KR20210046493A - Hardmask composition, hardmask layer and method of forming patterns - Google Patents

Abstract

The present invention relates to a hardmask composition comprising a polymer including a structural unit represented by chemical formula 1, a hardmask layer, and a pattern forming method. In the chemical formula 1, the definitions of Ar^1, L^1, and X^1 are the same as described in the specification.

Description

Hardmask composition, hardmask layer and pattern formation method {HARDMASK COMPOSITION, HARDMASK LAYER AND METHOD OF FORMING PATTERNS}

It relates to a hardmask composition, a hardmask layer including a cured product of the hardmask composition, and a pattern forming method using the hardmask composition.

Recently, the semiconductor industry is developing from a pattern of several hundred nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. Effective lithographic techniques are essential to realize such ultra-fine technology.

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

In recent years, as the size of the pattern to be formed decreases, it is difficult to form a fine pattern having a good profile using only the above-described typical lithographic technique. Accordingly, a fine pattern may be formed by forming an auxiliary layer called a hardmask layer between the material layer to be etched and the photoresist layer.

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

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

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

According to one embodiment, there is provided a hardmask composition comprising a polymer including a first structural unit represented by the following Chemical Formula 1, and a solvent.

[Formula 1]

In Formula 1,

Ar ¹ is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,

X ¹ is a substituted or unsubstituted C3 to C10 branched alkyl group,

L ¹ is a divalent organic group.

Ar ¹ may be any one substituted or unsubstituted selected from the group 1 below.

[Group 1]

Ar ¹ may contain a condensed aromatic ring.

X ¹ is a substituted or unsubstituted iso-propyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted iso- It may be a pentyl group, a substituted or unsubstituted sec-pentyl group, a substituted or unsubstituted tert-pentyl group, or a substituted or unsubstituted neo-pentyl group.

L ¹ may include at least one secondary carbon.

L ¹ may include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a combination thereof.

L ¹ may further include a substituted or unsubstituted C6 to C30 arylene group.

L ¹ may be represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

Y ¹ is a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ and R ² are each independently present or linked to each other to form a ring,

R ³ and R ⁴ are each independently present or linked to each other to form a ring,

n ¹ is 0 or 1,

m ¹ is an integer of 0 to 3.

Y ¹ may be a substituted or unsubstituted any one selected from the following group 2.

[Group 2]

In group 2 above,

W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,

R ^a to R ^c are each independently hydrogen, halogen, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to A C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

p is an integer from 1 to 30,

* Is the point of connection with other moieties in the polymer of formula (2).

L ¹ may be any one selected from Group 3 below.

[Group 3]

The polymer further includes a second structural unit different from the first structural unit, and the second structural unit may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

Ar ² is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,

X ² is a substituted or unsubstituted C3 to C10 branched alkyl group,

L ² is a divalent organic group.

The polymer may be represented by the following formula (7).

[Formula 7]

In Chemical Formula 7,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,

X ¹ and X ² are each independently a substituted or unsubstituted C3 to C10 branched alkyl group,

Y ¹ and Y ² are each independently a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ and R ² are each independently present or linked to each other to form a ring,

R ³ and R ⁴ are each independently present or linked to each other to form a ring,

R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,

R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,

n ¹ and n ² are 0 or 1,

m ¹ and m ² are integers from 0 to 3,

a and b are molar ratios.

The polymer further includes a third structural unit, and the third structural unit may be represented by Formula 8 below.

[Formula 8]

In Chemical Formula 8,

Ar ³ is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,

L ³ is a divalent organic group,

Ar ³ is the same as or different from ^{Ar 1,}

L ³ is the same as or different from ^{L 1.}

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

According to another embodiment, the steps of forming a hardmask layer by applying the above-described hardmask composition on a material layer and heat treatment, forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer to Forming a photoresist pattern, selectively removing the hardmask layer using the photoresist pattern, exposing a portion of the material layer, and etching the exposed portion of the material layer Provides a method of formation.

The solubility of the polymer, the film density and etch resistance of the hardmask layer can be secured at the same time.

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

Hereinafter, unless otherwise defined herein, the term'substituted' means that the hydrogen atom in the compound is deuterium, a halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, amidino Group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, 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 It means substituted with a substituent selected from a C15 cycloalkynyl group, a C2 to C30 heterocyclic group, and 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 salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to Two adjacent substituents among a C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, and a C2 to C30 heterocyclic group It can also 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.

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

In the present specification, "aromatic ring" refers to a single ring; A condensed aromatic ring in which two or more aromatic rings are condensed; Two or more aromatic rings include a single bond, a C1 to C5 alkylene group, a non-condensed aromatic ring linked by O or C(=O), or a combination thereof.

In the present specification, "heterocycle" is a concept including a heteroaromatic ring, and in addition to N, O, instead of carbon (C) in a ring compound such as an aromatic ring, an aliphatic ring, a fused ring thereof, or a combination thereof It means containing at least one hetero atom selected from S, P and Si. When the heterocycle is a fused ring, one or more heteroatoms may be included in the entire heterocycle or each ring.

In the present specification, "aryl group" refers to a group having one or more hydrocarbon aromatic moieties, and broadly, hydrocarbon aromatic moieties are linked by a single bond and non-aromatic in which hydrocarbon aromatic moieties are directly or indirectly fused. Also includes fused rings. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

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

More specifically, the substituted or unsubstituted 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 phenanthryl group, a substituted or unsubstituted flu Orenyl group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted chlorine A senyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a combination thereof, or a combination thereof may be fused, but is not limited thereto. .

More specifically, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted Substituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazole Diary, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted A substituted 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 quinazoli Nyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazineyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted acridinyl group, substituted Or unsubstituted phenazineyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazineyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted A substituted carbazolyl group, a substituted or unsubstituted pyridoindolyl group, a substituted or unsubstituted benzopyridooxazineyl group, a substituted or unsubstituted benzopyridothiazinyl group, a substituted or unsubstituted 9,9-dimethyl9 ,10 dihydroacridinyl group, a combination thereof, or a combination thereof may be a fused form, but is not limited thereto. In one example of the present invention, the heterocyclic group or the heteroaryl group may be a pyrrole group, an indolyl group, or a carbazolyl group.

In the present specification, “arylene group” means that there are two linking groups in the substituted or unsubstituted aryl group defined above, for example, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a substituted or Unsubstituted anthracenylene group, substituted or unsubstituted phenanthrylene group, substituted or unsubstituted naphthacenylene group, substituted or unsubstituted pyrenylene group, substituted or unsubstituted biphenylene group, substituted or unsubstituted terphenyl A ene group, a substituted or unsubstituted quarterphenylene group, a substituted or unsubstituted cryenylene group, a substituted or unsubstituted triphenylenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indenylene group, these A combination of or a combination thereof may be in a condensed form, but is not limited thereto.

In addition, in the present specification, the polymer refers to an oligomer and a polymer.

Hereinafter, a hardmask composition according to one embodiment will be described.

The hardmask composition according to one embodiment includes a polymer and a solvent.

The polymer may comprise a carbonate moiety, for example, the polymer may comprise a carbonate moiety as a side chain, for example, the polymer may contain a carbonate moiety as a side chain in a main chain comprising an aromatic ring and/or a hetero ring. May contain tea. The carbonate moiety located in the side chain of the polymer may include, for example, a bulky functional group, such as an alkyl carbonate moiety, such as a C3 or higher alkyl carbonate moiety, such as a C3 or higher branched alkyl carbonate moiety. Polymers can improve solubility in solvents by having such bulky side chains to reduce or prevent interaction and/or stacking between polymers.

Accordingly, the polymer includes an aromatic ring and/or a heterocycle having a high carbon content in the main chain, thereby forming a polymer layer having a hard film, thereby improving etch resistance, and at the same time, the carbonate moiety is included in the side chain. Since the solubility in a solvent can be improved, the coatability of the hardmask composition can be improved.

For example, the polymer may include a structural unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

Ar ¹ is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,

X ¹ is a substituted or unsubstituted C3 to C10 branched alkyl group,

L ¹ is a divalent organic group.

In Formula 1, in ^{the definition of Ar 1} ,'substituted' means that it is further substituted with a substituent other than *-O(C=O)OX ^{1 shown in Formula 1, and'unsubstituted' is Formula 1} It means that it is not further substituted with a substituent other than *-O(C=O)OX ^{1 shown in.}

The aromatic ring is a single ring; A fused ring in which two or more aromatic rings are fused; Two or more aromatic rings may be unfused rings linked by a single bond, a C1 to C5 alkylene group, O, C(=O) or OC(=O).

The hetero ring is a single ring; A fused ring in which two or more hetero rings are fused; Two or more hetero rings are unfused rings linked by a single bond, a C1 to C5 alkylene group, O, C(=O) or OC(=O); A fused ring in which at least one aromatic ring and at least one hetero ring are fused; At least one aromatic ring and at least one hetero ring may be a single bond, a C1 to C5 alkylene group, a non-fused ring connected by O, C(=O) or OC(=O).

When the polymer has an aromatic ring and/or a hetero ring, it is possible to increase the carbon content of the polymer to form a hard layer, so that high corrosion resistance can be imparted.

For example, Ar ¹ may be any one substituted or unsubstituted selected from the group 1 below.

[Group 1]

In Group 1, each aromatic ring and hetero ring may be unsubstituted or may be substituted with one or more substituents. Here, the substituent is, for example, deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkylamino group, substituted or unsubstituted C1 to C30 arylamino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted Or an unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted It may be a C3 to C30 heteroaryl group or a combination thereof, but is not limited thereto. For example, it may be a phenyl group, a naphthyl group, an N-phenylamino group, an N,N-phenylamino group, or a combination thereof.

For example, Ar ¹ may be a polycyclic aromatic ring, may be a condensed aromatic ring and/or a non-condensed aromatic ring, but preferably may be a condensed aromatic ring

As described above, the polymer may include an aromatic ring and/or a hetero ring having a branched alkyl carbonate moiety, for example, a bulky (such as a C3 to C10 branched alkyl group in which ^{X 1 is substituted or unsubstituted) (} It may be a bulky) alkyl group. Accordingly, by weakening the intermolecular interaction of the polymer, the solubility of the polymer in an organic solvent can be further increased, and the polymer layer can be further enhanced by a solution process such as spin-on coating. It can be formed effectively.

For example, X ¹ is a substituted or unsubstituted C3 to C10 iso-alkyl group, a substituted or unsubstituted C3 to C10 sec-alkyl group, a substituted or unsubstituted C4 to C10 tert-alkyl group, or a substituted or unsubstituted C5 to C10 It may be a neo-alkyl group, preferably a substituted or unsubstituted C4 to C10 tert-alkyl group.

For example, X ¹ is a substituted or unsubstituted iso-propyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted Iso-pentyl group, substituted or unsubstituted sec-pentyl group, substituted or unsubstituted tert-pentyl group, or substituted or unsubstituted neo-pentyl group, but preferably substituted or unsubstituted tert-butyl group. I can.

For example, L ¹ may include at least one secondary carbon, for example, may include a secondary carbon in the main chain of the polymer, for example, in L ¹ , the bonding point with ^{Ar 1 is secondary} It can be carbon. Here, the secondary carbon is defined as a central carbon in which two of the four bonds that the central carbon can make are each bonded to a different carbon.

Since L ¹ contains secondary carbon, a layer made of a polymer containing the structural unit represented by Formula 1 may exhibit high film strength and film density. Accordingly, when a layer having a narrow line width pattern is formed on a layer made of a polymer containing the structural unit represented by Formula 1, the warpage of the pattern can be reduced, and long vias or holes When a layer having a pattern including (hole) is formed, bowing of the pattern can be reduced.

For example, L ¹ may include a substituted or unsubstituted C1 to C15 alkylene group, for example, a substituted or unsubstituted C1 to C10 alkylene group, for example, a substituted or unsubstituted C1 to C7 An alkylene group, for example, a substituted or unsubstituted C1 to C5 alkylene group, for example, a substituted or unsubstituted C1 to C4 alkylene group may be included.

For example, L ¹ may include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a combination thereof.

For example, L ¹ may further include a substituted or unsubstituted C6 to C30 arylene group in addition to at least one secondary carbon, for example, L ¹ is a substituted or unsubstituted arylene selected from the following group 2 It may further include a group.

[Group 2]

In group 2 above,

W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,

R ^a to R ^c are each independently hydrogen, halogen, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to A C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,

p is an integer from 1 to 30,

* Is the point of connection with other moieties in the polymer.

In Group 2, each arylene group may be unsubstituted or substituted with one or more substituents. Here, the substituent is, for example, deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 alkenyl group, substituted or unsubstituted C1 To C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 arylalkyl group, It may be a substituted or unsubstituted C6 to C30 heteroarylalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof, but is not limited thereto.

For example, L ¹ may be represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

Y ¹ is a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ¹ and R ² are each independently present or linked to each other to form a ring,

R ³ and R ⁴ are each independently present or linked to each other to form a ring,

n ¹ is 0 or 1,

m ¹ is an integer of 0 to 3.

For example, Y ¹ may be any one of substituted or unsubstituted selected from Group 2.

For example, R ¹ to R ⁴ may be the same as or different from each other, for example, R ¹ and R ² may be the same as or different from each other, and R ³ and R ⁴ may be the same or different from each other.

For example, ^{at least two of R 1} to R ⁴ may be hydrogen, for example, ^{at least one of R 1} and R ² may be hydrogen, and at least one of R ³ and R ⁴ may be hydrogen, for example , R ¹ to R ⁴ may all be hydrogen.

For example, m ¹ may be an integer of 0 to 2, and m ¹ may be 0 or 1.

When m ¹ is an integer of 2 or more, a plurality of R ³ may be the same as or different from each other, and a plurality of R ⁴ may be the same or different from each other.

For example, both m ¹ and n ¹ may be 0, and both m ¹ and n ¹ may be 1.

For example, L ¹ may be any one selected from Group 3 below, but is not limited thereto.

[Group 3]

The polymer may include one or a plurality of the first structural units described above, and the number and arrangement of the first structural units included in the polymer are not limited.

For example, the polymer may further include a second structural unit different from the first structural unit, for example, in the polymer, the first structural units may be connected to each other in succession, and the second structural units may be connected to each other. The first structural unit and the second structural unit may be connected alternately, and the first structural unit and the second structural unit may be connected randomly, but are not limited thereto.

For example, the second structural unit may be represented by Formula 3 below.

[Formula 3]

In Formula 3, Ar ² is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,

X ² is a substituted or unsubstituted C3 to C10 branched alkyl group,

L ² is a divalent organic group.

For example, Ar ² may be any one of substituted or unsubstituted selected from Group 1.

For example, Ar ² may be a polycyclic aromatic ring, may be a condensed aromatic ring and/or a non-condensed aromatic ring, but preferably may be a condensed aromatic ring

In ^{the definition of Ar 2} ,'substituted' means that it is further substituted with a substituent other than *-O(C=O)OX ² shown in Formula 3, and'unsubstituted' is *- shown in Formula 3 It means that it is not further substituted with a substituent other than O(C=O)OX ^2.

For example, X ² is a substituted or unsubstituted C3 to C10 iso-alkyl group, a substituted or unsubstituted C3 to C10 sec-alkyl group, a substituted or unsubstituted C4 to C10 tert-alkyl group, or a substituted or unsubstituted C5 to C10 It may be a neo-alkyl group, preferably a substituted or unsubstituted C4 to C10 tert-alkyl group.

For example, X ² is a substituted or unsubstituted iso-propyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted Iso-pentyl group, substituted or unsubstituted sec-pentyl group, substituted or unsubstituted tert-pentyl group, or substituted or unsubstituted neo-pentyl group, but preferably substituted or unsubstituted tert-butyl group. I can.

For example, L ² may include at least one secondary carbon, for example, may include a secondary carbon in the main chain of the polymer, for example, in L ² , the bonding point with ^{Ar 2 is secondary} It can be carbon. Here, the secondary carbon is defined as a central carbon in which two of the four bonds that the central carbon can make are each bonded to a different carbon.

For example, L ² may include a substituted or unsubstituted C1 to C15 alkylene group, for example, a substituted or unsubstituted C1 to C10 alkylene group, for example, a substituted or unsubstituted C1 to C7 An alkylene group, for example, a substituted or unsubstituted C1 to C5 alkylene group, for example, a substituted or unsubstituted C1 to C4 alkylene group may be included.

For example, L ² may include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a combination thereof.

For example, L ² may further include a substituted or unsubstituted C6 to C30 arylene group in addition to at least one secondary carbon, for example, L ² is a substituted or unsubstituted arylene selected from Group 2 It may further include a group.

For example, L ² may be represented by Formula 4 below.

[Formula 4]

In Chemical Formula 4,

Y ² is a substituted or unsubstituted C6 to C30 arylene group,

R ⁵ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,

R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,

R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,

n ² is 0 or 1,

m ² is an integer from 0 to 3

For example, Y ² may be any one of substituted or unsubstituted selected from Group 2.

For example, R ⁵ to R ⁸ may be the same as or different from each other, for example, R ⁵ and R ⁶ may be the same as or different from each other, and R ⁷ and R ⁸ may be the same or different from each other.

For example, ^{at least two of R 5} to R ⁸ may be hydrogen, for example, ^{at least one of R 5} and R ⁶ may be hydrogen, and at least one of R ⁷ and R ⁸ may be hydrogen, but preferably All of R ⁵ to R ⁸ may be hydrogen.

For example, m ² may be an integer of 0 to 2, and m ² may be 0 or 1.

When m ² is an integer of 2 or more, a plurality of R ⁷ may be the same as or different from each other, and a plurality of R ⁸ may be the same or different from each other.

For example, both m ² and n ² may be 0, and both m ² and n ² may be 1.

For example, L ² may be any one selected from Group 3, but is not limited thereto.

The polymer may include one or a plurality of the second structural units described above, and the number and arrangement of the second structural units included in the polymer are not limited.

The polymer may include the first structural unit represented by Formula 5 below and optionally a second structural unit represented by Formula 6 below.

[Formula 5]

[Formula 6]

In Formulas 5 and 6, Ar ¹ , Ar ² , X ¹ , X ² , Y ¹ , Y ² , R ¹ to R ⁸ , n ¹ , n ² , m ¹ and m ² are the same as described above, and a And b is the molar ratio.

For example, Ar ¹ and Ar ² are the same as or different from each other, X ¹ and X ² are the same or different from each other, Y ¹ and Y ² are the same or different from each other, R ¹ and R ⁵ are the same or different from each other, R ² and R ⁶ are the same or different, R ³ and R ⁷ are the same or different, R ⁴ and R ⁸ are the same or different, n ¹ and n ² are the same or different, and m ¹ and m ² are the same or can be different.

However, Ar ¹ and Ar ² are the same, X ¹ and X ² are the same, Y ¹ and Y ² are the same, R ¹ and R ⁵ are the same, R ² and R ⁶ are the same, R ³ and Polymers in which R ⁷ are the same, R ⁴ and R ⁸ are the same, n ¹ and n ² are the same, and m ¹ and m ² are the same are excluded.

For example, Ar ¹ and Ar ² are different from each other, X ¹ and X ² are the same, Y ¹ and Y ² are the same, R ¹ and R ⁵ are the same, R ² and R ⁶ are the same, R ³ And R ⁷ may be the same, R ⁴ and R ⁸ may be the same, n ¹ and n ² may be the same, and m ¹ and m ² may be the same.

For example, the polymer may be represented by the following formula (7).

[Formula 7]

In Formula 7, Ar ¹ , Ar ² , X ¹ , X ² , Y ¹ , Y ² , R ¹ to R ⁸ , n ¹ , n ² , m ¹ , m ² , a and b are as described above.

The polymer may further include one or more structural units represented by Chemical Formula 1 but different from the first structural unit, and may further include one or more structural units that are represented by Chemical Formula 3 but different from the second structural unit.

The polymer further includes a third structural unit, and the third structural unit may be represented by Formula 8 below.

[Formula 8]

In Chemical Formula 8,

Ar ³ is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,

L ³ is a divalent organic group,

Ar ³ is the same as or different from ^{Ar 1,}

L ³ is the same as or different from ^{L 1.}

For example, Ar ³ may be any one of substituted or unsubstituted selected from Group 1.

For example, Ar ³ may be a polycyclic aromatic ring, may be a condensed aromatic ring and/or a non-condensed aromatic ring, but preferably may be a condensed aromatic ring.

In Formula 8, in ^{the definition of Ar 3} ,'substituted' means that it is further substituted with a substituent other than a hydroxy group (shown in Formula 8), and'unsubstituted' is a substituent other than a hydroxy group (shown in Formula 8). Means no further substitution.

For example, Ar ³ may not have a (branched alkoxycarbonyl) oxy group as a substituent.

For example, L ³ may include at least one secondary carbon, for example, may include a secondary carbon in the main chain of the polymer, for example, in L ³ , the bonding point with ^{Ar 3 is secondary} It can be carbon. Here, the secondary carbon is defined as a central carbon in which two of the four bonds that the central carbon can make are each bonded to a different carbon.

For example, L ³ may include a substituted or unsubstituted C1 to C15 alkylene group, for example, a substituted or unsubstituted C1 to C10 alkylene group, for example, a substituted or unsubstituted C1 to C7 An alkylene group, for example, a substituted or unsubstituted C1 to C5 alkylene group, for example, a substituted or unsubstituted C1 to C4 alkylene group may be included.

For example, L ³ may include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a combination thereof.

For example, L ³ may further include a substituted or unsubstituted C6 to C30 arylene group, and for example, may further include a substituted or unsubstituted arylene group selected from Group 2.

For example, L ³ may be represented by Formula 2, for example, L ³ may be any one selected from Group 3, but is not limited thereto.

The polymer may include one or a plurality of the above-described third structural units, and the number and arrangement of the above-described third structural units included in the polymer are not limited.

For example, the polymer is represented by Chemical Formula 3 and may further include a fourth structural unit different from the third structural unit.

For example, the polymer is represented by Formula 3, but may further include at least one structural unit different from the third structural unit and the fourth structural unit.

For example, the third structural units may be connected in series, the fourth structural units may be connected in succession, the third structural unit and the fourth structural unit may be alternately connected, and the third structural unit may be connected to each other. The fourth structural unit may be connected at random, but is not limited thereto.

The polymer including the above-described first structural unit may be synthesized through a condensation reaction using the polymer including the above-described third structural unit and a branched alkyl carbonate as a reactant, but is not limited thereto. The polymer containing the first structural unit (synthesized by using the polymer containing the third structural unit and the branched alkyl carbonate as a reactant) may no longer contain the third structural unit, and the third It may contain some structural units.

The polymer containing the above-described first structural unit and the above-described second structural unit can be synthesized through a condensation reaction using a polymer containing the above-described third structural unit and the above-described fourth structural unit and a branched alkyl carbonate as a reactant. However, it is not limited thereto. The polymer containing the first structural unit and the second structural unit (synthesized using the polymer containing the third structural unit and the fourth structural unit and the branched alkyl carbonate as a reactant) is the third structural unit and/or The fourth structural unit may no longer be included, and the third structural unit and/or the fourth structural unit may be partially included.

The polymer may further include one or more structural units not represented by Chemical Formula 1, Chemical Formula 3, and/or Chemical Formula 8.

The polymer may have a weight average molecular weight of about 500 to 200,000. More specifically, the polymer may have a weight average molecular weight of about 700 to 100,000, about 1,000 to 50,000, or about 1,200 to 10,000. By having a weight average molecular weight in the above range, it can be optimized by adjusting the carbon content of the polymer and the solubility in a solvent.

On the other hand, the solvent contained in the hardmask composition is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer, for example, 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- It may include at least one selected from dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate, but is not limited thereto.

The polymer may be included in, for example, about 0.1 to 60% by weight, such as about 0.5 to 50% by weight, about 1 to 35% by weight, or about 3 to 30% by weight, based on the total content of the hardmask composition. When the polymer is included in the above range, the thickness, surface roughness, and leveling degree of the hard mask can be adjusted.

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

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

Examples of the crosslinking agent include melamine-based, substituted urea-based, or these polymers. Preferably, a crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoruryl, butoxymethylated glycoruryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Compounds such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea may be used.

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

The thermal acid generator is 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, benzointosylate, 2-nitrobenzyltosylate, and other organic fonate alkyl esters may be used, but are not limited thereto.

The additive may be included in an amount of about 0.001 to 40 parts by weight, about 0.01 to 30 parts by weight, or about 0.1 to 20 parts by weight based on 100 parts by weight of the hardmask composition. By including it in the above range, the solubility can be improved without changing the optical properties of the hardmask composition.

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

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

For example, the cured product includes a condensed polycyclic aromatic hydrocarbon.

For example, the condensed polycyclic aromatic hydrocarbon is substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted naphthacene, 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 benzoperylene , Substituted or unsubstituted coronene, a combination thereof, or a combination thereof may be a fused form, but is not limited thereto.

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

Hereinafter, a method of forming a pattern using the above-described hardmask composition will be described.

A pattern formation method according to an embodiment includes forming a material layer on a substrate, applying a hardmask composition including the above-described polymer and solvent on the material layer, and forming a hardmask layer by heat treatment of the hardmask composition. Forming a photoresist layer on the hardmask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hardmask layer using the photoresist pattern, and Exposing a portion of the material layer, and etching the exposed portion of the material layer.

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

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

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

The step of heat-treating the hardmask composition may be performed at, for example, about 100 to 700° C. for about 10 seconds to 1 hour.

For example, it 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, a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and/or SiN.

For example, 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.

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

The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, 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, for example, a semiconductor integrated circuit device.

The above-described implementation examples 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 rights.

Polymer synthesis

Synthesis Example 1: Synthesis of Comparative Polymer 1

In a 100 ml flask, hydroxypyrene (12.5 g, 0.057 mol) 1,4-bis (methoxymethyl) benzene (9.6 g, 0.057 mol) was sequentially added, and propylene glycol monomethyl ether acetate (PGMEA, 51 g) I put it and melted it. P-toluenesulfonic acid monohydrate (0.001 mol) was added and stirred at 100° C. for 15 hours to perform a polymerization reaction, and the reaction was completed when the weight average molecular weight was 3,500 to 4,000. After the polymerization reaction is completed, residual acid is removed using PGMEA and deionized water (DIW), and residual monomers and oligomers are removed using cyclohexanone and n-hexane. Refine. After purification, a comparative polymer 1 including a structural unit represented by the following formula 1a was obtained. (MW: 4,500)

[Formula 1a]

Synthesis Example 2: Synthesis of Comparative Polymer 2

In a 100 ml flask, hydroxypyrene (6.5 g, 0.03 mol), hydroxyacenaphthylene (4.5 g, 0.027 mol) and 1,4-bis(methoxymethyl)benzene (9.6 g, 0.057 mol) Was sequentially added, and propylene glycol monomethyl ether acetate (PGMEA, 60 g) was added to dissolve. P-toluenesulfonic acid monohydrate (0.001 mol) was added, and the mixture was stirred at 100° C. for 20 hours to proceed with the synthesis. After the reaction, purification was performed in the same manner as in Synthesis Example 1 to obtain a comparative polymer 2 including a structural unit represented by the following formula (1a) and a structural unit represented by the following formula (1b). (MW: 4,600)

[Formula 1a] [Formula 1b]

Synthesis Example 3: Synthesis of Comparative Polymer 3

In a 100 ml flask, hydroxypyrene (21.8 g, 0.1 mol) and p-formaldehyde (p-formaldehyde, 3.5 g, 0.1 mol) were sequentially added, and propylene glycol monomethyl ether acetate (PGMEA, 60 g) was added. Melted. P-toluenesulfonic acid monohydrate (0.001 mol) was added, and the mixture was stirred at 70° C. for 24 hours to proceed with the synthesis. After the reaction, it was purified in the same manner as in Synthesis Example 1 to obtain a comparative polymer 3 including a structural unit represented by the following formula (1c). (MW: 4,200)

[Formula 1c]

Synthesis Example 4: Synthesis of Comparative Polymer 4

In a 100ml flask, hydroxypyrene (11g, 0.05mol), 1-naphthol (7.2g, 0.05mol) and p-formaldehyde (p-formaldehyde, 3.5g, 0.1mol) were sequentially added. , Propylene glycol monomethyl ether acetate (PGMEA, 100 g) was added and dissolved. P-toluenesulfonic acid monohydrate (0.001 mol) was added, and the mixture was stirred at 70° C. for 24 hours to proceed with the synthesis. After the reaction, purification was performed in the same manner as in Synthesis Example 1 to obtain a comparative polymer 4 including a structural unit represented by the following formula (1c) and a structural unit represented by the following formula (1d). (MW: 4,350)

[Formula 1c] [Formula 1d]

Synthesis Example 5: Synthesis of Comparative Polymer 5

9-phenanthrol (9-phenanthrol, 19.4 g, 0.1 mol) and p-formaldehyde (p-formaldehyde, 3.5 g, 0.1 mol) were sequentially added to a 100 ml flask, and propylene glycol monomethyl ether acetate (PGMEA, 100 g) I put it and melted it. P-toluenesulfonic acid monohydrate (0.001 mol) was added, and the mixture was stirred at 70° C. for 24 hours to proceed with the synthesis. After the reaction, it was purified in the same manner as in Synthesis Example 1 to obtain a comparative polymer 5 including a structural unit represented by the following formula (1e). (MW: 4,200)

[Formula 1e]

Synthesis Example 6: Synthesis of Polymer 1

After dissolving the comparative polymer 1 (10 g) and tetrahydrofuran (80 g) obtained in Synthesis Example 1 in a 100 ml flask, di-tert-butyl dicarbonate (7.5 g), triethylamine (triethylamine, 3.44g) and 4-dimethylaminopyridine (DMAP, 0.26g) were added and stirred for 12 hours to proceed with synthesis. After the reaction, the mixed solution was added dropwise to 300 g of n-hexane to obtain a precipitate. The precipitate was filtered, washed several times with n-hexane, and then dried in an oven for one day to obtain Polymer 1 containing a structural unit represented by the following formula (1f). (Mw: 6,700)

[Formula 1f]

Synthesis Example 7: Synthesis of Polymer 2

In the same manner as in Synthesis Example 6, except that Comparative Polymer 2 (10g) obtained in Synthesis Example 2 was used instead of Comparative Polymer 1 (10g) obtained in Synthesis Example 1, the structural unit represented by the following Formula 1f and the following Formula 1g were used. Polymer 2 containing the structural unit represented was obtained. (Mw: 7,000)

[Formula 1f] [Formula 1g]

Synthesis Example 8: Synthesis of Polymer 3

In the same manner as in Synthesis Example 6, except that Comparative Polymer 3 (10g) obtained in Synthesis Example 3 was used instead of Comparative Polymer 1 (10g) obtained in Synthesis Example 1, Polymer 3 containing a structural unit represented by the following Formula 1h Got it. (Mw: 5,100)

[Formula 1h]

Synthesis Example 9: Synthesis of Polymer 4

In the same manner as in Synthesis Example 6, except that Comparative Polymer 4 (10g) obtained in Synthesis Example 4 was used instead of Comparative Polymer 1 (10g) obtained in Synthesis Example 1, the structural unit represented by the following Formula 1h and the following Formula 1i were used. Polymer 4 containing the structural unit represented was obtained. (Mw: 6,750)

[Formula 1h] [Formula 1i]

Synthesis Example 10: Synthesis of Polymer 5

In the same manner as in Synthesis Example 6, except that Comparative Polymer 5 (10g) obtained in Synthesis Example 5 was used instead of Comparative Polymer 1 (10g) obtained in Synthesis Example 1, Polymer 5 containing a structural unit represented by Formula 1j Got it. (Mw: 6,900)

[Formula 1j]

Evaluation 1. Solubility evaluation

Each 0.5 g of Comparative Polymers 1 to 5 and Polymers 1 to 5 obtained in Synthesis Examples 1 to 10 were added to 100 g of PGMEA and dissolved using a stirrer. When the polymer is added, the amount of the polymer added to the point where the polymer that is no longer soluble is present is the maximum amount of the polymer dissolved in 100 g of PGMEA.

In addition, 10 ml of solutions obtained by dissolving each of the comparative polymers 1 to 5 and polymers 1 to 5 at the maximum in 100 g of PGMEA with a 1.0 μm syringe filter were respectively filtered to confirm whether or not the solution was filtered.

The results are shown in Table 1.

Dissolved in 100 g of PGMEA
Amount of polymer (g) 1.0μm syringe filter
Whether or not to filter the solution Comparative Polymer 1 21g X Polymer 1 32g O Comparative Polymer 2 25g Δ Polymer 2 42g O Comparative Polymer 3 12g X Polymer 3 22g O Comparative Polymer 4 22g Δ Polymer 4 45g O Comparative Polymer 5 15g X Polymer 5 28g O

O: All 10 ml of solution can be filtered

Δ: Filter clogging during solution filtration.

X: solution filtration not possible

Referring to Table 1, it can be seen that polymers 1 to 5 have improved solubility compared to comparative polymers 1 to 5.

Formation of hardmask composition

Comparative polymers 1 to 5 and polymers 1 to 5 obtained in Synthesis Examples 1 to 10 were uniformly dissolved in 100 g of PGMEA by 8 g each, and filtered through a 0.1 μm Teflon filter, respectively, of Comparative Examples 1 to 5 and Examples 1 to 5, respectively. A hardmask composition was prepared.

Evaluation 2. Membrane density

After spin-coating each of the hardmask compositions according to Comparative Examples 1 to 5 and Examples 1 to 5 on a silicon wafer, heat treatment was performed on a hot plate at about 400° C. for about 2 minutes to form an organic film having a thickness of about 1,000 Å. Formed.

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

The results are shown in Table 2.

Membrane density (g/cm ³ ) Comparative Example 1 (Comparative Polymer 1) 1.33 Example 1 (polymer 1) 1.33 Comparative Example 2 (Comparative Polymer 2) 1.35 Example 2 (polymer 2) 1.35 Comparative Example 3 (Comparative Polymer 3) 1.40 Example 3 (polymer 3) 1.40 Comparative Example 4 (Comparative Polymer 4) 1.34 Example 4 (polymer 4) 1.34 Comparative Example 5 (Comparative Polymer 5) 1.37 Example 5 (polymer 5) 1.37

Referring to Table 2, it can be seen that the organic film formed from the hardmask composition according to Examples 1 to 5 exhibited a film density equivalent to that of the organic film formed from the hardmask composition according to Comparative Examples 1 to 5.

Evaluation 3. Erosion resistance evaluation

After spin-coating each of the hardmask compositions according to Comparative Examples 1 to 5 and Examples 1 to 5 on a silicon wafer, heat treatment at about 400°C for 2 minutes on a hot plate to form an organic film having a thickness of about 4,000 I did. Subsequently, the organic layer _{was dry-etched for 100 seconds and 60 seconds using CFx gas and N 2} /O ₂ gas, respectively, and the thickness of the organic layer was measured again.

From the difference in thickness of the organic layer before and after dry etching and the etching time, the bulk etch rate (BER) was calculated according to the following equation (1).

[Calculation 1]

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

The results are shown in Table 3.

Bulk etch rate(Å/sec) CF _x etch rate (Å/s) N ₂ /O ₂ etch rate (Å/s) Comparative Example 1 (Comparative Polymer 1) 29.7 24.0 Example 1 (polymer 1) 29.8 23.8 Comparative Example 2 (Comparative Polymer 2) 28.3 23.9 Example 2 (polymer 2) 28.5 24.2 Comparative Example 3 (Comparative Polymer 3) 27.2 23.0 Example 3 (polymer 3) 27.1 22.5 Comparative Example 4 (Comparative Polymer 4) 26.5 24.3 Example 4 (polymer 4) 26.8 24.5 Comparative Example 5 (Comparative Polymer 5) 28.2 22.4 Example 5 (polymer 5) 28.0 22.5

Referring to Table 3, the organic film prepared with the hardmask composition according to Examples 1 to 5 has an etch resistance equivalent to that of the organic film prepared with the hardmask composition according to Comparative Examples 1 to 5, and sufficient for etching gas. It can be confirmed that it has corrosion resistance.

In summary, the film density and etch resistance of the organic film formed from the hardmask composition containing polymers 1 to 5 are at the same level as the organic film formed from the hardmask composition containing the comparative polymers 1 to 5, but polymers 1 to 5 It can be seen that it exhibits improved solubility compared to Comparative Polymers 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 by those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It is within the scope of the invention's rights.

Claims (15)

A hardmask composition comprising a polymer including a first structural unit represented by the following formula (1) and a solvent:
[Formula 1]

In Formula 1,
Ar ¹ is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,
X ¹ is a substituted or unsubstituted C3 to C10 branched alkyl group,
L ¹ is a divalent organic group.
In claim 1,
Ar ¹ is any one substituted or unsubstituted selected from the following group 1 hardmask composition.
[Group 1]

In claim 1,
Ar ¹ is a hard mask composition containing a condensed aromatic ring.
In claim 1,
X ¹ is a substituted or unsubstituted iso-propyl group, a substituted or unsubstituted iso-butyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted iso- A hardmask composition that is a pentyl group, a substituted or unsubstituted sec-pentyl group, a substituted or unsubstituted tert-pentyl group, or a substituted or unsubstituted neo-pentyl group.
In claim 1,
L ¹ is a hardmask composition comprising at least one secondary carbon.
In claim 1,
L ¹ is a hard mask composition comprising a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or a combination thereof.
In paragraph 6,
L ¹ is a hard mask composition further comprising a substituted or unsubstituted C6 to C30 arylene group.
In claim 1,
L ¹ is a hard mask composition represented by the following Chemical Formula 2:
[Formula 2]

In Chemical Formula 2,
Y ¹ is a substituted or unsubstituted C6 to C30 arylene group,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ¹ and R ² are each independently present or linked to each other to form a ring,
R ³ and R ⁴ are each independently present or linked to each other to form a ring,
n ¹ is 0 or 1,
m ¹ is an integer of 0 to 3.
In clause 8,
Y ¹ is any one substituted or unsubstituted selected from the following group 2 hardmask composition:
[Group 2]

In group 2 above,
W is a single bond, oxygen (-O-), sulfur (-S-), -SO ₂ -, substituted or unsubstituted ethenylene, carbonyl (-C(=O)-), CR ^a R ^b , NR ^c or a combination thereof,
R ^a to R ^c are each independently hydrogen, halogen, carboxyl group, substituted or unsubstituted C2 to C30 oxoalkyl group, substituted or unsubstituted C1 to C30 alkoxycarbonyl group, substituted or unsubstituted C1 to C30 alkoxy group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to A C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof,
p is an integer from 1 to 30,
* Is the point of connection with other moieties in the polymer of formula (2).
In claim 1,
L ¹ is any one selected from the following group 3 hardmask composition.
[Group 3]

In claim 1,
The polymer further comprises a second structural unit different from the first structural unit,
The second structural unit is a hard mask composition represented by the following formula (3).
[Formula 3]

In Chemical Formula 3,
Ar ² is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,
X ² is a substituted or unsubstituted C3 to C10 branched alkyl group,
L ² is a divalent organic group.
In claim 1,
The polymer is a hard mask composition represented by the following formula (7).
[Formula 7]

In Chemical Formula 7,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,
X ¹ and X ² are each independently a substituted or unsubstituted C3 to C10 branched alkyl group,
Y ¹ and Y ² are each independently a substituted or unsubstituted C6 to C30 arylene group,
R ¹ to R ⁸ are each independently hydrogen, deuterium, a halogen group, a nitro group, an amino group, a hydroxy group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof,
R ¹ and R ² are each independently present or linked to each other to form a ring,
R ³ and R ⁴ are each independently present or linked to each other to form a ring,
R ⁵ and R ⁶ are each independently present or linked to each other to form a ring,
R ⁷ and R ⁸ are each independently present or linked to each other to form a ring,
n ¹ and n ² are 0 or 1,
m ¹ and m ² are integers from 0 to 3,
a and b are molar ratios.
In claim 1,
The polymer further includes a third structural unit, and the third structural unit is represented by Chemical Formula 8.
[Formula 8]

In Chemical Formula 8,
Ar ³ is a substituted or unsubstituted C6 to C30 aromatic ring, a substituted or unsubstituted C3 to C30 heterocycle, or a combination thereof,
L ³ is a divalent organic group,
Ar ³ is the same as or different from ^{Ar 1,}
L ³ is the same as or different from ^{L 1.}
A hardmask layer comprising a cured product of the hardmask composition according to any one of claims 1 to 13.
Applying the hardmask composition according to any one of claims 1 to 13 on the material layer and heat treatment to form a hardmask layer,
Forming a photoresist layer on the hardmask layer,
Exposing and developing the photoresist layer to form a photoresist pattern,
Selectively removing the hardmask layer using the photoresist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
Pattern forming method comprising a.