KR20230101485A - Hardmask composition, hardmask layer and method of forming patterns - Google Patents

Abstract

[화학식 2]

상기 화학식 1 및 상기 화학식 2의 정의는 명세서 내 기재한 바와 같다.A hard mask composition including a polymer including structural units represented by Formula 1 and structural units represented by Formula 2 below, and a solvent, a hard mask layer prepared from the hard mask composition, and a pattern formed from the hard mask composition. It is about how to form:
[Formula 1]

[Formula 2]

The definitions of Formula 1 and Formula 2 are as described in the specification.

Description

Hard mask composition, hard mask layer and pattern forming method {HARDMASK COMPOSITION, HARDMASK LAYER AND METHOD OF FORMING PATTERNS}

It relates to 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.

In recent years, the semiconductor industry has been developing from hundreds of nanometer-sized patterns to ultra-fine technologies having several to several tens of nanometer-sized patterns. Effective lithographic techniques are essential to realize these ultra-fine technologies.

A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the 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 decreases, it is difficult to form a fine pattern having a good profile only with the above-described typical lithographic techniques. 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 hardmask composition that can be effectively applied to a hardmask layer.

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

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

A hard mask composition according to an embodiment includes a polymer including a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2 below, and a solvent.

[Formula 1]

[Formula 2]

In Formula 1,

A is a heterocycle in which two or more substituted or unsubstituted hexagonal rings are condensed and contain one or more hetero atoms, and one or more hexagonal rings are condensed with one or more substituted or unsubstituted pentagonal rings and contain two or more different heteroatoms. a heterocyclic ring, or a combination thereof;

B is represented by the following formula (3),

[Formula 3]

In Formula 2 and Formula 3,

R ¹ and R ² are each independently deuterium, a hydroxyl group, a cyano group, a nitro group, Halogen atom, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 A heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, -COOR ^a (where R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted A substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.), -C (= O) R ^b {Wherein, R ^b is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or -NR'R” (where R' and R” are each independently hydrogen or C1 to C20 alkyl group).}, -NR ^c R ^d (where R ^c and R ^d are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group) is), or a combination thereof,

m and n are, each independently, an integer of 0 to 4, and in Formula 1 to Formula 3, * is a connection point.

A in Formula 1 may be any one of the substituted or unsubstituted heterocycles listed in Group 1 below.

[Group 1]

In Group 1, Z ¹ and Z ² are each independently NR ^e , O, S, Te or Se, but not the same as each other, and R ^e is hydrogen, deuterium, a halogen atom, substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

A in Formula 1 is a hydroxyl group, a halogen atom, an amino group, a thiol group, a cyano group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted heterocycle selected from Group 1, It may be substituted with one or more substituents that are unsubstituted C6 to C30 aryl groups or a combination thereof, or may be an unsubstituted heterocyclic ring.

A in Formula 1 may be any one of a substituted or unsubstituted heterocyclic ring selected from Group 1-1 below.

[Group 1-1]

A in Formula 1 may be any one of a substituted or unsubstituted heterocyclic ring selected from Groups 1-2 below.

[Group 1-2]

In the group 1-2,

Z ¹ and Z ² are, each independently, NR ^e , O, S, Te or Se, but not the same as each other;

R ^e is hydrogen, deuterium, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.

R ¹ and R ² in Formula 3 are each independently deuterium, a hydroxyl group, a cyano group, Halogen atom, substituted or unsubstituted C1 to C10 alkoxy group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C20 heteroaryl group, a substituted or unsubstituted C6 to C20 aryl group, -COOR ^a (wherein R ^a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl ), -C(=O)R ^b {where R ^b is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or -NR'R" (where R' and R" are each independently hydrogen or a C1 to C10 alkyl group).}, -NR ^c R ^d (where R ^c and R ^d are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 an aryl group), or a combination thereof.

m and n in Chemical Formula 3 may each be 0.

Chemical Formula 1 may be represented by one or more of Chemical Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

The polymer may have a weight average molecular weight of 1,000 g/mol to 200,000 g/mol.

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

The solvent is propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexa Non, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone or ethyl 3-ethoxypropionateyl can

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

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

Forming the hard mask layer may include heat treatment at 100°C to 1,000°C.

The hardmask composition according to one embodiment has excellent solubility in a solvent and can be effectively applied to a hardmask layer.

A hardmask layer formed from the hardmask composition according to an exemplary embodiment may secure excellent gap-fill characteristics, planarization characteristics, and etch resistance, as well as excellent heat resistance and chemical resistance.

1 is a reference diagram schematically illustrating a cross-section of a hard mask layer to explain a method for evaluating gap-fill characteristics and planarization characteristics.

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

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group A dino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a vinyl group, a C1 to C20 alkyl group, a C2 to C20 alkene Nyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C6 to C30 allyl 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, C3 to C30 heterocycloalkyl group, and means substituted with a substituent selected from combinations thereof.

In addition, the substituted halogen atom (F, Br, Cl, or I), hydroxy group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl 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, or C2 to C30 heterocyclic group. Substituents may be fused to form a ring. 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.

Unless otherwise defined herein, “hetero” means containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

Unless otherwise defined herein, "aryl group" means a group having one or more hydrocarbon aromatic moieties, and broadly refers to a form in which hydrocarbon aromatic moieties are connected by a single bond and hydrocarbon aromatic moieties are directly or indirectly linked. Fused non-aromatic fused rings are also included. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.

More specifically, the substituted or unsubstituted C6 to C30 aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted phenanthrenyl group. An unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o- Terphenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted perylenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted It may be an unsubstituted furanyl group, or a combination thereof, but is not limited thereto.

Unless otherwise defined herein, a "heterocyclic group" is a concept including a heteroaryl group, in addition to 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 heteroatom selected from N, O, S, P, and Si instead of carbon (C) within. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may include one or more heteroatoms.

More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group is a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, Substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazole group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted 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 benzothiophenyl group, A substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a 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 phenazine substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazinyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuranyl group, or substituted or unsubstituted dibenzothiophene It may be a diary, or a combination thereof, but is not limited thereto.

Unless otherwise defined herein, "heteroaryl group" means containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si in the aryl group. Two or more heteroaryl groups may be directly connected through a sigma bond, or if the heteroaryl group includes two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 hetero atoms.

Unless otherwise defined herein, "heteroalkyl group" means a group containing a hetero element selected from the group consisting of N, O, S, P and Si instead of one or more carbon atoms forming an alkyl group. do.

In the present specification, the polymer may include both an oligomer and a polymer.

Unless otherwise specified herein, "weight average molecular weight" is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) ( The column was Shodex LF-804, and the standard sample was Shodex polystyrene).

In the semiconductor industry, there is an ever-increasing demand to reduce the size of chips, and in order to cope with this, the line width of a resist patterned in lithography technology must have a size of several tens of nanometers. Accordingly, the height capable of withstanding the line width of the resist pattern is limited, and sometimes the resists do not have sufficient resistance in the etching step. To compensate for this, an auxiliary layer called a hardmask layer is used between the material layer to be etched and the photoresist layer. Since the hard mask layer serves as an intermediate film that transfers the fine pattern of the photoresist to the material layer through selective etching, the hard mask layer requires etching resistance and heat resistance to withstand the etching process required for pattern transfer.

On the other hand, conventionally, the hard mask layer was formed by chemical or physical deposition, but this has a problem of low economic feasibility due to the large equipment scale and high process cost, so a spin-coating technique was recently developed to form the hard mask layer. The spin-coating technique is easier to process than the conventional method, and the gap-fill characteristics and planarization characteristics of the hard mask layer produced therefrom may be better, but the etch resistance required for the hard mask layer described above tends to be somewhat inferior show

Recently, in order to improve the etch resistance of the hard mask layer, research on maximizing the carbon content of the hard mask composition has been actively conducted. However, as the carbon content of the hardmask composition is maximized, solubility of the composition in a solvent decreases, making it difficult to apply the spin-coating technique. Therefore, the hard mask composition is required to have improved etching resistance and not lower solubility in a solvent.

The inventors of the present application have made efforts to prepare a hard mask composition for forming a hard mask having excellent gap-fill and planarization properties due to excellent solvent solubility and improved etch resistance.

As a result, the polymer included in the hardmask composition contains an aromatic hydrocarbon ring to increase the carbon content in the composition, thereby improving the etching resistance of the hardmask layer formed therefrom, and at the same time, the polymer includes a heterocycle containing a hetero element. By including it, the solubility in the solvent was improved so as not to decrease.

Specifically, a hard mask composition according to an embodiment includes a polymer including structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2 below, and a solvent.

[Formula 1]

[Formula 2]

In Formula 1,

A is a heterocycle in which two or more substituted or unsubstituted hexagonal rings are condensed and contain one or more hetero atoms, and one or more hexagonal rings are condensed with one or more substituted or unsubstituted pentagonal rings and contain two or more different heteroatoms. a heterocyclic ring, or a combination thereof;

B is represented by the following formula (3),

[Formula 3]

In Formula 2 and Formula 3,

R ¹ and R ² are, each independently, a deuterium, a hydroxy group, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C30 heteroalkyl group , A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, -COOR ^a (wherein R ^a is hydrogen, substituted or unsubstituted A substituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group , Or a substituted or unsubstituted C2 to C30 heteroaryl group.), -C(=O)R ^b {Where, R ^b is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to A C20 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or -NR'R” (where R' and R” are each independently hydrogen or a C1 to C20 alkyl group)}, -NR ^c R ^d (where R ^c and R ^d are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), or a combination thereof;

m and n are each independently an integer from 0 to 4;

In Formula 1 to Formula 3,

* is a connection point.

As described above, the polymer in the composition according to one embodiment includes at least one heteroatom and includes a heterocycle in which two or more substituted or unsubstituted hexagonal rings are condensed, or includes two or more heteroatoms different from each other and is substituted or unsubstituted. Solubility in a solvent may be increased by including a heterocycle in which one or more pentagonal rings and one or more hexagonal rings are condensed.

In addition, since the polymer includes the structural unit represented by Chemical Formula 2, the carbon content in the polymer is increased so that a hardmask layer formed from a hardmask composition including the polymer may have high etch resistance.

In addition, since the polymer includes the moiety represented by Chemical Formula 3 in both the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2, flexibility of the polymer is increased. The flexible structure not only improves the solubility of the composition including it by increasing the free volume of the polymer, but also increases the reflow during the bake process by lowering the glass transition temperature (Tg), thereby forming a composition formed from such a composition. Gap-fill characteristics and planarization characteristics of the hard mask layer may be improved.

Since the polymer includes both the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2, it has appropriate solubility in a solvent, so that the gap-fill and planarization characteristics of a hard mask layer formed from a composition containing the polymer are improved. At the same time as being improved, the corrosion resistance may be excellent.

In one embodiment, A in Formula 1 may be any one of the substituted or unsubstituted heterocycles listed in Group 1 below.

[Group 1]

In the group 1 above,

Z ¹ and Z ² are each independently NR ^e , O, S, Te or Se, but not identical to each other, wherein R ^e is hydrogen, deuterium, a halogen atom, a substituted or unsubstituted 1 to C30 alkyl group, or A substituted or unsubstituted C6 to C30 aryl group.

In one embodiment, A in Formula 1 is a hydroxyl group, a halogen atom, an amino group, a thiol group, a cyano group, a substituted or unsubstituted 1 to C30 alkyl group, or a substituted or unsubstituted 1 to C30 alkoxy group selected from Group 1. group, a substituted or unsubstituted C6 to C30 aryl group, or a combination of one or more substituents thereof, or may be an unsubstituted heterocyclic ring.

For example, A in Formula 1 may be any one of a substituted or unsubstituted heterocyclic ring selected from Group 1-1 below.

[Group 1-1]

As another example, A in Formula 1 may be any one of a substituted or unsubstituted heterocyclic ring selected from Groups 1-2 below.

[Group 1-2]

In the group 1-2,

Z ¹ and Z ² are each independently NR ^e , O, S, Te or Se, but not identical to each other, wherein R ^e is hydrogen, deuterium, a halogen atom, a substituted or unsubstituted 1 to C30 alkyl group, or A substituted or unsubstituted C6 to C30 aryl group.

In one embodiment, the Z ¹ and Z ² may each independently be any one of NH, O, and S, wherein Z ¹ and Z ² are different from each other.

In one embodiment, Chemical Formula 1 may be represented by one or more of Chemical Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In one embodiment, R ¹ and R ² in Formula 3 are each independently deuterium, a hydroxyl group, a cyano group, a halogen atom, a substituted or unsubstituted C1 to C10 alkoxy group, or a substituted or unsubstituted C1 to C20 alkyl group. , A substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C20 heteroaryl group, a substituted or unsubstituted C6 to C20 aryl group, -COOR ^a (wherein R ^a is hydrogen, substituted or unsubstituted C1 to C10 alkyl), -C(=O)R ^b {wherein R ^b is hydrogen, C1 to C10 an alkyl group, or -NR'R” (where R' and R” are each independently hydrogen or a C1 to C10 alkyl group)}, -NR ^c R ^d (where R ^c and R ^d are each independently , hydrogen, a C1 to C10 alkyl group, or a C6 to C20 aryl group), or a combination thereof

For example, the substituted or unsubstituted C1 to C10 alkoxy group is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, or a pentoxy group. It may be a period and the like, and may be, for example, a methoxy group or an ethoxy group.

For example, the C1 to C20 alkyl group may be unsubstituted, or may be substituted with an aryl group or a halogen atom. For example, it is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, such as a methyl group and an ethyl group. Other examples include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a chloroethyl group, a chloropropyl group, a bromomethyl group, a bromoethyl group, a bromopropyl group, an iodoethyl group, or an iodopropyl group, Not limited.

For example, the C1 to C20 heteroalkyl group may include one in which one or more of the carbon atoms forming the alkyl group is replaced with oxygen (O-), and for example, may include an ether (-O-) bond. there is. Thus, the C1 to C20 heteroalkyl group may include a monovalent substituent derived from dimethyl ether, diethyl ether, methyl ethyl ether, methyl propyl ether, or ethyl propyl ether.

In addition, the C1 to C20 heteroarylalkyl group may be a substituent in which an alkyl group and an aryl group are connected to both sides of an ether bond, and may include, for example, a monovalent substituent derived from methyl benzyl ether, ethyl benzyl ether, or propyl benzyl ether. may, but are not limited thereto.

R ¹ and R ² in Formula 3 are each independently -COOH, -C(=O)H, -C(=O)CH ₃ , -NH ₂ , -C(=O)NH ₂ , or any of these can be a combination.

The polymer may have a weight average molecular weight of 1,000 g/mol to 200,000 g/mol. for example, from about 1,000 g/mol to 150,000 g/mol, such as from about 1,000 g/mol to 100,000 g/mol, such as from about 1,000 g/mol to 10,000 g/mol, such as from about It may have a weight average molecular weight of 1,200 g/mol to 5,000 g/mol, but is not limited thereto. By having the weight average molecular weight within the above range, the carbon content and solubility of the hardmask composition including the polymer in a solvent may be adjusted and optimized.

The polymer may be included in an amount of 0.1 wt % to 30 wt % based on the total weight of the hard mask composition. For example, from about 0.2% to 30% by weight, such as from about 0.5% to 30% by weight, such as from about 1% to 30% by weight, such as from about 1% to 25% by weight. %, for example, about 1% to 20% by weight, but is not limited thereto. By including the compound within the above range, the thickness, surface roughness, and degree of planarization of the hard mask can be easily adjusted.

The hard mask composition according to one embodiment may include a solvent, and in one embodiment, the solvent is propylene glycol, propylene glycol diacetate, methoxy propanediol, 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, methyl phy It may include at least one selected from rolidone, methylpyrrolidinone, acetylacetone, ethyl 3-ethoxypropionate, and the like, but is not limited thereto. The solvent is not particularly limited as long as it has sufficient solubility and/or dispersibility for the compound.

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 alkylbenzenesulfonic acid salt, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, and the like, but is not limited thereto.

The crosslinking agent may include, for example, melamine-based, substituted urea-based, or polymer-based such. Preferably, a crosslinking agent having at least two cross-linking substituents, for example methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Compounds 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 the crosslinking agent having high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in a molecule may be used.

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

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

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

A method of forming a pattern according to an embodiment includes providing a material layer on a substrate, applying a hardmask composition including the above-described polymer and a solvent on the material layer, and heat-treating the hardmask composition to form a hardmask layer. Forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern Selectively removing the hard mask layer to expose a portion of the material layer, and etching the exposed portion of the material layer. The substrate may be, for example, a silicon wafer, a glass substrate or a polymer substrate.

The material layer is a material to be finally patterned, and may be, 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 by, for example, a chemical vapor deposition method.

The hard mask composition is 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 coating thickness of the organic film composition is not particularly limited, but may be, for example, about 50 to 200,000 Å thick.

The heat treatment of the hardmask composition may be performed at, for example, about 100° C. to 1,000° C. for about 10 seconds to 1 hour. For example, the heat treatment of the hardmask composition may include a plurality of heat treatment steps, and may include, for example, a first heat treatment step and a second heat treatment step.

In one embodiment, the heat treatment of the hardmask composition may include, for example, one heat treatment step performed at about 100° C. to about 1000° C. for about 10 seconds to 1 hour. For example, the heat treatment step Can be carried out in an atmosphere of air, nitrogen or oxygen concentration of 1wt% or less.

In one embodiment, the step of thermally treating the hardmask composition is, for example, about 100 °C to 1,000 °C, such as about 100 °C to 800 °C, such as about 100 °C to 500 °C, such as , including a first heat treatment step performed at about 100 ° C to 400 ° C for about 10 seconds to 1 hour, for example, about 100 ° C to 1,000 ° C, for example, about 300 ° C to 1,000 ° C, for example , a second heat treatment step performed at about 500 ° C to 1,000 ° C, for example, about 500 ° C to 800 ° C for about 10 seconds to 1 hour may be continuously included. For example, the first and second heat treatment steps may be performed in an atmosphere of air, nitrogen, or oxygen concentration of 1 wt% or less.

By performing at least one step of heat treatment of the hardmask composition at a high temperature of 200° C. or higher, high etching resistance capable of withstanding etching gas and chemical liquid exposed in a subsequent process including an etching process may be exhibited.

In one embodiment, the forming of the hard mask layer may include a UV/Vis curing step and/or a near IR curing step.

In one embodiment, the forming of the hard mask layer includes at least one of the first heat treatment step, the second heat treatment step, a UV/Vis curing step, and a near IR curing step, or two or more steps. may be included consecutively.

In an embodiment, the method may further include forming a silicon-containing thin film layer on the hard mask layer. The silicon-containing thin film layer may be formed of, for example, materials such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and/or SiN.

In an embodiment, before 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.

In one embodiment, exposing 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.

In one embodiment, the etching of the exposed portion of the material layer may be performed by dry etching using an etching gas, for example, N ₂ /O ₂ , CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and mixed gases thereof may be used.

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, and an insulating pattern, and may be applied as various patterns in a semiconductor integrated circuit device, for example.

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

Example

Synthesis Examples 1 to 3: Polymer Synthesis

Synthesis Example 1

9-methylacridine (9-methylacridine) 19.3　g (0.1mol), 1-hydroxypyrene (1-hydroxypyrene) 21.8g (0.1mol), 1,1'-oxybis [4- (methoxy methyl) benzene] (1, 1'-oxybis [4- (methoxymethyl) benzene]) 51.6 g (0.2 mol), p-TSA 1.3 g (6 mmol) and propylene glycol monomethyl ether acetate (PGMEA) 78.2 g were added After that, samples were taken from the polymerization reaction product at intervals of 1 hour, and the weight average molecular weight of the sample was measured, and the reaction was completed when the weight average molecular weight was 1,800 g/mol to 2,500 g/mol. When the reaction is completed, precipitate in 200 g of hexane, filter the precipitate formed by adding methanol and water, and remove the remaining monomer using methanol to obtain a structural unit represented by Formula 1-1 and Formula 2-1 below A polymer containing the structural units shown was obtained.

[Formula 1-1] [Formula 2-1]

Synthesis Example 2

Structural units represented by Chemical Formula 1-2 and Chemical Formula 2- A polymer containing the structural unit represented by 1 was obtained.

[Formula 1-2] [Formula 2-1]

Synthesis Example 3

Structural units represented by Chemical Formulas 1-3 and the following Chemical Formulas in the same manner as in Synthesis Example 1, except that 11.9 g (0.1 mol) of benzoxazole was used instead of 9-methylacridine. A polymer containing the structural unit represented by 2-1 was obtained.

[Formula 1-3] [Formula 2-1]

Comparative Synthesis Example 1

In a flask, 19.3 g (0.1 mol) of 9-methylacridine, 13.8 g (0.1 mol) of 1,4-bis (methoxymethyl) benzene, paratoluene After adding 1.3 g (6 mmol) of phonic acid (p-Toluenesulfonic acid, p-TSA) and 78.2 g of propylene glycol monomethyl ether acetate (PGMEA), the mixture was stirred at 100° C. for 2 to 15 hours to perform a polymerization reaction. Samples were taken from the polymerization reactant at intervals of 1 hour, and the reaction was completed when the weight average molecular weight was 2,000 g/mol to 3,500 g/mol. After the polymerization reaction was completed, the reactant was slowly cooled to room temperature, and then the reactant was added to 40 g of distilled water and 400 g of methanol, vigorously stirred, and allowed to stand to form a precipitate. After dissolving the formed precipitate in 80 g of propylene glycol monomethyl ether acetate (PGMEA), 320 g of methanol and 320 g of water were strongly stirred to form a precipitate. The precipitate obtained at this time was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA). The purification process of forming the precipitate twice was performed a total of three times. After dissolving the purified polymer in 80 g of propylene glycol monomethyl ether acetate (PGMEA), methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer containing a structural unit represented by the following formula P (Mw: 2,000 g /mol).

[Formula P]

Comparative Synthesis Example 2

In the flask, 12.9　g (0.1　mol) of Quinoline, 18.82g (0.1mol) of 2,6-dimethoxymethylnaphthalene, p-Toluenesulfonic acid (p-Toluenesulfonic acid, p After adding 1.3 g (6 mmol) of -TSA) and 78.2 g of propylene glycol monomethyl ether acetate (PGMEA), the mixture was stirred at 100° C. for 2 to 15 hours to perform a polymerization reaction. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight was 2,000 g/mol to 3,500 g/mol. After the polymerization reaction was completed, the reactant was slowly cooled to room temperature, and then the reactant was added to 40 g of distilled water and 400 g of methanol, vigorously stirred, and allowed to stand to form a precipitate. After dissolving the formed precipitate in 80 g of propylene glycol monomethyl ether acetate (PGMEA), 320 g of methanol and 320 g of water were strongly stirred to form a precipitate. The precipitate obtained at this time was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA). The purification process of forming the precipitate twice was performed a total of three times. After dissolving the purified polymer in 80 g of propylene glycol monomethyl ether acetate (PGMEA), methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer containing a structural unit represented by the following formula Q (Mw: 2,000 g /mol).

[Formula Q]

Comparative Synthesis Example 3

21.8 g (0.1 mol) of 1-hydroxypyrene instead of Quinoline, 1,1'-oxybis[4-( instead of 2,6-Dimethoxymethylnaphthalene) Methoxymethyl) benzene] (1,1'-oxybis [4- (methoxymethyl) benzene]) Except for using 51.6 g (0.2 mol), in the same manner as in Comparative Synthesis Example 2, the structural unit represented by the following formula R A polymer containing

[Formula R]

Comparative Synthesis Example 4

1,4-bismethoxymethylbenzene (1,4-bis (methoxymethyl)benzene) was obtained in the same manner as in Synthesis Example 1 except that a polymer containing a structural unit represented by the following formula S was obtained.

[Formula S]

Comparative Synthesis Example 5

1-hydroxypyrene (1-hydroxypyrene) 21.8g (0.1mol), 1-naphthol (1-Naphthol) 14.4g (0.1mol) represented by the following formula T in the same manner as in Synthesis Example 3 except for using A polymer containing structural units to be obtained was obtained.

[Formula T]

Examples and Comparative Examples: Preparation of Hard Mask Compositions

Example 1

After dissolving 3 g of the polymer obtained in Synthesis Example 1 in 10 g of propylene glycol monomethyl ether acetate (PGMEA), it was filtered through a 0.1 μm Teflon filter to prepare a hard mask composition.

Example 2

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

Example 3

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

Comparative Example 1

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

Comparative Example 2

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

Comparative Example 3

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

Comparative Example 4

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1.

Comparative Example 5

A hardmask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 5 was used instead of the polymer obtained in Synthesis Example 1.

Evaluation 1: Gap-fill characteristics and flattening characteristics

1 is a reference diagram illustratively illustrating a level difference of a hard mask layer in order to explain a method for evaluating planarization characteristics. The hardmask composition according to Examples 1 to 3 and Comparative Examples 1 to 5 was spin-coated on a silicon wafer by adjusting the mass ratio of solute to solvent to 3:97, and then subjected to a bake process and cut surfaces using V-SEM. Observed. Under the above conditions, the thickness of the mask on the bare wafer was about 1,100 angstroms. The gap-fill and flattening characteristics were determined by the presence or absence of voids by observing the cross-section of the pattern using a scanning electron microscope (SEM), and the flattening characteristics were determined by the values of (h ₁ -h ₂ ) in FIG. was measured.

Referring to Figure 1, h ₁ means the average value of the thickness of the thin film measured at any three points where the pattern is not formed on the substrate, h ₂ is measured at any three points where the pattern is formed on the substrate It means the average value of the thickness of one thin film. Gap-fill characteristics and planarization characteristics are better when the difference (step difference) between h ₁ and h ₂ is not large.

Presence of Void Step (Å) Comparative Example 1 doesn't exist 170 Comparative Example 2 doesn't exist 175 Comparative Example 3 doesn't exist 130 Comparative Example 4 doesn't exist 149 Comparative Example 5 doesn't exist 161 Example 1 doesn't exist 105 Example 2 doesn't exist 103 Example 3 doesn't exist 118

In Table 1, comparing the presence or absence of voids showing gap-fill characteristics and the step difference results showing planarization characteristics, the organic films formed from the hardmask compositions according to Examples 1 to 3 were organic films formed from the hardmask compositions according to Comparative Examples 1 to 5 It can be seen that it has gap-fill characteristics and planarization characteristics superior to those of the film.

Evaluation 2: Erosion resistance evaluation

The hard mask composition according to Examples 1 to 3 and Comparative Examples 1 to 5 was spin-coated on a silicon wafer by adjusting the mass ratio of solute to solvent to 15:85, and then heat-treated on a hot plate at 400 ° C. for 2 minutes to form 4,000 Å. A thin film was formed to a thickness, and the thickness of the formed thin film was measured. Subsequently, the thin film was dry etched using a CHF ₃ /CF ₄ mixed gas and a N ₂ /O ₂ mixed gas for 100 seconds and 60 seconds, respectively, and the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated from the thickness of the thin film before and after dry etching and the etching time by Equation 1 below.

[Calculation 1]

Etch rate (Å/sec) = (Initial thin film thickness - Thin film thickness after etching) / Etching time (sec)

CHF ₃ /CF ₄ bulk etch rate (Å/sec) N ₂ /O ₂ bulk etch rate (Å/sec) Comparative Example 1 28.3 27.5 Comparative Example 2 31.5 26.0 Comparative Example 3 27.4 26.4 Comparative Example 4 28.5 27.0 Comparative Example 5 32.6 30.5 Example 1 24.3 22.4 Example 2 25.6 23.1 Example 3 24.9 21.6

Referring to Table 2, it can be confirmed that the organic films formed from the hardmask compositions according to Examples 1 to 3 have excellent etching resistance to etching gas compared to the organic films formed from the hardmask compositions according to Comparative Examples 1 to 5.

Although the 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 of those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It falls within the scope of the right of invention.

Claims (14)

A hard mask composition comprising a polymer including a structural unit represented by Formula 1 below and a structural unit represented by Formula 2 below, and a solvent:
[Formula 1]

[Formula 2]

In Formula 1,
A is a heterocycle in which two or more substituted or unsubstituted hexagonal rings are condensed and contain one or more hetero atoms, and one or more hexagonal rings are condensed with one or more substituted or unsubstituted pentagonal rings and contain two or more different heteroatoms. a heterocyclic ring, or a combination thereof;
B is represented by the following formula (3),
[Formula 3]

In Formula 2 and Formula 3,
R ¹ and R ² are each independently deuterium, a hydroxyl group, a cyano group, a nitro group, Halogen atom, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 A heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, -COOR ^a (where R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted A substituted C2 to C30 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.), -C (= O) R ^b {Wherein, R ^b is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or -NR'R” (where R' and R” are each independently hydrogen or C1 to C20 alkyl group).}, -NR ^c R ^d (where R ^c and R ^d are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group) is), or a combination thereof,
m and n are each independently an integer from 0 to 4;
In Formulas 1 to 3,
* is a connection point.
The hardmask composition of claim 1, wherein A in Formula 1 is any one of the substituted or unsubstituted heterocycles listed in Group 1 below:
[Group 1]

In the group 1 above,
Z ¹ and Z ² are, each independently, NR ^e , O, S, Te or Se, but not the same as each other;
R ^e is hydrogen, deuterium, a halogen atom, a substituted or unsubstituted 1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.
The method of claim 2, wherein A in Formula 1 is a heterocyclic group selected from Group 1 is a hydroxyl group, a halogen atom, an amino group, a thiol group, a cyano group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C1 to C30 group. A hardmask composition that is unsubstituted or substituted with at least one substituent that is a C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
The hardmask composition of claim 1, wherein A in Formula 1 is any one of a substituted or unsubstituted heterocyclic ring selected from Group 1-1:
[Group 1-1]

The hardmask composition of claim 1, wherein A in Formula 1 is any one of substituted or unsubstituted heterocyclic rings selected from Groups 1-2 below:
[Group 1-2]

In the group 1-2,
Z ¹ and Z ² are, each independently, NR ^e , O, S, Te or Se, but not the same as each other;
R ^e is hydrogen, deuterium, a halogen atom, a substituted or unsubstituted 1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group.
The method of claim 1, wherein R ¹ and R ² in Formula 3 are each independently a deuterium, a hydroxyl group, a cyano group, a halogen atom, a substituted or unsubstituted C1 to C10 alkoxy group, or a substituted or unsubstituted C1 to C20 Alkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C20 heteroaryl group, substituted or unsubstituted C2 to C20 heteroaryl group cyclic C6 to C20 aryl group, -COOR ^a (wherein R ^a is hydrogen, substituted or unsubstituted C1 to C10 alkyl), -C(=O)R ^b {wherein R ^b is hydrogen, substituted or An unsubstituted C1 to C10 alkyl group, or -NR'R” (where R' and R” are each independently hydrogen or a C1 to C10 alkyl group)}, -NR ^c R ^d (where R ^c and Each R ^d is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), or a combination thereof.
The hardmask composition of claim 1 , wherein m and n in Chemical Formula 3 are each 0.
The hardmask composition of claim 1, wherein Chemical Formula 1 is represented by one or more of the following Chemical Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

The hard mask composition of claim 1, wherein the polymer has a weight average molecular weight of 1,000 g/mol to 200,000 g/mol.
The hardmask composition of claim 1 , wherein the polymer is included in an amount of 0.1% to 30% by weight based on the total weight of the hardmask composition.
In claim 1, the solvent is propylene glycol, propylene glycol diacetate, methoxy propanediol, 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, methylpyrrolidinone, acetylacetone or ethyl 3-ethene A hard mask composition that is toxypropionate.
A hard mask layer comprising a cured product of the hard mask composition according to any one of claims 1 to 11.
providing a layer of material over a substrate;
applying a hardmask composition according to any one of claims 1 to 11 onto the material layer;
heat-treating the hardmask composition to form a hardmask layer;
forming a photoresist layer over the hard mask 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;
Pattern forming method comprising a.
The pattern forming method of claim 13 , wherein the forming of the hard mask layer comprises heat treatment at 100° C. to 1,000° C.

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