Hard mask composition, hard mask layer, and pattern forming method

Abstract

The present invention relates to a hard mask composition comprising a compound represented by Chemical Formula 1 and a solvent, a hard mask layer comprising a cured product of the hard mask composition, and a pattern forming method using the hard mask composition. In Chemical Formula 1, A, R 1 to R 5 and n are defined in the specification.[Chemical Formula 1]

Description

TECHNICAL FIELD

[0001] Disclosed are a hard mask composition, a hard mask layer including a cured product of the hard mask composition, and a pattern forming method using the hard mask composition. BACKGROUND

[0002] Recently, the semiconductor industry has developed into a super-fine technology having a pattern of several nanometers to several tens of nanometers in size. Such a super-fine technology essentially requires an effective photolithography technique. A typical photolithography technique includes: providing a material layer on a semiconductor substrate; coating a photoresist layer thereon; exposing and developing the photoresist layer to provide a photoresist pattern; and etching the material layer using the photoresist pattern as a mask. Now, according to the small size of a pattern to be formed, it is difficult to provide a fine pattern having an excellent profile only by the above-described typical photolithography technique. Therefore, an auxiliary layer called a hard mask layer can be formed between the material layer and the photoresist layer to provide a fine pattern. SUMMARY

[0003]

Technical Problem

[0004] One embodiment provides a hard mask composition capable of improving etch resistance.

[0005] Another embodiment provides a hard mask layer including a cured product of the hard mask composition.

[0006] Another embodiment provides a pattern forming method using the hard mask composition.

[0007]

Technical Solution

[0008] According to one embodiment, a hard mask composition including a compound represented by Chemical Formula 1 and a solvent is provided.

[0009] [Chemical Formula 1]

[0010]

[0011] In Chemical Formula 1,

[0012] A is a C6 to C30 aromatic moiety,

[0013] R 1 to R 5 each independently is hydrogen, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof, or a group represented by Chemical Formula 2,

[0014] R 1 to R 5 at least one of R

[0015] n is an integer greater than or equal to 2,

[0016] [Chemical Formula 2]

[0017]

[0018] wherein, in Chemical Formula 2,

[0019] X is a substituted or unsubstituted C6 to C30 arylene,

[0020] Y is a substituted C6 to C60 aryl group or a substituted or unsubstituted C3 to C60 heteroaryl group, wherein the substituted C6 to C60 aryl group includes a substituent selected from the group consisting of a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

[0021] m is 0 or 1, and

[0022] represents a connection point with Chemical Formula 1.

[0023] A can be a benzene moiety, a naphthalene moiety, an anthracene moiety, a naphthacene moiety, a pentacene moiety,

[0024] a biphenyl moiety, a terphenyl moiety, a quaterphenyl moiety, or a quinquephenyl moiety,

[0025] a phenanthrene moiety, a pyrene moiety, a fluoranthene moiety, a triphenylene moiety, a chrysene moiety, a perylene moiety, a benzopyrene moiety, a naphthacene moiety, a benzophenanthrene moiety, a tetracene moiety, a coronene moiety, a naphthanthrene moiety, or a triphenylene moiety.

[0026] A can be any one selected from Group 1.

[0027] [Group 1]

[0028]

[0029] R 1 , R 2 , R 4 , and R 5 may each independently be hydrogen or a substituted or unsubstituted group selected from Group 2, and

[0030] R 3 may be a group represented by Chemical Formula 2.

[0031] [Group 2]

[0032]

[0033] R 1 and R 4 may each independently be a substituted or unsubstituted phenyl group, and R 5 may be hydrogen.

[0034] X can be any one selected from substituted or unsubstituted groups of Group 3.

[0035] [Group 3]

[0036]

[0037] In Group 3, is a connection point.

[0038] The group represented by Chemical Formula 2 can be represented by Chemical Formula 3 or 4.

[0039]

[0040] In Chemical Formula 3 and Chemical Formula 4,

[0041] X is a substituted or unsubstituted C6 to C30 arylene group,

[0042] Y is a substituted or unsubstituted C3 to C30 heteroaryl group; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof,

[0043] R 6 to R 10 are each independently hydrogen, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

[0044] R 6 to R 10 at least one is a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl group; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof, and

[0045] represents a connection point with Chemical Formula 1.

[0046] Y of Chemical Formula 3 can be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 4; or a C6 to C30 aryl substituted with a hydroxyl, amine, thiol, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl thiol, substituted or unsubstituted C1 to C20 alkyl amine, or a combination thereof, selected from Group 5.

[0047] [Group 4]

[0048]

[0049] [Group 5]

[0050]

[0051] R of Chemical Formula 4 6 to R 10 may each independently be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6, or a substituted or unsubstituted C6 to C30 aryl selected from Group 7, and

[0052] R 7 , R 8 , and R 10 at least one of R, R, and R is a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6; or a C6 to C30 aryl substituted with a hydroxyl, amine, thiol, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl thiol, substituted or unsubstituted C1 to C20 alkyl amine, or a combination thereof, selected from Group 7.

[0053] [Group 6]

[0054]

[0055] [Group 7]

[0056]

[0057] R 6 and R 9 may each independently be a substituted or unsubstituted phenyl.

[0058] R 8 may be a C6 to C30 aryl substituted with a hydroxyl, amine, thiol, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl thiol, substituted or unsubstituted C1 to C20 alkyl amine, or a combination thereof, selected from Group 7, and

[0059] R 10may be substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6; or C6 to C30 aryl substituted with hydroxyl, amine, mercapto, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkylthiol, substituted or unsubstituted C1 to C20 alkylamine, or a combination thereof, selected from Group 7.

[0060] n can be an integer satisfying the range of 2 ≤ n ≤ k / 2, and k can be the number of substitutable positions of A in Chemical Formula 1.

[0061] The molecular weight of the compound represented by Chemical Formula 1 can be 900 to 7,000.

[0062] The compound represented by Chemical Formula 1 can be included in an amount of 0.01 wt% to 30 wt% based on the total content of the hard mask composition.

[0063] According to another embodiment, a hard mask layer including a cured product of a hard mask composition is provided.

[0064] The cured product can include condensed polycyclic aromatic hydrocarbons.

[0065] According to another embodiment, a pattern forming method includes: applying a hard mask composition on a material layer and heat-treating the resultant to form a hard mask layer; forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer; and etching the exposed portion of the material layer.

[0066]

Advantageous Effects

[0067] Etch resistance of the hard mask layer can be ensured. DETAILED DESCRIPTION

[0068] Hereinafter, exemplary embodiments of the present disclosure will be described in detail, and those skilled in the art can easily carry out the exemplary embodiments. However, the present disclosure can be embodied in many different forms, and is not interpreted as being limited to the exemplary embodiments set forth herein.

[0069] In the present specification, when not otherwise provided by definition, "substituted" means that a hydrogen atom of a compound is replaced with a substituent selected from the group consisting of deuterium, a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, a guanidino group, a hydrazine group, a hydrazono group, a carbonyl group, a carbamoyl group, a mercapto group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C30 alkylmercapto group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaralkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclic group, and combinations thereof.

[0070] Further, two adjacent substituents of a substituted halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, a guanidino group, a hydrazine group, a hydrazono group, a carbonyl group, a carbamoyl group, a mercapto group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C30 alkylmercapto group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaralkyl 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 can be fused to form a ring. For example, a substituted C6 to C30 aryl group can be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

[0071] In the present specification, when not otherwise provided by definition, "hetero" means including 1 to 3 heteroatoms selected from N, O, S, Se, and P.

[0072] In the present specification, "aryl" means a group comprising at least one hydrocarbon aromatic moiety, and includes hydrocarbon aromatic moieties connected by single bonds and hydrocarbon aromatic moieties directly or indirectly fused to provide non-aromatic fused rings. The aryl group can include a monocyclic, polycyclic, or fused polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional group.

[0073] In the present specification, "heterocyclic group" is a concept including heteroaryl, and can include at least one heteroatom selected from N, O, S, P, and Si in place of carbon (C) in a cyclic compound such as aryl, cycloalkyl, a fused ring thereof, or a combination thereof. When the heterocyclic group is a fused ring, the entire ring or each ring of the heterocyclic group can contain one or more heteroatoms.

[0074] More specifically, the substituted or unsubstituted aryl group can be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthraquinone, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted tetraphenyl, a substituted or unsubstituted pyrene, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted tetraphenyl, a substituted or unsubstituted trefene, a substituted or unsubstituted triphenylene, a substituted or unsubstituted perylene, a substituted or unsubstituted indene, a substituted or unsubstituted fluorenyl, a combination thereof, or a fused ring of the above groups, but is not limited thereto.

[0075] More specifically, the substituted or unsubstituted heterocyclic group can be a substituted or unsubstituted furanyl group, a substituted or unsubstituted phenylthio group, a substituted or unsubstituted pyrroleyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazoyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazoyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzophenylthio group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indoleyl group, or a substituted... The heterocyclic group may be an unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxolinyl group, a substituted or unsubstituted naphridyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridineyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenthiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiaphenyl group, a substituted or unsubstituted carbazoleyl group, a pyridindolyl group, a benzopyridinoxazinyl group, a benzopyridinthiazinyl group, a 9,9-dimethyl-9,10-dihydroacridinyl group, a combination thereof, or a combination of the above groups, but is not limited thereto. In one embodiment of the invention, the heterocyclic group or heteroaryl group may be a pyridylyl group, a carbazoleyl group, or a pyridindolyl group.

[0076] The following describes a hard mask composition according to one embodiment.

[0077] A hard mask composition according to one embodiment comprises a compound and a solvent.

[0078] The compound can include a core (A) that is an aromatic moiety, and the core (A) can be substituted with a substituent (B) that is a substituted or unsubstituted aromatic moiety. The substituent (B) can be a substituted phenyl, where the substituted phenyl can include a structure in which one or more aromatic rings and / or heterocyclic rings are connected by a single bond, a vinylene group, and / or an ethynylene group, and specifically can include a group represented by Chemical Formula 2, which will be described later. In addition, the compound can include one or more substituted or unsubstituted C3 to C30 heteroaryl groups; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkylthiol group, a substituted or unsubstituted C1 to C20 alkylamine group, or a combination thereof.

[0079] As one embodiment, the compound can be represented by Chemical Formula 1.

[0080] [Chemical Formula 1]

[0081]

[0082] In Chemical Formula 1,

[0083] A is a C6 to C30 aromatic moiety,

[0084] R 1 to R 5 each independently is hydrogen, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof, or a group represented by Chemical Formula 2,

[0085] R 1 to R 5 at least one of R

[0086] n is an integer greater than or equal to 2,

[0087] [Chemical Formula 2]

[0088]

[0089] where, in Chemical Formula 2,

[0090] X is a substituted or unsubstituted C6 to C30 arylene group,

[0091] Y is a substituted C6 to C60 aryl group or a substituted or unsubstituted C3 to C60 heteroaryl group, wherein the substituted C6 to C60 aryl group includes a substituent selected from the group consisting of a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

[0092] m is 0 or 1, and

[0093] represents a connection point with Chemical Formula 1.

[0094] For example, the compound represented by Chemical Formula 1 can be synthesized by a Diels-Alder reaction and an elimination reaction using a compound having a substituted diene and a substituted ethynyl moiety as a reactant, but is not limited thereto, and can include a functional group, for example, a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, or a substituted or unsubstituted C1 to C20 alkyl amine group, which is not favorable for the Diels-Alder reaction.

[0095] For example, the compound can be obtained from a compound including a C≡C triple bond and a cyclopentadienone, but is not limited thereto.

[0096] For example, A can be a non-condensed aromatic moiety, a condensed aromatic moiety, a moiety in which the aromatic moiety is connected by a single bond, a moiety in which each ring condensed to two non-parallel sides on the benzene ring is fused, a moiety in which each ring condensed to two non-parallel sides on the benzene ring is connected by a single bond or a double bond, or a combination thereof.

[0097] For example, A can be a benzene moiety, a naphthalene moiety, an anthracene moiety, a tetracene moiety, a pentacene moiety,

[0098] a biphenyl moiety, a terphenyl moiety, a quaterphenyl moiety, or a quinquephenyl moiety,

[0099] a phenanthrene moiety, a pyrene moiety, a fluoranthene moiety, a benzophenanthrene moiety, a chrysene moiety, a perylene moiety, a benzopyrene moiety, a dibenzoanthracene moiety, a benzofluoranthene moiety, a dibenzofluoranthene moiety, a benzoperylene moiety, a coronene moiety, a naphthanthracene moiety, or a triphenylene moiety.

[0100] When the compound includes the above-described aromatic moiety in the core (A), the carbon content of the compound can be increased to form a hard layer, and thus high corrosion resistance can be imparted.

[0101] For example, A can be a benzene moiety or a moiety in which a benzene moiety is connected by a single bond, and can be, for example, a benzene moiety, a biphenyl moiety, an ortho-terphenyl moiety, a meta-terphenyl moiety, or a para-terphenyl moiety, but is not limited thereto.

[0102] Due to the benzene moiety or the moiety in which a benzene moiety is connected by a single bond in the nucleus (A), high rotational freedom of the compound can be ensured, due to the high rotational freedom, solubility in a solvent is further improved, and a hard layer can be formed to impart higher etching resistance.

[0103] For example, A can be selected from any one of Group 1.

[0104] [Group 1]

[0105]

[0106] For example, A can be selected from any one of Group 1-1.

[0107] [Group 1-1]

[0108]

[0109] In Group 1-1, represents a connection point.

[0110] The compound has a substituent (B) which is a phenyl group substituted with at least one group represented by Chemical Formula 2 in the nucleus (A), and a fused structure is formed by a reaction of an aromatic moiety of the nucleus (A) with the substituent (B) connected thereto in the process of curing the compound, and thus a hard film layer containing condensed polycyclic aromatic hydrocarbons can be provided.

[0111] The substituent (B) is a phenyl group substituted with at least one group represented by Chemical Formula 2 connected to the nucleus (A), and can be the same as or different from each other, but desirably the same as each other, R 1 can be the same as or different from each other, but desirably the same as each other, R 2 can be the same as or different from each other, but desirably the same as each other, R 3 can be the same as or different from each other, but desirably the same, R 4 can be the same as or different from each other, R 5 can be the same as or different from each other, but desirably the same as each other, X can be the same as or different from each other, and Y can be the same as or different from each other, but desirably the same as each other.

[0112] For example, in R 1 to R 5In the definition, “substituted” for substituted or unsubstituted C6 to C30 aryl and substituted or unsubstituted C3 to C30 heteroaryl can mean substituted by: hydroxyl, mercapto, C1 to C30 alkyl, C1 to C30 alkoxy, C1 to C30 alkylthiol, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 aralkyl, C1 to C20 heteroalkyl, C3 to C20 heteroaralkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocyclic group, C1 to C30 ester group, C0 to C30 amino group, C1 to C20 alkylamino group, C1 to C30 thioester group, C1 to C30 sulfone group, halogen group or combinations thereof.

[0113] For example, in R 1 To R 5 In the definition, the substituted or unsubstituted C6 to C30 aryl group can be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthraquinone, a substituted or unsubstituted tetraphenyl, a substituted or unsubstituted pentaphenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted tetraphenyl, a substituted or unsubstituted pentaphenyl, a substituted or unsubstituted phenanthyl, a substituted or unsubstituted trefyl, a substituted or unsubstituted alizarin, or a substituted or unsubstituted aryl group. Triphenylene, substituted or unsubstituted pyrene, substituted or unsubstituted fluorenyl, substituted or unsubstituted fluoranthyl, substituted or unsubstituted acenaphthene, substituted or unsubstituted acenaphthene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted benzofluoranthyl, substituted or unsubstituted perylene, substituted or unsubstituted benzopyrene, substituted or unsubstituted naphthanethyl, substituted or unsubstituted benzoperylene, substituted or unsubstituted dibenzopyrene, substituted or unsubstituted crownenyl, or combinations thereof,

[0114] In R 1 To R 5 In the definition, the substituted or unsubstituted C3 to C30 heteroaryl group can be a substituted or unsubstituted pyrroleyl group, a substituted or unsubstituted indoleyl group, a substituted or unsubstituted carbazoyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazineyl group, a substituted or unsubstituted imidazoyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted isoindoleyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indazoleyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazoyl group, or a combination thereof.

[0115] For example, in the definition of R 1 to R 5 , the substituted or unsubstituted C6 to C30 aryl can be a substituted or unsubstituted C6 to C30 condensed aryl or a substituted or unsubstituted C6 to C30 non-condensed aryl, but can be a substituted or unsubstituted C6 to C30 non-condensed aryl, and

[0116] For example, in the definition of R 1 to R 5 , the substituted or unsubstituted C3 to C30 heteroaryl can be a substituted or unsubstituted C3 to C30 condensed heteroaryl or a substituted or unsubstituted C3 to C30 non-condensed heteroaryl, but desirably can be a substituted or unsubstituted C3 to C30 non-condensed heteroaryl.

[0117] Accordingly, the compound can ensure a high rotational freedom, and due to the high rotational freedom, can have improved solubility in a solvent, and can provide a hard layer to impart higher etch resistance.

[0118] For example, in the definition of R 1 to R 5 , the substituted or unsubstituted C3 to C30 heteroaryl can include at least one nitrogen.

[0119] For example, in the definition of R 1 to R 5 , the substituted or unsubstituted C3 to C30 heteroaryl can include one nitrogen, two nitrogens, or three nitrogens.

[0120] For example, R 1 to R 5 may each independently be hydrogen or a substituted or unsubstituted group selected from Group 2.

[0121] [Group 2]

[0122]

[0123] For example, R 1 to R 5 may each independently be hydrogen or a substituted or unsubstituted group selected from Group 2-1.

[0124] [Group 2-1]

[0125]

[0126] In Group 2-1, denotes a point of attachment.

[0127] In Group 2 and Group 2-1, each group can be unsubstituted or substituted with one or more substituents. In this context, a substituent can be, for example, a hydroxyl group, a mercapto group, a Ci to C30 alkyl group, a Ci to C30 alkoxy group, a Ci to C30 alkyl thiol group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a Ci to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclic group, a Ci to C30 ester group, a Co to C30 amine group, a Ci to C20 alkyl amine group, a Ci to C30 thioester group, a Ci to C30 sulfone group, a halogen, or a combination thereof.

[0128] For example, R 1 , R 2 , R 4 , and R 5 may each independently be hydrogen, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof.

[0129] For example, R 1 , R 2 , R 4 , and R 5 may each independently be hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted acenaphthenyl group, a substituted or unsubstituted acenaphthyl group, or a combination thereof.

[0130] For example, at least one of R 1 to R 5 may be a substituted or unsubstituted phenyl group. For example, 1 to 3 of R 1 to R 5 may be a substituted or unsubstituted phenyl group. For example, one or two of R 1 to R 5 may be a substituted or unsubstituted phenyl group.

[0131] For example, R 1 and R 4 may each independently be a substituted or unsubstituted phenyl group, but are desirably unsubstituted phenyl groups.

[0132] For example, at least one of R 1 to R 5 may be hydrogen.

[0133] For example, R 5 may be hydrogen.

[0134] For example, R 1 and R 4 may each independently be a substituted or unsubstituted phenyl group, and R 5 may be hydrogen.

[0135] As described above, at least one of R 1 to R 5 may be a group represented by Chemical Formula 2. Thus, because the compound contains a hydrophilic functional group and ensures a high rotational freedom, the solubility of the compound in a solvent can be increased even if the compound has a high molecular weight. In addition, the compound contains a plurality of aromatic moieties, which can increase the carbon content, and thus can provide higher etch resistance.

[0136] For example, R 3 may be a group represented by Chemical Formula 2. Since R 3 is a group represented by Chemical Formula 2, the compound can not only ensure a higher rotational freedom, but also form a harder layer during curing, providing higher etch resistance.

[0137] For example, R 1 , R 2 , R 4 , and R 5 may each independently be hydrogen or a substituted or unsubstituted group selected from Group 2, and R 3 may be a group represented by Chemical Formula 2.

[0138] For example, R 1 , R 2 , R 4 , and R 5 may each independently be hydrogen or a substituted or unsubstituted group selected from Group 2-1, and R 3 may be a group represented by Chemical Formula 2.

[0139] For example, R 1 , R 2 , R 4 , and R 5 may each independently be hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted acenaphthenyl group, a substituted or unsubstituted acenaphthyl group, or a combination thereof, and R 3 may be a group represented by Chemical Formula 2.

[0140] For example, R 1 and R 4 may each independently be a substituted or unsubstituted phenyl group, R 5may be hydrogen, and R 3 may be a group represented by Chemical Formula 2.

[0141] For example, X can be a substituted or unsubstituted C6 to C30 arylene, and desirably an unsubstituted C6 to C30 arylene as described above.

[0142] For example, X can be a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted anthrylene, a substituted or unsubstituted tetracenylene, a substituted or unsubstituted pentacenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted quaterphenylene, a substituted or unsubstituted quinquephenylene, or a combination thereof.

[0143] For example, X can be any one substituted or unsubstituted selected from Group 3, and in Group 3, each moiety can be unsubstituted or substituted with one or more substituents.

[0144] [Group 3]

[0145]

[0146] In Group 3, represents a point of attachment.

[0147] For example, in the definition of Y, “substituted” in substituted C6 to C60 aryl and substituted or unsubstituted C3 to C60 heteroaryl can mean substituted with a hydroxyl, a mercapto, a C1 to C30 alkyl, a C1 to C30 alkoxy, a C1 to C30 alkylthiol, a C2 to C30 alkenyl, a C2 to C30 alkynyl, a C6 to C30 aryl, a C7 to C30 aralkyl, a C1 to C20 heteroalkyl, a C3 to C20 heteroaralkyl, a C3 to C30 cycloalkyl, a C3 to C15 cycloalkenyl, a C6 to C15 cycloalkynyl, a C2 to C30 heterocyclyl, a C1 to C30 ester, a C0 to C30 amine, a C1 to C20 alkylamine, a C1 to C30 thioester, a C1 to C30 sulfone, a halogen, or a combination thereof.

[0148] Specifically, in the definition of Y, the substituted C6 to C60 aryl group can include at least one substituent selected from a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted isoindolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, or a combination thereof.

[0149] Accordingly, the solubility of the compound to a solvent can be increased, so that the compound can be more effectively applied to a solution process such as spin coating, and when coated and cured, the affinity to an underlying film is increased, which can not only greatly improve the film flatness of a film formed therefrom, but the film can exhibit high etch resistance to etching gas exposed thereto during a subsequent process such as an etching process.

[0150] For example, in the definition of Y, the substituted or unsubstituted C3 to C60 heteroaryl group can be a substituted or unsubstituted C3 to C40 heteroaryl group or a substituted or unsubstituted C3 to C30 heteroaryl group, and can be specifically selected from a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzobenzothiophenyl group, a substituted or unsubstituted dibenzobenzothiophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted isoindolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, or a combination thereof, but is not limited thereto.

[0151] For example, in the definition of Y, the substituted C6 to C60 aryl group can be a substituted C6 to C40 aryl group or a substituted C6 to C30 aryl group, and can be specifically selected from a substituted phenyl group, a substituted naphthyl group, a substituted anthryl group, a substituted tetracenyl group, a substituted pentacenyl group, a substituted biphenyl group, a substituted terphenyl group, a substituted quaterphenyl group, a substituted quinphenyl group, a substituted phenanthryl group, a substituted chrysenyl group, a substituted xanthenyl group, a substituted acenaphthylenyl group, a substituted acenaphthyl group, a substituted phenanthrylenyl group, a substituted fluoranthenyl group, a substituted fluoranthenyl group, a substituted coronenyl group, a substituted pyrenyl group, a substituted benzofluorenyl group, a substituted benzofluoranthenyl group, a substituted perylenyl group, a substituted benzopyrenyl group, a substituted naphthacene group, a substituted benzoperylenyl group, a substituted dibenzopyrenyl group, a substituted coronamyl group, or a combination thereof, but is not limited thereto.

[0152] For example, in the definition of Y, the substituted C6 to C60 aryl group can be a fused ring or a non-fused ring, and the substituted or unsubstituted C3 to C60 heteroaryl group can be a fused heterocycle or a non-fused heterocycle.

[0153] For example, in the definition of Y, the substituted or unsubstituted C3 to C60 heteroaryl group can include at least one nitrogen.

[0154] For example, in the definition of Y, the substituted or unsubstituted C3 to C60 heteroaryl group can include one nitrogen, two nitrogens, or three nitrogens.

[0155] For example, in the definition of Y, the substituted or unsubstituted C3 to C60 heteroaryl group can be any substituted or unsubstituted group selected from Group 4, and the substituted C6 to C60 aryl group can be any substituted one selected from Group 5.

[0156] [Group 4]

[0157]

[0158] [Group 5]

[0159]

[0160] For example, in Y, the substituted or unsubstituted C3 to C60 heteroaryl group can be any substituted or unsubstituted group selected from Group 4-1, and the substituted C6 to C60 aryl group can be any substituted one selected from Group 5-1.

[0161] [Group 4-1]

[0162]

[0163] [Group 5-1]

[0164]

[0165] In Group 4-1 and Group 5-1, represents a connecting point.

[0166] For example, the group represented by Chemical Formula 2 can be represented by Chemical Formula 3 or 4.

[0167]

[0168]

[0169] In Chemical Formula 3 and Chemical Formula 4, X and Y are the same as described above,

[0170] R 6 to R 10 each independently is hydrogen, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,

[0171] R 6 to R 10 at least one of R is a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl group; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof, and

[0172] represents a connecting point to Chemical Formula 1.

[0173] For example, Y of Chemical Formula 3 can be a substituted or unsubstituted C3 to C30 heteroaryl group; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof.

[0174] For example, Y of Chemical Formula 3 can be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl group selected from Group 4; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof, selected from Group 5.

[0175] For example, Y of Chemical Formula 3 can be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl group selected from Group 4-1; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof, selected from Group 5-1.

[0176] For example, Y of Chemical Formula 3 can be a substituted or unsubstituted C3 to C30 heteroaryl; or a C6 to C30 aryl substituted with a hydroxyl, amine, thiol, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or combinations thereof.

[0177] In Chemical Formula 4, R 6 to R 10 include a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl; or a C6 to C30 aryl substituted with a hydroxyl, amine, thiol, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkylthiol, substituted or unsubstituted C1 to C20 alkylamine, or combinations thereof, to further improve solubility in solvents when the compound is cured and can provide a harder layer.

[0178] For example, in the definition of R 6 to R 10 of Chemical Formula 4, the “substituted” of the substituted or unsubstituted C6 to C30 aryl and the substituted or unsubstituted C3 to C30 heteroaryl can refer to substitution with a hydroxyl, thiol, C1 to C30 alkyl, C1 to C30 alkoxy, C1 to C30 alkylthiol, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 aralkyl, C1 to C20 heteroalkyl, C3 to C20 heteroaralkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocyclyl, C1 to C30 ester, C0 to C30 amine, C1 to C20 alkylamine, C1 to C30 thioester, C1 to C30 sulfone, halogen, or combinations thereof.

[0179] For example, in the definition of R 6 to R 10In the definition, the substituted or unsubstituted C6 to C30 aryl group can be selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraquinone, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pentaphenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pentaphenyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted trefyl, substituted or unsubstituted alizarin, substituted or unsubstituted aryl group, etc. Substituted triphenylene, substituted or unsubstituted pyrene, substituted or unsubstituted fluorenyl, substituted or unsubstituted fluoranthyl, substituted or unsubstituted acenaphthene, substituted or unsubstituted acenaphthene, substituted or unsubstituted benzophenanthrene, substituted or unsubstituted benzofluoranthyl, substituted or unsubstituted perylene, substituted or unsubstituted benzopyrene, substituted or unsubstituted naphthanethyl, substituted or unsubstituted benzoperylene, substituted or unsubstituted dibenzopyrene, substituted or unsubstituted crownenyl, or combinations thereof,

[0180] In chemical formula 4, R 6 To R 10 In the definition, the substituted or unsubstituted C3 to C30 heteroaryl group may be selected from substituted or unsubstituted pyrrole, substituted or unsubstituted indole, substituted or unsubstituted carbazolyl, substituted or unsubstituted furanyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted phenylthio, substituted or unsubstituted benzophenylthio, substituted or unsubstituted dibenzophenylthio, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted imidazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted isoindole, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indazole, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, or combinations thereof.

[0181] For example, in chemical formula 4, R 6 To R 10 In the definition, the substituted or unsubstituted C6 to C30 aryl group can be a substituted or unsubstituted C6 to C30 condensed aryl group or a substituted or unsubstituted C6 to C30 noncondensed aryl group, and the substituted or unsubstituted C3 to C30 heteroaryl group can be a substituted or unsubstituted C3 to C30 condensed heteroaryl group or a substituted or unsubstituted C3 to C30 noncondensed heteroaryl group.

[0182] For example, in chemical formula 4, R 6 To R 10 In the definition, substituted or unsubstituted C3 to C30 heteroaryl groups may contain at least one nitrogen atom.

[0183] For example, in the definition of R 6 to R 10 , the substituted or unsubstituted C3 to C30 heteroaryl group can contain one nitrogen, two nitrogens, or three nitrogens.

[0184] For example, in the definition of R 6 to R 10 , the substituted or unsubstituted C3 to C30 heteroaryl group can be a C3 to C30 nitrogen-containing heteroaryl group selected from Group 6, and the substituted or unsubstituted C6 to C30 aryl group can be a C6 to C30 aryl group selected from Group 7.

[0185] [Group 6]

[0186]

[0187] [Group 7]

[0188]

[0189] For example, in the definition of R 6 to R 10 , the substituted or unsubstituted C3 to C30 heteroaryl group can be a C3 to C30 nitrogen-containing heteroaryl group selected from Group 6-1, and the substituted or unsubstituted C6 to C30 aryl group can be a C6 to C30 aryl group selected from Group 7-1.

[0190] [Group 6-1]

[0191]

[0192] [Group 7-1]

[0193]

[0194] In Groups 6-1 and 7-1, represents a point of attachment.

[0195] In Groups 6, 7, 6-1, and 7-1, each group can be unsubstituted or substituted with one or more substituents.

[0196] For example, at least one of R 7 , R 8 , and R 10 in Chemical Formula 4 can be a substituted or unsubstituted C3 to C30 heteroaryl group; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof.

[0197] For example, R6 to R 10 may each independently be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6 or a substituted or unsubstituted C6 to C30 aryl selected from Group 7, and

[0198] In Chemical Formula 4, R 7 , R 8 , and R 10 may each independently be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6 or a substituted or unsubstituted C6 to C30 aryl selected from Group 7, and

[0199] For example, R 6 to R 10 may each independently be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6-1 or a substituted or unsubstituted C6 to C30 aryl selected from Group 7-1, and

[0200] In Chemical Formula 4, R 7 , R 8 , and R 10 may each independently be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6-1 or a substituted or unsubstituted C6 to C30 aryl selected from Group 7-1, and

[0201] For example, R 8 may be a C6 to C30 aryl substituted with a hydroxyl, amine, mercapto, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl mercaptan, substituted or unsubstituted C1 to C20 alkyl amine, or a combination thereof, selected from Group 7, and

[0202] R 10 of Chemical Formula 4 may be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl selected from Group 6 or a C6 to C30 aryl substituted with a hydroxyl, amine, mercapto, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl mercaptan, substituted or unsubstituted C1 to C20 alkyl amine, or a combination thereof, selected from Group 7.

[0203] For example, R 8may be a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof, selected from Group 7-1, and

[0204] R of Chemical Formula 4 10 may be a substituted or unsubstituted C3 to C30 nitrogen-containing heteroaryl group selected from Group 6-1; or a C6 to C30 aryl group substituted with a hydroxyl group, an amine group, a mercapto group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl mercaptan group, a substituted or unsubstituted C1 to C20 alkyl amine group, or a combination thereof, selected from Group 7-1.

[0205] For example, R of Chemical Formula 4 8 may be a methoxyphenyl group, a methoxynaphthyl group, a methoxyanthryl group, a methoxyl biphenyl group, a methoxytriphenyl group, or a methoxyphenalenyl group, and

[0206] R of Chemical Formula 4 10 may be a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrimidyl group, a methoxyphenyl group, a methoxynaphthyl group, a methoxyanthryl group, a methoxyl biphenyl group, a methoxytriphenyl group, or a methoxyphenalenyl group.

[0207] For example, in Chemical Formula 4, R 6 to R 10 may be a substituted or unsubstituted phenyl group, for example, R 6 to R 10 one to three of R 6 to R 10 may be a substituted or unsubstituted phenyl group.

[0208] For example, R 6 and R 9 of Chemical Formula 4 may each independently be a substituted or unsubstituted phenyl group, but desirably an unsubstituted phenyl group.

[0209] For example, in Chemical Formula 4, all of R 6 to R 10 may not be hydrogen, or only one can be hydrogen, and desirably, all of R 6 to R 10 may not be hydrogen. Thus, since the carbon content of the compound can be further increased, a hard layer can be formed, and thus high etch resistance can be imparted.

[0210] For example, R 6 to R 10They can exist independently, or two adjacent groups can connect to each other to form a ring, and specifically, R 1 To R 5 Two adjacent groups in a ring can be connected by a single or double bond, or two adjacent groups can fused together to form a ring.

[0211] For example, R in chemical formula 4 7 and R 8 They can exist independently, connected by single or double bonds, or two adjacent groups can fused together to form a ring.

[0212] For example, n can be an integer satisfying the range 2≤n≤k / 2, and k can be the number of substituted positions of A in chemical formula 1.

[0213] For example, when A is a substituted or unsubstituted benzene moiety, n can be 2 or 3; when A is a substituted or unsubstituted naphthalene moiety, n can be an integer greater than 2 and less than 4; when A is a substituted or unsubstituted anthracene moiety, n can be an integer greater than 2 and less than 5; when A is a substituted or unsubstituted pyrene moiety, n can be an integer greater than 2 and less than 5; when A is a substituted or unsubstituted triphenylene moiety, n can be an integer greater than 2 and less than 6; when A is a substituted or unsubstituted biphenyl moiety, n can be an integer greater than 2 and less than 5; and when A is a substituted or unsubstituted terphenyl moiety, n can be an integer greater than 2 and less than 7.

[0214] For example, A can be an integer from 2 to 4, 3 or 4.

[0215] The compounds described above may have molecular weights of, for example, about 900 to 7,000 g / mol, about 1,000 to 6,000 g / mol, or about 1,500 to 5,000 g / mol, but are not limited thereto.

[0216] Typically, when using compounds containing multiple aromatic moieties but with molecular weights within this range, pinholes and voids may form or the thickness distribution may decrease during the baking process, resulting in a non-uniform film. However, the compound represented by Formula 1, with a molecular weight within this range, can form a more uniform film without forming pinholes and voids or decreasing the thickness distribution during the baking process. Furthermore, because the film is formed as a hard layer, it exhibits high resistance to etching gases exposed in subsequent processes, such as etching processes.

[0217] On the other hand, the solvent used in the hard mask composition can be any solvent with respect to the compound having sufficient solubility or dispersibility, and can include, for example, at least one selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropylene glycol, 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-dimethylacetamide, methylpyrrolidone, acetylacetone, and 3-ethoxypropyl acetate, but is not limited thereto.

[0218] The compound can be included in an amount of, for example, about 0.01 to 30 wt%, for example, about 1 to 25 wt%, about 3 to 20 wt%, or about 5 to 15 wt%, based on the total amount of the hard mask composition. When the compound is included within this range, the thickness, surface roughness, and planarization of the hard mask can be controlled.

[0219] The hard mask composition can further include an additive of a surfactant, a crosslinking agent, a thermal acid generator, or a plasticizer.

[0220] The surfactant can include, for example, a fluoroalkyl-based compound, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

[0221] The crosslinking agent can be, for example, a melamine-based, a substituted urea-based, or a polymer-based crosslinking agent. Desirably, it can be a crosslinking agent having at least two crosslink-forming substituents, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea, etc.

[0222] The crosslinking agent can be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance can be a compound including a crosslinking substituent containing an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule.

[0223] The thermal acid generator can be, for example, an acidic compound such as p-toluenesulfonic acid, triflic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carbonic acid, etc., or / and 2,4,4,6-tetrabromocyclohexadienone, benzosulfonic acid ester, 2-nitrophenyl toluenesulfonate, other organic sulfonic acid alkyl ester, etc., but is not limited thereto.

[0224] The additive can be included in an amount of about 0.001 to 10 parts by weight, about 0.01 to 5 parts by weight, or about 0.05 to 1 part by weight, based on 100 parts by weight of the hard mask composition. Within this range, solubility can be improved while not changing the optical properties of the hard mask composition.

[0225] According to another embodiment, there is provided an organic film produced using the hard mask composition. The organic film can be formed, for example, by coating the hard mask composition on a substrate and heat-treating it for curing, and can include, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, etc. for electronic devices.

[0226] According to another embodiment, there is provided a hard mask layer including a cured product of the above-described hard mask composition.

[0227] For example, the cured product includes condensed polycyclic aromatic hydrocarbons.

[0228] For example, the condensed polycyclic aromatic hydrocarbons can be substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted tetracene, substituted or unsubstituted pyrene, substituted or unsubstituted benzopyrene, substituted or unsubstituted chrysene, substituted or unsubstituted triphenylene, substituted or unsubstituted perylene, substituted or unsubstituted benzofluoranthene, substituted or unsubstituted benzo-perylene, substituted or unsubstituted coronene, combinations thereof, or combinations of the above groups, but are not limited thereto.

[0229] For example, the cured product can further include a heterocycle.

[0230] For example, the cured product can further include a heterocycle containing at least one nitrogen atom.

[0231] For example, the cured product can further include a heterocycle containing one nitrogen atom, a heterocycle containing two nitrogen atoms, and a heterocycle containing three nitrogen atoms.

[0232] Since the cured product includes condensed polycyclic aromatic hydrocarbons, it can exhibit high etch resistance and chemical resistance to resist etching gases and chemical liquids exposed in subsequent processes including an etching process.

[0233] Hereinafter, a pattern forming method using the above-described hard mask composition is described.

[0234] The pattern forming method according to one embodiment includes forming a material layer on a substrate; applying a hard mask composition including the above-described compound and a solvent on the material layer; heat-treating the hard mask composition to form a hard mask layer; forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer; and etching the exposed portion of the material layer.

[0235] The substrate can be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

[0236] The material layer is a finally patterned material, for example, a metal layer such as an aluminum layer and a copper layer, a semiconductor layer such as a silicon layer, or an insulating layer such as a silicon oxide layer and a silicon nitride layer. The material layer can be formed by a method such as a chemical vapor deposition (CVD) process.

[0237] The hard mask composition is the same as described above, and can be applied in the form of a solution by spin coating. In this context, the thickness of the hard mask composition is not particularly limited, but can be, for example, about 10 nm to 1 μm. to

[0238] For example, the heat treatment of the hard mask composition can be performed at about 100 to 700°C for about 10 seconds to 1 hour.

[0239] For example, the method can further include forming a silicon-containing thin layer on the hard mask layer. The silicon-containing thin layer can be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and / or SiN, etc.

[0240] For example, the method can further include forming a bottom anti-reflective coating (BARC) on an upper surface of the silicon-containing thin layer or on the upper surface hard mask layer before forming the photoresist layer.

[0241] The exposure of the photoresist layer can be performed using, for example, ArF, KrF, or EUV. After the exposure, a heat treatment can be performed at about 100 to 700°C.

[0242] The etching process of the exposed portion of the material layer can be performed by a dry etching process using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, BCl3, and a mixed gas thereof.

[0243] The etched material layer can be formed into a plurality of patterns, and the plurality of patterns can be a metal pattern, a semiconductor pattern, an insulating pattern, etc., for example, different patterns of a semiconductor integrated circuit device. DETAILED DESCRIPTION

[0245] Hereinafter, the embodiments are explained in more detail with reference to examples. However, these examples are exemplary, and the scope is not limited thereto.

[0246] Preparation of hard mask composition

[0247] Example 1

[0248] After placing a stirrer in a 60 mL vial, 1,3,5-triethynylbenzene (150 mg), 2,4,5-triphenyl-3-(4-pyridylethynyl)phenylcyclopentadienone (1.46 g), and propylene glycol monomethyl ether acetate (PGMEA, 4 mL) were placed therein, and then the reaction was performed while stirring at 150°C for 3 hours, to synthesize a compound represented by Chemical Formula 1a. Subsequently, the mixture was cooled to room temperature, PGMEA (5 ml) was further added thereto, and then filtered with a TEFLON (tetrafluoroethylene) filter (pore size: 0.1 µm) to prepare a hard mask composition. (MW: 1,526 g / mol)

[0249] [Chemical Formula 1a]

[0250]

[0251] Example 2

[0252] After placing a stirrer in a 60 mL vial, 1,3,5-triethynylbenzene (150 mg), 2,5-diphenyl-3-(4-pyridylethynyl)phenyl-4-biphenylcyclopentadienone (1.69 g), and PGMEA (5 mL) were placed therein, and then the reaction was performed while stirring at 150°C for 3 hours, to synthesize a compound represented by Chemical Formula 2a. Subsequently, the mixture was cooled to room temperature, PGMEA (7 ml) was further added thereto, and then filtered with a TEFLON (tetrafluoroethylene) filter (pore size: 0.1 µm) to prepare a hard mask composition. (MW: 1,754 g / mol)

[0253] [Chemical Formula 2a]

[0254]

[0255] Example 3

[0256] After placing a stirrer in a 60 mL vial, 1,3,5-triethynylbenzene (150 mg), 2,4,5-triphenyl-3-(4-methoxynaphthylethynyl)phenylcyclopentadienone (1.69 g), and PGMEA (5 mL) were placed therein, and then the reaction was performed while stirring at 150°C for 3 hours, to synthesize a compound represented by Chemical Formula 3a. Subsequently, the mixture was cooled to room temperature, PGMEA (7 ml) was further added thereto, and then filtered with a TEFLON (tetrafluoroethylene) filter (pore size: 0.1 µm) to prepare a hard mask composition. (MW: 1,760 g / mol)

[0257] [Chemical Formula 3a]

[0258]

[0259] Example 4

[0260] After placing a stirrer in a 60 mL vial, a compound represented by Chemical Formula 1a (1.53 g) obtained by drying the mixture of Example 1, 2,4,5-triphenyl-3-[2-(6-methoxy)naphthyl]cyclopentadienone (1.39 g), and PGMEA (8 mL) were placed therein, and then, the reaction was performed while stirring at 250°C for 3 hours to synthesize a compound represented by Chemical Formula 4a. Subsequently, the mixture was cooled to room temperature, and further, 11 ml of PGMEA was added thereto, and then, filtered with a TEFLON (tetrafluoroethylene) filter (pore diameter: 0.1 μm) to prepare a hard mask composition. (MW: 2,836 g / mol)

[0261] [Chemical Formula 4a]

[0262]

[0263] Example 5

[0264] After placing a stirrer in a 60 mL vial, a compound represented by Chemical Formula 2a (1.75 g) obtained by drying the mixture of Example 2, 2,5-diphenyl-3,4-di[2-(6-methoxy)naphthyl]cyclopentadienone (1.63 g), and PGMEA (9 mL) were placed therein, and then, the reaction was performed while stirring at 250°C for 3 hours to synthesize a compound represented by Chemical Formula 5a. Subsequently, the mixture was cooled to room temperature, and further, 12 ml of PGMEA was added thereto, and then, filtered with a TEFLON (tetrafluoroethylene) filter (pore diameter: 0.1 μm) to prepare a hard mask composition. (MW: 3,076 g / mol)

[0265] [Chemical Formula 5a]

[0266]

[0267] Example 6

[0268] After placing a stirrer in a 60 mL vial, 3,3',5'5'-tetraethynyl biphenyl (250 mg), 2,5-diphenyl-3-(4-pyridyl ethynyl)phenyl-4-biphenyl cyclopentadienone (2.25 g), and PGMEA (7 mL) were placed therein, and then, the reaction was performed while stirring at 150°C for 3 hours to synthesize a compound represented by Chemical Formula 6a. Subsequently, the mixture was cooled to room temperature, and further, PGMEA (9 ml) was added thereto, and then, filtered with a TEFLON (tetrafluoroethylene) filter (pore diameter: 0.1 μm) to prepare a hard mask composition. (MW: 2,389 g / mol)

[0269] [Chem. 6a]

[0270]

[0271] Example 7

[0272] After placing a stirrer in a 60 mL vial, 3,3',5'5'-tetraethynylbiphenyl (250 mg), 2,4,5-triphenyl-3-(4-methoxynaphthylacetylenyl)phenylcyclopentadienone (2.26 g), and PGMEA (7 mL) were placed therein, and then, a compound represented by Chemical Formula 7a was synthesized while reacting for 3 hours with stirring at 150°C. Subsequently, the mixture was cooled to room temperature, and further PGMEA (9 ml) was added thereto, and then, a hard mask composition was prepared by filtering with a TEFLON (tetrafluoroethylene) filter (pore size: 0.1 μm). (MW: 2,397 g / mol)

[0273] [Chem. 7a]

[0274]

[0275] Example 8

[0276] After placing a stirrer in a 60 mL vial, a compound represented by Chemical Formula 6a (2.39 g) obtained by drying the mixture of Example 6, 2,5-diphenyl-3,4-di[2-(6-methoxynaphthyl)]cyclopentadienone (2.18 g), and PGMEA (13 mL) were placed therein, and then, a compound represented by Chemical Formula 8a was synthesized while reacting for 3 hours with stirring at 250°C. Subsequently, the mixture was cooled to room temperature, and further PGMEA (17 ml) was added thereto, and then, a hard mask composition was prepared by filtering with a TEFLON (tetrafluoroethylene) filter (pore size: 0.1 μm). (MW: 4,456 g / mol)

[0277] [Chem. 8a]

[0278]

[0279] Example 9

[0280] After placing a stirrer in a 60 mL vial, a compound represented by Chemical Formula 7a (2.40 g) obtained by drying the mixture of Example 7, 2,5-diphenyl-3,4-di[2-(6-methoxy)naphthyl]cyclopentadienone (2.18 g), and PGMEA (13 mL) were placed therein, and then, the reaction was performed while stirring at 250°C for 3 hours to synthesize a compound represented by Chemical Formula 9a. Subsequently, the mixture was cooled to room temperature, and further PGMEA (17 ml) was added thereto, and then, filtered with a TEFLON (tetrafluoroethylene) filter (pore diameter: 0.1 μm) to prepare a hard mask composition. (MW: 4,464 g / mol)

[0281] [Chemical Formula 9a]

[0282]

[0283] Comparative Example 1

[0284] After placing a stirrer in a 60 mL vial, 1,3,5-triethynylbenzene (150 mg), 2,4,5-triphenyl-3-(4-phenylethynyl)phenylcyclopentadienone (1.45 g), and PGMEA (4 mL) were placed therein, and then, the reaction was performed while stirring at 150°C for 3 hours to synthesize a compound represented by Chemical Formula A. Subsequently, the mixture was cooled to room temperature, and further PGMEA (5 ml) was added thereto, and then, filtered with a TEFLON (tetrafluoroethylene) filter (pore diameter: 0.45 μm) to prepare a hard mask composition. (MW: 1,520 g / mol)

[0285] [Chemical Formula A]

[0286]

[0287] Comparative Example 2

[0288] After placing a stirrer in a 60 mL vial, 3,3',5,5'-tetraethynylbiphenyl (250 mg), 2,4,5-triphenyl-3-(4-phenylethynyl)phenylcyclopentadienone (1.94 g), and PGMEA (6 mL) were placed therein, and then, the reaction was performed while stirring at 150°C for 3 hours to synthesize a compound represented by Chemical Formula B. Subsequently, the mixture was cooled to room temperature, and further PGMEA (8 ml) was added thereto, and then, filtered with a TEFLON (tetrafluoroethylene) filter (pore diameter: 0.45 μm) to prepare a hard mask composition. (MW: 2,077 g / mol)

[0289] [Chemical Formula B]

[0290]

[0291] Comparative Example 3

[0292] After placing a stirrer in a 60 mL vial, 1.52 g of the compound represented by chemical formula A, obtained by drying the mixture of Comparative Example 1, tetraphenylcyclopentadienone (1.15 g), and PGMEA (7 mL), was added. The reaction was then carried out with stirring at 250 °C for 3 hours to synthesize the compound represented by chemical formula C. Subsequently, the mixture was cooled to room temperature, and 8 mL of PGMEA was added. The mixture was then filtered through a TEFLON (tetrafluoroethylene) filter (pore size: 2.7 μm) to prepare a hard mask composition. (MW: 2,589 g / mol)

[0293] [Chemical formula C]

[0294]

[0295] Comparative Example 4

[0296] After placing a stirrer in a 60 mL vial, 2.08 g of the compound represented by chemical formula B, obtained by drying the mixture of Comparative Example 2, tetraphenylcyclopentadienone (1.54 g), and PGMEA (9 mL), was added. The reaction was then carried out with stirring at 250 °C for 3 hours to synthesize the compound represented by chemical formula D. Subsequently, the mixture was cooled to room temperature, and 12 mL of PGMEA was further added. The mixture was then filtered through a TEFLON (tetrafluoroethylene) filter (pore size: 2.7 μm) to prepare a hard mask composition. (MW: 3,503 g / mol)

[0297] [Chemical formula D]

[0298]

[0299] Formation of organic film

[0300] The hard mask compositions according to Examples 1 to 9 and Comparative Examples 1 to 4 were spin-coated onto the following silicon wafers, cured for 30 minutes in a UV curing machine under a nitrogen atmosphere, and heat-treated at 550°C for 2 minutes under a nitrogen atmosphere to form each to A thick organic film.

[0301] Evaluation: etch resistance

[0302] The organic films formed from the hard mask compositions according to Examples 1 to 9 and Comparative Examples 1 to 4 were checked for delamination, and then the thickness of the organic films was measured. Subsequently, the thickness of the organic films was measured using CF... xThe mixed gas dry-etched the organic film for 100 seconds, and then measured the thickness thereof after dry-etching.

[0303] The thickness difference of each organic film before and after dry-etching and the etching time were used to calculate the bulk etch rate (BER) according to calculation equation 1.

[0304] [Calculation Equation 1]

[0305]

[0306] The results are shown in Table 1.

[0307] [Table 1]

[0308]

[0309] Referring to Table 1, the organic films according to Comparative Examples 1 to 4 delaminated and were not uniform, and thus were not suitable for use as a hard mask, and thus, it was not possible to measure the thickness thereof and thus it was difficult to evaluate the etch resistance.

[0310] On the other hand, the organic films according to Examples 1 to 9 did not delaminate but were uniform, and thus exhibited sufficient etch resistance to the etching gas.

[0311] While the present application has been described in connection with what is presently considered to be the actual exemplary embodiments, it is to be understood that the application is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A hard mask composition comprising a compound represented by Chemical Formula 1 and a solvent: [Chemical Formula 1] in Chemical Formula 1, A is a C 6 to C 30 aromatic moiety, wherein, in Chemical Formula 3 and Chemical Formula 4, X is a substituted or unsubstituted C 6 to C 30 arylene, Y is a substituted or unsubstituted C 3 to C 30 heteroaryl; or a C 6 to C 30 aryl substituted with a hydroxyl, an amine, a mercapto, a substituted or unsubstituted C 1 to C 30 alkoxy, a substituted or unsubstituted C 1 to C 30 alkyl thiol, a substituted or unsubstituted C 1 to C 20 alkyl amine, or a combination thereof. 2.The hard mask composition according to claim 1, wherein A is a benzene moiety, a naphthalene moiety, an anthracene moiety, a tetracene moiety, a pentacene moiety, a biphenyl moiety, a terphenyl moiety, a quaterphenyl moiety, or a quinquephenyl moiety, a phenanthrene moiety, a pyrene moiety, a fluoranthene moiety, a benzophenanthrene moiety, a chrysene moiety, a perylene moiety, a benzopyrene moiety, a dibenzoanthracene moiety, a benzofluoranthene moiety, a dibenzofluoranthene moiety, a benzo-perylene moiety, a coronene moiety, a naphthanthracene moiety, or a triphenylene moiety. wherein 3.The hard mask composition according to claim 1, wherein A is any one selected from Group 1: [Group 1] 4.The hard mask composition according to claim 1, wherein A is any one selected from Group 2: [Group 2] R 1 to R 5 each independently is hydrogen, substituted or unsubstituted C6to C30aryl, substituted or unsubstituted C3to C30heteroaryl, or a combination thereof, or a group represented by Formula 3 or Formula 4, wherein R 1 at least two of R 5 at least two of the groups are other than hydrogen, and wherein at least one of the at least two groups is a group represented by Formula 3 or Formula 4, 5.The hard mask composition according to claim 1, wherein A is any one selected from Group 3: [Group 3] 6.The hard mask composition according to claim 1, wherein A is any one selected from Group 4: [Group 4] 7.The hard mask composition according to claim 1, wherein Y of Chemical Formula 3 is a substituted or unsubstituted C 3 to C 30 nitrogen-containing heteroaryl selected from Group 4; or a C 6 to C 30 aryl substituted with a hydroxyl, an amine, a mercapto, a substituted or unsubstituted C 1 to C 30 alkoxy, a substituted or unsubstituted C 1 to C 30 alkyl thiol, a substituted or unsubstituted C 1 to C 20 alkyl amine, or a combination thereof, wherein the C 6 to C 30 aryl is selected from Group 5: [Group 4] [Group 5] R 6 to R 10 each independently is hydrogen, substituted or unsubstituted C6to C30aryl, substituted or unsubstituted C3to C30heteroaryl, or a combination thereof, R 6 at least one of R to R 10 is a substituted or unsubstituted C3to C30nitrogen-containing heteroaryl; or a C6to C30aryl substituted with a substituted or unsubstituted C1to C30alkoxy, and represents a point of attachment to the chemical formula 1. 8.The hard mask composition according to claim 1, wherein X is any one selected from Group 6: [Group 6] 9.The hard mask composition according to claim 8, wherein X is any one selected from Group 7: [Group 7] 10.The hard mask composition according to claim 8, wherein the C 6 to C 30 aryl substituted with a substituted or unsubstituted C 1 to C 30 alkoxy is selected from Group 7. 11.The hard mask composition according to claim 1, wherein n is an integer satisfying the range of 2 ≤ n ≤ k / 2, and k is the number of substitutable positions of A in Chemical Formula 1. 12.The hard mask composition according to claim 1, wherein the compound represented by Chemical Formula 1 has a molecular weight of 900 to 7,000 g / mol. 13.The hard mask composition according to claim 1, wherein the compound represented by Chemical Formula 1 is contained in an amount of 0.01 wt% to 30 wt% based on the total content of the hard mask composition. R 1 , R 2 , R 4 and R 5 are each independently hydrogen or a substituted or unsubstituted group selected from Set 2, and R 3 is a group represented by Chemical Formula 3 or Chemical Formula 4, wherein R 1 , R 2 , R 4 , and R 5 are at least one substituted or unsubstituted group selected from Group 2: 14.A hard mask layer comprising a cured product of the hard mask composition according to any one of claims 1 to 13. ​ R 1 and R 4 each independently is substituted or unsubstituted phenyl, and R 5 is hydrogen. ​ ​ ​ ​ represents a connection point. ​ ​ ​ ​ ​ R of Chemical Formula 4 6 to R 10 each independently is a substituted or unsubstituted C3to C30nitrogen-containing heteroaryl selected from Group 6, or a substituted or unsubstituted C6to C30aryl selected from Group 7, and R 7 , R 8 , and R 10 is at least one substituted or unsubstituted C3to C30nitrogen-containing heteroaryl selected from Group 6; or a C6to C30aryl substituted with a substituted or unsubstituted C1to C30alkoxy, wherein the C6to C30aryl is selected from Group 7: ​ ​ ​ R 6 and R 9 each independently is substituted or unsubstituted phenyl. ​ R 8 is C6 to C30 aryl substituted with substituted or unsubstituted C1 to C30 alkoxy, wherein the C6 to C30 aryl is selected from Group 7, and R 10 is a substituted or unsubstituted C3to C30nitrogen-containing heteroaryl selected from Group 6; or ​ ​ ​ ​ ​ ​ 13. The hardmask composition of claim 1, wherein, ​ ​ 15. The hardmask layer of claim 14, wherein, the cured product comprises condensed polycyclic aromatic hydrocarbons.

16. A method of patterning comprising: applying the hardmask composition of any one of claims 1 to 13 on a material layer and heat treating the result 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 to expose a portion of the material layer; and etching the exposed portion of the material layer.

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