 aryl group substituted with a hydroxyl group.

For example, C ¹ to C ³ and E ¹ to E ³ may each independently include a condensed ring, for example, C ¹ to C ³ and E ¹ to E ³ are each independently a hydroxynaphthyl group, hydroxy Anthracenyl group, hydroxyphenanthrenyl group, hydroxyacenaphthylenyl group, hydroxyacenaphthenyl group, hydroxypyrenyl group, hydroxybenzophenanthrenyl group, hydroxybenzanthracenyl group, hydroxychrysenyl group, It may be a hydroxytriphenyl group, a hydroxytetracenyl group, a hydroxypentacenyl group, a hydroxyperylenyl group, a hydroxybenzofluoranthenyl group, a hydroxybenzofurylenyl group or a hydroxycoronenyl group.

The molecular weight of the above-described compound may be, for example, about 100 to 5,000, about 120 to 3,000, or about 150 to 2,000, but is not limited thereto.

When the compound having the above molecular weight is used, a more uniform thin film can be formed without the formation of pin-holes and voids or deterioration of thickness distribution during the baking process, and when there is a step or pattern in the lower substrate (or film) In the case of forming , better gap-fill and planarization properties may be provided.

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

The solvent included in the hard mask composition is not particularly limited as long as it has sufficient solubility or dispersibility for the compound, for example, propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether , tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethyl It may include at least one selected from acetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate, but is not limited thereto.

The compound may be included, for example, in an amount of about 0.1 to 60% by weight, about 0.5 to 50% by weight, or about 1 to 45% by weight based on the total content of the hardmask composition. By including the compound in the above range, the thickness, surface roughness, and planarization degree of the hard mask can be adjusted.

The hard mask 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, a substituted urea-based, or these polymers. Preferably, a crosslinking agent having at least two crosslinking substituents is, for example, methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy A compound such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea can 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 30 parts by weight, about 0.05 to 25 parts by weight, or about 0.01 to 20 parts by weight based on 100 parts by weight of the hard mask composition. By including in the above range, solubility can be improved without changing the optical properties of the hard mask composition.

According to another embodiment, there is provided an organic layer prepared using the above-described hard mask composition. The organic film may be in a form cured through a heat treatment process after coating the above-described hard mask 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. have.

According to another embodiment, a hardmask layer including a cured product of the hardmask composition is provided.

For example, the cured product includes condensed polycyclic aromatic hydrocarbons.

For example, the condensed polyaromatic hydrocarbon may be a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted naphthacene, a substituted or unsubstituted pyrene, a substituted or Unsubstituted benzopyrene, substituted or unsubstituted chrysene, substituted or unsubstituted triphenylene, substituted or unsubstituted perylene, substituted or unsubstituted benzofluoranthene, substituted or unsubstituted benzoperylene , substituted or unsubstituted coronene, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.

As an example, the cured product may further include a heterocycle.

Since the cured product contains condensed polyaromatic hydrocarbons, it may exhibit high corrosion resistance and chemical resistance capable of withstanding etching gases and chemical liquids exposed in subsequent processes including the etching process.

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

The method for forming a pattern according to an exemplary embodiment includes forming a material layer on a substrate, applying a hardmask composition including the compound and solvent described above on the material layer, and heat-treating the hardmask composition to form a hardmask layer forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hardmask layer using the photoresist pattern, and exposing 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, 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 hard mask composition is the same as described above, and may be prepared in the form of a solution and applied by a spin-on 　 coating method. At this time, the thickness of the hard mask composition is not particularly limited, but may be applied, for example, to a thickness of about 50 Å to 200,000 Å.

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

For example, the method may further include forming a silicon-containing thin film layer on the hardmask layer. The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and/or SiN.

For example, 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 or on the hard mask 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 for example, may be applied as various patterns in a semiconductor integrated circuit device.

The above-described embodiment 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 rights.

synthesis of compounds

Synthesis Example 1

[Formula 1a]

Terephthalaldehyde (13.4 g, 0.1 mol) was dissolved in tetrahydrofuran (THF, 300 ml), and the temperature was reduced to 0° C. under nitrogen atmosphere. Thereafter, a THF mixed solution (0.5M, 30ml) in which ethynylmagnesium bromide was dissolved was slowly added dropwise to react for 1 hour. Thereafter, the temperature was raised to room temperature, and after further reaction with stirring for 12 hours, it was quenched with a saturated aqueous ammonium chloride solution (saturated NH ₄ Cl(aq)) (quenching). The aqueous solution layer and the organic layer were separated (work-up) with ethyl acetate for the reaction mixture solution, and the aqueous layer was removed to obtain an organic layer. The solvent of the separated organic layer was removed to obtain a compound represented by Chemical Formula 1a. (yield rate 90%)

[Scheme 1]

Synthesis Example 2

[Formula 1b]

After dissolving the compound (5.3 g, 0.09 mol) of the formula 1a obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA, 200 ml), hydroxypyrene (HO-Pyrene, 43 g, 0.2 mol) was added put The mixed solution was heated to 90° C. and reacted until the compound represented by Formula 1a did not remain. After the reaction, it was purified to obtain a compound represented by Formula 1b.

[Scheme 2]

Synthesis Example 3

[Formula 1c]

A compound represented by Formula 1c was prepared in the same manner as in Synthesis Example 1 except that 4,4'-biphenyldicarboxyaldehyde (21 g, 0.1 mol) was used instead of terephthalaldehyde (13.4 g, 0.1 mol). .

Synthesis Example 4

[Formula 1d]

In the same manner as in Synthesis Example 2, except that the compound represented by Formula 1c obtained in Synthesis Example 3 (23 g, 0.9 mol) was used instead of the compound represented by Formula 1a obtained in Synthesis Example 1, and represented by Formula 1d compound was prepared.

Synthesis Example 5

[Formula 1e]

4a,12a-dihydroindeno[1,2-b]fluorene-6,12-dione (14g, 0.05mol) was dissolved in THF (150ml), and then the temperature was reduced to -78°C under a nitrogen atmosphere. Thereafter, n-hexane (2M, 50ml) in which n-butyllithium was dissolved was added dropwise to react for 30 minutes. Thereafter, while 1 mol of ethynyl trimethylsilane was added dropwise, the reaction was further carried out at a low temperature (about -78 ° C.) for 1 hour, the temperature was raised to room temperature, and quenched with a saturated aqueous ammonium chloride solution (saturated NH ₄ Cl(aq)). quenching. The aqueous solution layer and the organic layer were separated (work-up) with ethyl acetate for the reaction mixture solution, and the aqueous layer was removed to obtain an organic layer. The solvent of the separated organic layer was removed to obtain a compound represented by Chemical Formula 1e.

Synthesis Example 6

[Formula 1f]

After dissolving the compound (15 g, 0.045 mol) represented by Formula 1e obtained in Synthesis Example 5 in PGMEA (200 ml), hydroxypyrene (21 g, 0.1 mol) was added. The mixture solution was heated to 90° C. and reacted until the compound represented by Formula 1e did not remain. After the reaction, it was purified to obtain a compound represented by Formula 1f.

Synthesis Example 7

1) Synthesis of benzo[a]indeno[2,1-c]fluorene-5,10-dione

Dimethyl 2,3-diphenylnaphthalene-1,4-dicarboxylate (Dimethyl 2,3-Diphenylnaphthalene-1,4-Dicarboxylate, 66 g, 0.17 mol) was dissolved in concentrated sulfuric acid (conc.H ₂ SO ₄ , 200 mL) It was added slowly and the reaction stirred at room temperature (rt) until the solid was dissolved. After 12 hours, the mixed solution was slowly put into 3 L of ice water, and extracted with a diethyl ether/THF mixed solution (2 L) in a 2:1 volume ratio to obtain an organic layer. After adding distilled water to the obtained organic layer again, the aqueous layer and the organic layer were separated (work-up), only the organic layer was collected again, and the residue was removed with magnesium sulfate. Then, the solvent was removed by distillation under reduced pressure, and the obtained solid was recrystallized from ethanol to obtain a yellow solid. (yield rate 87%)

[Scheme 3]

2) Synthesis of the compound represented by Formula 1g

[Formula 1g]

Instead of 4a,12a-dihydroindeno[1,2-b]fluorene-6,12-dione (14g, 0.05mol), benzo[a]indeno[2,1-c] obtained in 1) above A compound represented by Formula 1g was prepared in the same manner as in Synthesis Example 5 except that fluorene-5,10-dione (16.5 g, 0.05 mol) was used.

Synthesis Example 8

[Formula 1h]

In the same manner as in Synthesis Example 6, except that the compound represented by Formula 1g obtained in Synthesis Example 7 (17.2 g, 0.45 mol) was used instead of the compound represented by Formula 1e obtained in Synthesis Example 5, to Formula 1h The compound represented was prepared.

Synthesis Example 9

[Formula 1i]

Instead of 4a,12a-dihydroindeno[1,2-b]fluorene-6,12-dione (14g, 0.05mol), coronene-1,7-diylbis(naphthalen-2-ylmethanone) ) (coronene-1,7-diylbis(naphthalen-2-ylmethanone), 30 g, 0.5 mol) was prepared in the same manner as in Synthesis Example 5 to prepare a compound represented by Formula 1i.

Synthesis Example 10

[Formula 1j]

In the same manner as in Synthesis Example 6, except that the compound represented by Formula 1i obtained in Synthesis Example 9 (30 g, 0.45 mol) was used instead of the compound represented by Formula 1e obtained in Synthesis Example 5, and expressed by Formula 1j compound was prepared.

Synthesis Example 11

[Formula 1k]

Instead of 4a,12a-dihydroindeno[1,2-b]fluorene-6,12-dione (14g, 0.05mol), 1,4-phenylenebis((7-hydroxypyrene-2- 1) Methanone) (1,4-phenylenebis((7-hydroxypyren-2-yl)methanone), 28 g, 0.5 mol) was prepared in the same manner as in Synthesis Example 5 to prepare a compound represented by Formula 1k did

Synthesis Example 12

[Formula 1l]

In the same manner as in Synthesis Example 6, except that the compound represented by Formula 1k obtained in Synthesis Example 11 (24 g, 0.45 mol) was used instead of the compound represented by Formula 1e obtained in Synthesis Example 5. compound was prepared.

Comparative Synthesis Example 1

[Formula A]

9,9-bis(4-hydroxyphenyl)fluorene (BPF, 14g) and paraformaldehyde (2.5g) were added to PGMEA (70g), and the mixture solution was heated to 70°C. Then, p-toluene sulfonic acid monohydrate (p-TsOH, 0.3 g) was added and the synthesis was carried out for 3 hours. After the reaction, the reaction was repeatedly purified using a mixed solution of n-hexane (200ml) and PGMEA (200ml) until there was no unreacted reactant as measured by GPC, and a polymer represented by the formula A was obtained. . (MW: 3,350)

Comparative Synthesis Example 2

[Formula B]

Fluorene (7 g) and hydroxypyrene (10 g) were put in PGMEA (30 g), and the mixture solution was heated to 110 °C. Then, 1 g of p-toluene sulfonic acid monohydrate was added and the synthesis was carried out for 12 hours. After the reaction, the reaction was repeatedly purified using a mixed solution of n-hexane (200ml) and PGMEA (200ml) until there was no unreacted reactant as measured by GPC, and the polymer represented by Formula B was obtained. (MW: 1,530)

Formation of hard mask composition: Examples 1 to 12, Comparative Examples 1 and 2

5 g of each compound obtained in Synthesis Examples 1 to 12 and each polymer obtained in Comparative Synthesis Examples 1 and 2 were respectively weighed and uniformly dissolved in 100 g of PGMEA, filtered through a 0.1 μm Teflon filter, Examples 1 to 12, Hard mask compositions of Comparative Examples 1 and 2 were prepared.

Evaluation 1. Membrane Density

After spin-coating the hard mask compositions according to Examples 1 to 12 and Comparative Examples 1 and 2 on a silicon wafer, respectively, heat treatment at about 400° C. for about 2 minutes on a hot plate to form an organic film with a thickness of about 1000 Å did

The film density of the formed organic film was measured with an X-ray reflectometer.

The results are shown in Table 1.

Membrane density (g/cm ³ ) Example 1 1.35 Example 2 1.32 Example 3 1.34 Example 4 1.33 Example 5 1.37 Example 6 1.35 Example 7 1.37 Example 8 1.36 Example 9 1.38 Example 10 1.36 Example 11 1.35 Example 12 1.34 Comparative Example 1 1.21 Comparative Example 2 1.25

Referring to Table 1, it can be seen that the organic film formed from the hardmask compositions according to Examples 1 to 12 has improved film density compared to the organic films formed from the hardmask compositions according to Comparative Examples 1 and 2.

Evaluation 2. Evaluation of corrosion resistance

After spin-coating the hard mask compositions according to Examples 1 to 12 and Comparative Examples 1 and 2 on a silicon wafer, respectively, heat treatment at about 400° C. for 2 minutes on a hot plate to form an organic film with a thickness of about 4,000 Å did Then, the organic layer was dry-etched using CFx gas and N ₂ /O ₂ gas for 100 seconds and 60 seconds, respectively, and then the thickness of the organic layer was measured again.

The bulk etch rate (BER) was calculated by Equation 1 below from the difference in the thickness of the organic layer before and after dry etching and the etching time.

[Formula 1]

Etching rate (Å/s) = (initial organic film thickness - organic film thickness after etching) / etch time

The results are shown in Table 2.

Bulk etch rate(Å/sec) CF _x etch rate (Å/s) N ₂ /O ₂ etch rate (Å/s) Example 1 28.0 26.2 Example 2 26.5 24.9 Example 3 28.2 25.9 Example 4 27.0 24.8 Example 5 25.6 24.2 Example 6 24.7 24.0 Example 7 25.6 23.4 Example 8 24.3 23.0 Example 9 24.5 24.2 Example 10 24.0 23.4 Example 11 26.7 24.5 Example 12 25.1 24.0 Comparative Example 1 28.6 28.9 Comparative Example 2 30.3 27.3

Referring to Table 2, the organic film prepared with the hard mask composition according to Examples 1 to 12 has sufficient etch resistance to etching gas compared to the organic film prepared with the hard mask composition according to Comparative Examples 1 and 2, so the etch resistance You can see this improvement.

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 belongs to the scope of the right of the invention.

Claims (20)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
A is a substituted or unsubstituted C6 to C30 aromatic ring,
B to E are each independently hydrogen, deuterium, a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
A to E are each independently present or at least two of A to E are linked to each other to form a ring,
At least one of B and C includes a condensed ring, and at least one of D and E includes a condensed ring. In claim 1,
A is a substituted or unsubstituted compound selected from the following group 1.
[Group 1]

In claim 1,
B and D are each independently hydrogen or a substituted or unsubstituted C6 to C30 aryl group,
C and E are each independently a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a substituted C6 to C30 aryl group,
When C or E is a substituted C6 to C30 aryl group, the substitution is substituted with a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof,
At least one of B and C includes a condensed ring, and at least one of D and E includes a condensed ring. delete In claim 1,
At least one of B and C comprises a C6 to C30 condensed ring substituted with a hydroxyl group,
At least one of D and E is a compound comprising a C6 to C30 condensed ring substituted with a hydroxyl group. In claim 1,
The substituted or unsubstituted C6 to C30 aryl group is each independently selected from the following group 2 A compound comprising any one of substituted or unsubstituted.
[Group 2]

In claim 6,
Any one selected from Group 2 is a compound substituted with at least one hydroxyl group. In claim 1,
A is connected to B to form a ring, or
connected to D to form a ring, or
A compound which is connected with B and D to form a ring. In claim 1,
The compound represented by Formula 1 is a compound represented by any one of Formulas 3 to 7.
[Formula 3]

[Formula 4] [Formula 5]

[Formula 6] [Formula 7]

In Formulas 3 to 7,
A is a substituted or unsubstituted C6 to C30 aromatic ring,
B ¹ and D ¹ are each independently a substituted or unsubstituted C10 to C30 condensed ring group,
A and B ² , A and D ² , A and B ⁴ , and A and D ⁴ are each linked to each other to form a condensed ring,
C ¹ , C ² , E ¹ , and E ² are each independently a C10 to C30 condensed ring group substituted with a hydroxy group,
B ³ and D ³ are each independently a substituted or unsubstituted C6 to C30 aryl group,
C ³ and E ³ are each independently a C6 to C30 aryl group substituted with a hydroxy group. A compound represented by the following formula (1), and
A hardmask composition comprising a solvent:
[Formula 1]

In Formula 1,
A is a substituted or unsubstituted C6 to C30 aromatic ring,
B to E are each independently hydrogen, deuterium, a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
A to E each independently exist, or at least two of A to E are linked to each other to form a ring. In claim 10,
A is a substituted or unsubstituted hard mask composition selected from the following group 1.
[Group 1]

In claim 10,
B and D are each independently hydrogen or a substituted or unsubstituted C6 to C30 aryl group,
C and E are each independently a hydroxyl group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a substituted C6 to C30 aryl group,
When C or E is a substituted C6 to C30 aryl group, the substitution is a hydroxy group, an amine group, a substituted or unsubstituted C1 to C30 alkoxy group, or a combination thereof. In claim 10,
At least one of B and C includes a condensed ring,
At least one of D and E is a hard mask composition comprising a condensed ring. In claim 13,
At least one of B and C comprises a C6 to C30 condensed ring substituted with a hydroxyl group,
At least one of D and E is a hard mask composition comprising a C6 to C30 condensed ring substituted with a hydroxyl group. In claim 10,
The substituted or unsubstituted C6 to C30 aryl group is each independently a substituted or unsubstituted hard mask composition selected from Group 2 below.
[Group 2]

In claim 15,
Any one selected from Group 2 is a hard mask composition substituted with at least one hydroxyl group. In claim 10,
A is connected to B to form a ring, or
connected to D to form a ring, or
A hard mask composition connected to B and D to form a ring. In claim 10,
The compound represented by Formula 1 is a hard mask composition represented by any one of Formulas 2 to 7.
[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

[Formula 6] [Formula 7]

In Formulas 2 to 7,
A is a substituted or unsubstituted C6 to C30 aromatic ring,
B ¹ to B ⁴ and D ¹ to D ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group,
C ¹ to C ³ and E ¹ to E ³ are each independently a C6 to C30 aryl group substituted with a hydroxyl group. A hard mask layer comprising a cured product of the hard mask composition according to any one of claims 10 to 18. 19. A method comprising: applying the hardmask composition according to any one of claims 10 to 18 on the material layer and heat-treating to form a hardmask layer;
forming a photoresist layer over the hardmask layer;
exposing and developing the photoresist layer to form a photoresist pattern;
selectively removing the hardmask layer using the photoresist pattern and exposing a portion of the material layer; and
etching the exposed portion of the material layer;
A pattern forming method comprising a.