KR102562337B1 - Hardmask composition and method of forming patterns - Google Patents

Abstract

A hard mask composition comprising a fullerene derivative including at least one substituent represented by Chemical Formula 1 below, and a polymer including a first structural unit represented by Chemical Formula 2 and a second structural unit represented by Chemical Formula 3 below; and a pattern forming method using the hard mask composition.
[Formula 1]

[Formula 2] [Formula 3]

In Chemical Formulas 1 to 3, definitions of X, Y, A ¹ , A ² , B ¹ , B ² , and * are as described in the specification.

Description

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

A 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 pattern forming method using the hard mask composition.

According to one embodiment, a fullerene derivative including at least one substituent represented by Formula 1 below; and a polymer including a first structural unit represented by Chemical Formula 2 below and a second structural unit represented by Chemical Formula 3 below.

[Formula 1]

In Formula 1,

X and Y are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, -OR ^a , -NR ^b R ^c , -L ¹ -C(=O )OR ^d , -L ² -C(=0)NR ^e R ^f , -L ³ -C(=0)N(-R ^g )C(=0)R ^h , or a combination thereof;

at least one of X and Y is -OR ^a ; -NR ^b R ^c ; -L ¹ -C(=O)OR ^d ; -L ² -C(=O)NR ^e R ^f ; -L ³ -C(=0)N(-R ^g )C(=0)R ^h ; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) a C6 to C30 aryl group substituted with C(=0)R ^h or a combination thereof; or a combination thereof;

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, or a substituted or unsubstituted C1 to C30 alkenylene group;

R ^a to R ^h are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a substituted or unsubstituted C1 to C30 alkynyl group. A C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof;

* is the connection point with the fullerene core.

[Formula 2] [Formula 3]

In Formulas 2 and 3,

A ¹ is a moiety represented by Formula 4 below;

A ² is a substituted or unsubstituted C6 to C40 aromatic ring;

B ¹ and B ² are each independently a substituted or unsubstituted C6 to C40 aryl group.

[Formula 4]

In Formula 4,

C is a substituted or unsubstituted tetragonal ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, a substituted or unsubstituted heptagonal ring or a fused ring thereof,

Z ¹ is hydrogen, a hydroxyl group, a halogen, 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, or a substituted or unsubstituted C2 to C30 alkoxy group. A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof ego,

Z ² is a hydroxy group, a halogen, a substituted or unsubstituted C1 to C20 alkoxy group, 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 C30 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

n is 0 or 1;

at least one of X and Y is -OR ^a ; -NR ^b R ^c ; -L ¹ -C(=O)OR ^d ; -L ² -C(=O)NR ^e R ^f ; -L ³ -C(=0)N(-R ^g )C(=0)R ^h ; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a phenyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=0)R ^h or a naphthyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) Anthracenyl group substituted with C(=0)R ^h or a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a phenanthrenyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a pyrenyl group substituted with a combination thereof; or a combination thereof.

L ¹ to L ³ are each independently a single bond, 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 substituted or unsubstituted pentyl group; It may be a rene group, a substituted or unsubstituted hexylene group, or a combination thereof.

R ^a to R ^h are each independently hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, or a substituted group. Or an unsubstituted hexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted pentenyl group, a substituted or unsubstituted hexenyl group, a substituted or It may be an unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted pentynyl group, a substituted or unsubstituted hexynyl group, or a combination thereof.

The fullerene derivative may include 1 to 6 substituents represented by Formula 1 above.

The fullerene core may be C60, C70, C74, C76, C78, C80, C82 or C84.

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

A ¹ may be substituted or unsubstituted selected from Group 1 below.

[Group 1]

In the group 1 above,

Z ¹ is hydrogen, a hydroxyl group, a halogen, 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, or a substituted or unsubstituted C2 to C30 alkoxy group. A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof am.

Z ¹ is hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted Unsubstituted ethenyl group, substituted or unsubstituted propenyl group, substituted or unsubstituted butenyl group, substituted or unsubstituted pentenyl group, substituted or unsubstituted hexenyl group, substituted or unsubstituted ethynyl group, substituted or unsubstituted Substituted propynyl group, substituted or unsubstituted butynyl group, substituted or unsubstituted pentynyl group, substituted or unsubstituted hexynyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthrayl group It may be a cenyl group, a substituted or unsubstituted pyrenyl group, or a combination thereof.

A ² may be a substituted or unsubstituted one selected from Group 2 below.

[Group 2]

Wherein A ² may be substituted with at least one -OR ⁱ , R ⁱ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, or a substituted or unsubstituted C2 to C30 An alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or any of these It is a combination.

B ¹ and B ² may each independently be a substituted or unsubstituted one selected from Group 3 below.

[Group 3]

.

B ¹ and B ² may be equal to each other.

At least one of A ² , B ¹ and B ² may include a condensed ring.

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

According to another embodiment, forming an organic hardmask layer by applying the above-described hardmask composition on a material layer and performing heat treatment, forming an inorganic hardmask layer on the organic hardmask layer, and photolithography on the inorganic hardmask layer. forming a resist layer, exposing and developing the photoresist layer to form a photoresist pattern, forming an inorganic hardmask pattern by selectively removing the inorganic hardmask layer using the photoresist pattern, A method of forming a pattern includes selectively removing an organic hard mask layer using the inorganic hard mask pattern to expose a portion of the material layer, and etching the exposed portion of the material layer.

Dispersion stability of the hard mask composition, etch resistance, uniform film formation, and heat resistance of the hard mask layer may 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 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 specified herein, 'substituted' means that a hydrogen atom in a compound is deuterium, a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, mercapto group, ester group, carboxyl group or its salt thereof, sulfonic acid group or its salt thereof, phosphoric acid group or its salt thereof, C1 to C30 alkyl group, C2 to C30 alkenyl group, C2 to C30 C30 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C30 alkylthiol group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 It means that it is substituted with a substituent selected from a cycloalkenyl group, a C6 to 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, mercapto group , Ester group, carboxyl group or a salt thereof, sulfonic acid group or a salt thereof, phosphoric acid or a 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 C30 alkoxy group, C1 to C30 alkylthiol group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C2 to C30 heterocycle Two adjacent substituents in a group 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.

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

As used herein, "aryl group" refers to 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 a non-aromatic hydrocarbon aromatic moiety directly or indirectly fused. Fused rings are also included. Aryl groups include monocyclic, polycyclic or fused polycyclic (ie, rings that divide 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, in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof, instead of carbon (C) It means containing at least one heteroatom selected from B, N, O, S, P, and. 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 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, or a substituted or unsubstituted naphthyl group. Cenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quaterphenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted triphenyl group A phenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a combination thereof, or a combination thereof may be fused, but is not limited thereto. .

More specifically, the substituted or unsubstituted heterocyclic group is 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 thiophenyl group, or a substituted or unsubstituted pyrazolyl group. 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 Dial, 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 group Substituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolyl group A substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzthiazinyl group, a substituted or unsubstituted acridinyl group, a substituted Or unsubstituted phenazinyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazinyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted A cyclic carbazolyl group, a pyridoindolyl group, a benzopyridooxazinyl group, a benzopyridothiazinyl group, a 9,9-dimethyl9,10dihydroacridinyl group, a combination thereof, or a combination thereof may be fused. However, it is not limited thereto. In one example of the present invention, the heterocyclic group or heteroaryl group may be a pyridyl group, a carbazolyl group or a pyridoindolyl group.

In this specification, “aromatic ring” refers to a non-condensed aromatic ring, a condensed aromatic ring, a form in which aromatic rings are connected by a single bond, a form in which each ring condensed on two non-parallel sides of a benzene ring is fused, and a benzene ring. Each ring condensed on two non-parallel sides above is connected by a single bond or a double bond, or a combination thereof.

Also, in the present specification, a polymer means including an oligomer and a polymer.

A fullerene derivative having a high carbon content can form a hard film-like organic layer, providing high etching resistance and heat resistance. However, it is difficult to form a hard mask layer having a uniform and sufficient film thickness by applying a fullerene derivative alone by a spin-on coating method. Therefore, there is a need for a hard mask composition capable of forming a hard mask layer having excellent uniformity and sufficient film thickness without deteriorating the etching resistance and heat resistance of the fullerene derivative.

According to one embodiment, a hard mask composition including a fullerene derivative and a polymer is provided.

The fullerene derivative may include a core fullerene structure and an outer substituent, and for example, the outer substituent may be substituted outward from the core fullerene structure. The fullerene derivative has at least one substituent substituted in the fullerene structure of the core, thereby increasing steric hindrance and reducing π-π stacking interactions compared to unsubstituted fullerene can make it Accordingly, the fullerene derivative can reduce aggregation compared to unsubstituted fullerene and obtain required uniformity in a solution and thin film state.

For example, the fullerene derivative may include at least one substituent represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

X and Y are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, -OR ^a , -NR ^b R ^c , -L ¹ -C(=O )OR ^d , -L ² -C(=0)NR ^e R ^f , -L ³ -C(=0)N(-R ^g )C(=0)R ^h , or a combination thereof;

at least one of X and Y is -OR ^a ; -NR ^b R ^c ; -L ¹ -C(=O)OR ^d ; -L ² -C(=O)NR ^e R ^f ; -L ³ -C(=0)N(-R ^g )C(=0)R ^h ; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) a C6 to C30 aryl group substituted with C(=0)R ^h or a combination thereof; or a combination thereof;

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, or a substituted or unsubstituted C1 to C30 alkenylene group;

R ^a to R ^h are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a substituted or unsubstituted C1 to C30 alkynyl group. A C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof;

* is the connection point with the fullerene core.

The substituted or unsubstituted C1 to C20 alkyl group, for example, a substituted or unsubstituted C1 to C15 alkyl group, for example, a substituted or unsubstituted C1 to C10 alkyl group, for example, a substituted or unsubstituted C1 to C10 alkyl group, It may be a C6 alkyl group, for example, a substituted or unsubstituted C1 to C4 alkyl group or a combination thereof. Specifically, the substituted or unsubstituted C1 to C20 alkyl group is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted phen It may be a ethyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted heptyl group, a substituted or unsubstituted octyl group, a substituted or unsubstituted nonyl group, a substituted or unsubstituted decyl group, or a combination thereof. Not limited.

The substituted or unsubstituted C2 to C20 alkenyl group, for example, a substituted or unsubstituted C2 to C15 alkenyl group, for example, a substituted or unsubstituted C2 to C10 alkenyl group, for example, a substituted or unsubstituted C2 to C10 alkenyl group may be a C2 to C8 alkenyl group, or a combination thereof. Specifically, the substituted or unsubstituted C2 to C20 alkenyl group is a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted pentenyl group, or a substituted or unsubstituted propenyl group. It may be a substituted hexenyl group, a substituted or unsubstituted heptenyl group, a substituted or unsubstituted octenyl group, a substituted or unsubstituted nonenyl group, a substituted or unsubstituted decenyl group, or a combination thereof, but is not limited thereto. does not

The substituted or unsubstituted C2 to C20 alkynyl group, for example, a substituted or unsubstituted C2 to C15 alkynyl group, for example, a substituted or unsubstituted C2 to C10 alkynyl group, for example, a substituted or unsubstituted C2 to C10 alkynyl group may be a C2 to C8 alkynyl group, or a combination thereof. Specifically, the substituted or unsubstituted C2 to C20 alkynyl group is a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted pentynyl group, or a substituted or unsubstituted propynyl group. It may be a substituted hexynyl group, a substituted or unsubstituted heptynyl group, a substituted or unsubstituted octynyl group, a substituted or unsubstituted noninyl group, a substituted or unsubstituted decynyl group, or a combination thereof, but is not limited thereto. .

The substituted or unsubstituted C6 to C30 aryl group may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted polycyclic aryl group, and the polycyclic aryl group may be a condensed cyclic aryl group and/or a non-fused cyclic aryl group. 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, or a substituted or unsubstituted naphthyl group. It may be a cyclic pyrenyl group or a combination thereof, but is not limited thereto.

At least one of X and Y is -OR ^a ; -NR ^b R ^c ; -L ¹ -C(=O)OR ^d ; -L ² -C(=O)NR ^e R ^f ; -L ³ -C(=0)N(-R ^g )C(=0)R ^h ; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) a C6 to C30 aryl group substituted with C(=0)R ^h or a combination thereof; Alternatively, by including a combination thereof, solubility and/or dispersibility of the fullerene derivative in an organic solvent may be increased, and phase separation may be reduced when mixed with a polymer described later.

For example, at least one of X and Y -OR ^a ; -NR ^b R ^c ; -L ¹ -C(=O)OR ^d ; -L ² -C(=O)NR ^e R ^f ; -L ³ -C(=0)N(-R ^g )C(=0)R ^h ; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a phenyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=0)R ^h or a naphthyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) Anthracenyl group substituted with C(=0)R ^h or a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a phenanthrenyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a pyrenyl group substituted with a combination thereof; or a combination thereof.

For example, L ¹ to L ³ may each independently be a single bond or a substituted or unsubstituted C1 to C30 alkylene group, and specifically, L ¹ to L ³ are each independently a single bond, substituted or unsubstituted methylene group group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted hexylene group, or a combination thereof.

For example, R ^a to R ^h are each independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof. A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, and a substituted or unsubstituted C2 to C20 alkynyl group are as described above, respectively.

For example, R ^a to R ^h may be the same as or different from each other, for example, R ^b and R ^c may be the same as or different from each other, R ^e and R ^f may be the same as or different from each other, and R ^g and R ^h are may be the same or different.

For example, X and Y may be the same as or different from each other.

For example, one of X and Y is -L ¹ -C(=O)OR ^d , and the other is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C30 aryl group; X and Y may both be -L ¹ -C(=O)OR ^d , where L ¹ , R ^d , a substituted or unsubstituted C1 to C20 alkyl group and a substituted or unsubstituted C6 to C30 aryl group, respectively, as described above It's like a bar.

For example, the fullerene derivative includes 1 to 6, for example, 1 to 4, for example, 1 to 3, for example, 1 or 2 substituents represented by Formula 1 can do. When there are a plurality of substituents represented by Chemical Formula 1 included in the fullerene derivative, each of the substituents represented by Chemical Formula 1 may be identical to or different from each other, but specifically may be identical to each other.

For example, the fullerene core may be C60, C70, C74, C76, C78, C80, C82, or C84, but is not limited to the number of carbon atoms because impurities having a small number of carbon atoms or a large number of carbon atoms may be included during synthesis of fullerene. , the fullerene core may be C60.

For example, the fullerene derivative may be included in an amount of, for example, 0.1 to 30 wt%, for example, about 0.5 to 25 wt%, or about 1 to 20 wt%, based on the total amount of the hardmask composition. By including the fullerene derivative in the above range, it is possible to provide a film having excellent etching resistance and heat resistance, as well as sufficient film thickness, surface roughness, and planarization characteristics.

As described above, the hardmask composition may further include a polymer, and the polymer may include a first structural unit including a heterocyclic ring as a main chain and a second structural unit including an aromatic ring as a main chain. can Accordingly, by not deteriorating the etching resistance and heat resistance of the fullerene derivative, it is possible to reduce or prevent damage caused by heat in a subsequent high-temperature process of the organic film formed of the hard mask composition including the fullerene derivative and the polymer, and in the subsequent etching process. Damage caused by an exposed etching gas may be reduced or prevented.

The first structural unit and the second structural unit of the polymer are each bonded to the main chain and may include a side chain including a substituted or unsubstituted aryl group, and the substituted or unsubstituted aryl of the side chain The group may be bonded to the main chain by a tertiary carbon. Here, tertiary carbon is defined as a central carbon in which three of the four bonds that a central carbon can make are bonded to different carbons. Accordingly, by increasing the carbon content of the polymer, not only the etching resistance can be improved, but also the solubility of the polymer in the solvent is increased, so that the polymer is prepared as a solution and has excellent uniformity and sufficient film in a solution process such as spin-on coating. An organic layer having a thickness may be formed.

For example, the polymer may include a polymer including a first structural unit represented by Chemical Formula 2 below and a second structural unit represented by Chemical Formula 3 below.

[Formula 2] [Formula 3]

In Formulas 2 and 3,

A ¹ is a moiety represented by Formula 4 below;

A ² is a substituted or unsubstituted C6 to C40 aromatic ring;

B ¹ and B ² are each independently a substituted or unsubstituted C6 to C40 aryl group.

[Formula 4]

In Formula 4,

C is a substituted or unsubstituted tetragonal ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, a substituted or unsubstituted heptagonal ring or a fused ring thereof,

Z ¹ is hydrogen, a hydroxyl group, a halogen, 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, or a substituted or unsubstituted C2 to C30 alkoxy group. A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof ego,

Z ² is a hydroxy group, a halogen, a substituted or unsubstituted C1 to C20 alkoxy group, 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 C30 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof ,

n is 0 or 1;

When the polymer includes the structural unit represented by Chemical Formula 2 and the structural unit represented by Chemical Formula 3, it may have compatibility with fullerene derivatives. Accordingly, as the fullerene derivative is mixed with the polymer and stably dispersed in the solvent, recrystallization of the fullerene derivative may be prevented, and adhesion between the formed organic layer and the lower substrate may be improved.

In Chemical Formula 4, the linking point with the polymer may be any two of carbon atoms forming a ring, and is not particularly limited.

Since the first structural unit represented by Chemical Formula 2 includes the moiety represented by Chemical Formula 4, one side of the pentagonal ring containing a nitrogen atom is blocked by a fused ring, but the other side is a ring. It is not fused by and has an open structure (ie, in Formula 4, one side of the pentagonal ring is fused with Ar, but the other side is not). Accordingly, compared to a polymer having a structural unit including a moiety (eg, carbazole) in which all pentagonal ring portions containing nitrogen atoms are blocked, as crosslinking is promoted during curing, an organic film having a high carbon content can be formed. and corrosion resistance can be further improved.

For example, C may be an aromatic ring or a non-aromatic ring, for example, C may be an aromatic ring, and may include, for example, at least one benzene ring.

For example, C may be a single ring or a polycyclic ring, the polycyclic ring may be a fused ring or a non-fused ring, and the fused ring may be, for example, a fused form of two, three or four benzene rings. It is not limited to this.

Specifically, A ¹ may be a substituted or unsubstituted one selected from Group 1 below, but is not limited thereto. In the definition of Group 1 below, 'substituted' means further substituted with another substituent, and 'unsubstituted' means not further substituted with another substituent. In the following group 1, the linking point with the polymer may be any two of carbon atoms forming a ring, and is not particularly limited.

[Group 1]

In the group 1 above,

Z ¹ is hydrogen, a hydroxyl group, a halogen, 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, or a substituted or unsubstituted C2 to C30 alkoxy group. A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof am. Here, the substituted or unsubstituted C1 to C30 alkyl group, the substituted or unsubstituted C2 to C30 alkenyl group, the substituted or unsubstituted C2 to C30 alkynyl group, and the substituted or unsubstituted C6 to C20 aryl group are as described above, respectively. .

For example, Z ¹ is hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted ethenyl group, or a substituted or unsubstituted propenyl group. , A substituted or unsubstituted butenyl group, a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted It may be an unsubstituted anthracenyl group, a substituted or unsubstituted pyrenyl group, or a combination thereof.

For example, A ² may be a substituted or unsubstituted one selected from Group 2 below. In the definition of group 2 below, 'substituted' means further substituted with another substituent, and 'unsubstituted' means not further substituted with another substituent. In the following group 2, the polymer and the linking point may be any two of carbon atoms forming a ring, and is not particularly limited.

[Group 2]

For example, A ² may be unsubstituted or substituted with at least one -OR ⁱ .

R ⁱ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroalkyl group, An unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, wherein a substituted or unsubstituted C1 to C20 alkyl group, a substituted Alternatively, the unsubstituted C2 to C20 alkenyl group and the substituted or unsubstituted C2 to C20 alkynyl group are as described above, respectively.

For example, A ² may be a polycyclic aromatic ring substituted with at least one -OR ⁱ , a condensed aromatic ring substituted with at least one -OR ⁱ , and/or a non-fused aromatic ring substituted with at least one -OR ⁱ . It may be, but preferably may be a condensed aromatic ring substituted with at least one -OR ⁱ . Accordingly, since the carbon content of the polymer can be further increased and a hard polymer layer can be formed, more excellent etching resistance can be imparted. Here, R ⁱ is as described above.

For example, B ¹ and B ² may each independently be a substituted or unsubstituted one selected from Group 3 below. In the definition of group 3 below, 'substituted' means further substituted with another substituent, and 'unsubstituted' means not further substituted with another substituent. In the following group 3, the polymer and the linking point may be any one of carbon atoms forming a ring, and is not particularly limited.

[Group 3]

.

For example, B ¹ and B ² may each independently represent a polycyclic aryl group, and the polycyclic ring may be a condensed ring and/or a non-condensed ring, but is preferably a condensed ring.

For example, B ¹ and B ² may be the same as or different from each other, but may be the same as each other.

For example, at least one of A ² , B ¹ and B ² may include a condensed ring, and A ² , B ¹ and B ² may each independently include a condensed ring.

The polymer may be obtained, for example, by reacting a reaction mixture comprising a substituted or unsubstituted heterocyclic compound, a substituted or unsubstituted aromatic compound, and a substituted or unsubstituted aromatic aldehyde compound, and the reaction may be a condensation reaction. there is.

For example, A ¹ of the first structural unit represented by Formula 2 may be derived from the substituted or unsubstituted heterocyclic compound, and A ² of the second structural unit represented by Formula 3 is the substituted or unsubstituted heterocyclic compound. It may be derived from an aromatic compound, and the side chain connected to the main chain of the polymer by a tertiary carbon (ie, B ¹ and B ² in Formulas 2 and 3) may be derived from a substituted or unsubstituted aromatic aldehyde compound.

Although not wishing to be bound by a particular theory, the side chain linked to the main chain by a tertiary carbon may be formed through a condensation reaction using the substituted or unsubstituted aromatic aldehyde compound as an electrophile. Accordingly, by connecting the main chain and the side chain with tertiary carbon, the polymer can reduce the number of hydrogen present at the bonding site of the main chain and the side chain, thereby exhibiting higher etching resistance to an etching gas exposed in a subsequent etching process. .

The polymer may include one or more of the aforementioned first structural unit and the second structural unit, respectively, and the number and arrangement of the aforementioned first structural unit and the second structural unit included in the polymer are not limited. . For example, in the polymer, the first structural units may be continuously connected, the second structural units may be continuously connected, the first structural units and the second structural units may be alternately connected, The first structural unit and the second structural unit may be randomly connected, but are not limited thereto.

The molar ratio of the aforementioned first structural unit to the second structural unit (ie, first structural unit: second structural unit) may be 9:1 to 1:9, for example, 8:2 to 2:8. It may be, for example, 7:3 to 3:7, and may be, for example, 7:3 to 5:5.

The polymer may further include one or two or more structural units not represented by Chemical Formula 2 and/or Chemical Formula 3.

For example, the polymer may have a weight average molecular weight of 1,000 to 200,000, 1,100 to 100,000, 1,200 to 50,000, 1,300 to 10,000, or 1,400 to 5,000, but is not limited thereto.

The polymer may be included in an amount of, for example, about 0.1 to 30 wt%, for example, about 0.5 to 25 wt%, about 1 to 20 wt%, or about 2 to 15 wt%, based on the total weight of the hardmask composition. By including the polymer within the above range, the thickness, surface roughness, and flatness of the hard mask may be adjusted.

The solvent (also referred to as a dispersion) included in the hard mask composition is not particularly limited as long as it has sufficient solubility and/or dispersibility for the fullerene derivative and the polymer. For example, benzene, toluene, p-xylene, o-dichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, 1,2,4-trimethylbenzene, tetrahydronaphthalene, 1,2,3-tribromopropane, chlorobenzene, tribromomethane, cumene, It may include at least one selected from cyclohexanone, anisole, and gamma butyrolactone. It is not limited to this.

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

As the surfactant, for example, fluoroalkyl-based compounds, alkylbenzenesulfonic acid salts, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, etc. may be used, but are 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 crosslinking substituents, for example, methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated 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.

The additive may be included in about 0.001 to 30 parts by weight, about 0.01 to 20 parts by weight, or about 0.1 to 10 parts by weight based on 100 parts by weight of the hard mask composition. When included within the above range, the solubility of the hard mask composition may be improved without changing the optical properties.

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

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

A pattern forming method according to an embodiment includes forming a material layer on a substrate, applying the hardmask composition described above to the material layer, heat-treating the hardmask composition to form a hardmask layer, and forming the hardmask layer. forming a photoresist layer over the layer, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern to selectively remove the hardmask layer and expose a portion of the material layer. and etching the exposed portion of the material layer. Here, the hard mask layer is also referred to as an organic hard mask layer hereinafter.

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 hard mask composition is not particularly limited, but may be, for example, about 50 Å to 200,000 Å thick.

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

For example, the method may further include forming an inorganic hard mask layer on the organic hard mask layer. The inorganic hardmask layer may contain silicon, and for example, the inorganic hardmask layer may be formed of 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 organic hard mask layer or the inorganic hard mask layer.

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.

When an inorganic hard mask layer is formed on the organic hard mask layer, the step of selectively removing the hard mask layer using the photoresist pattern and exposing a portion of the material layer may include using the photoresist pattern to form the inorganic hard mask layer. The method may include forming an inorganic hardmask pattern by selectively removing the mask layer, and selectively removing the organic hardmask layer using the inorganic hardmask pattern to expose a portion of the material layer.

Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, such as CHF ₃ , CF ₄ , Cl ₂ , N- ₂ /O ₂ , BCl ₃ and the like. Mixed gases 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 metal patterns, semiconductor patterns, and insulating patterns, and may be applied as various patterns in a semiconductor integrated circuit device, for example.

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

synthesis example

Synthesis Example 1

Indole (50.0 g, 0.43 mol), phenanthren-9-ol (Phenanthren-9-ol, 83.4 g, 0.43 mol), 1-naphthalaldehyde ( 1-naphtaldehyde, 133 g, 0.85 mol) and methanesulfonic acid (41.0 g, 0.43 mol) were added to 1,4-dioxane (1,4-Dioxane, 285.9 g), stirred well, and then heated at 100 ° C. The reaction is carried out with stirring for 24 hours. After completion of the reaction, the internal temperature is cooled to 60 to 70 ° C., and tetrahydrofuran (300 g) is added so as not to harden. Thereafter, a 7% sodium bicarbonate aqueous solution was added to adjust the pH to 5 to 6, ethyl acetate (1000ml) was added, stirred continuously, and only the organic layer was extracted using a separatory funnel. After adding water (500ml) to the separatory funnel and shaking to remove remaining acid and sodium salt, the organic layer was finally extracted after repeating the process three or more times. The extracted organic solution was concentrated with an evaporator, tetrahydrofuran (1L) was added thereto to dissolve it, and it was slowly added dropwise to a beaker containing hexane (5L) being stirred to obtain structural units represented by the following formula (2a) and chemical formula Polymer 1 containing the structural unit represented by 3a was obtained. The molar ratio of the structural unit represented by Chemical Formula 2a and the structural unit represented by Chemical Formula 3a included in Polymer 1 is 6:4

Polymer 1 obtained by gel permeation chromatography (GPC) had a weight average molecular weight (Mw) of 1,890 and a polydispersity (PD) of 1.35.

[Formula 2a] [Formula 3a]

Synthesis Example 2

Structural unit represented by Formula 2b in the same manner as in Synthesis Example 1, except that 9-phenanthrene carbaldehyde (9-phenanthrene carbaldehyde, 175 g, 0.85 mol) was used instead of 1-naphthalaldehyde (133 g, 0.85 mol) and Polymer 2 including a structural unit represented by Formula 3b below was obtained. The molar ratio of the structural unit represented by Chemical Formula 2b and the structural unit represented by Chemical Formula 3b included in Polymer 2 is 6:4

The weight average molecular weight (Mw) of Polymer 2 obtained using gel permeation chromatography was 2,108, and the polydispersity was 1.49.

[Formula 2b] [Formula 3b]

Synthesis Example 3

1-hydroxypyrene (1-hydroxypyrene, 94 g, 0.43 mol) was used instead of phenanthrene-9-ol (83.4 g, 0.43 mol), and pyrene-1 was used instead of 1-naphthaldehyde (133 g, 0.85 mol). Polymer 3 comprising structural units represented by the following Chemical Formula 2c and structural units represented by the following Chemical Formula 3c in the same manner as in Synthesis Example 1 except that carbaldehyde (Pyrene-1-carbaldehyde, 186 g, 0.85 mol) was used. got The molar ratio of the structural unit represented by Chemical Formula 2c and the structural unit represented by Chemical Formula 3c included in Polymer 3 is 5:5

The weight average molecular weight (Mw) of Polymer 3 obtained using gel permeation chromatography was 1,570, and the polydispersity was 1.26.

[Formula 2c] [Formula 3c]

Synthesis Example 4

Except for using perylene-3-carbaldehyde (Perylene-3-carbaldehyde, 238 g, 0.85 mol) instead of pyrene-1-carbaldehyde (186 g, 0.85 mol), the same method as in Synthesis Example 3 was used to formula 2d Polymer 4 including the structural unit represented by the structural unit and the structural unit represented by Chemical Formula 3d below was obtained. The molar ratio of the structural unit represented by Chemical Formula 2d and the structural unit represented by Chemical Formula 3d included in Polymer 4 is 6:4

The weight average molecular weight (Mw) of Polymer 4 obtained using gel permeation chromatography was 1,799, and the polydispersity was 1.39.

[Formula 2d] [Formula 3d]

Synthesis Example 5

Except for using 1H-benzoindole (1H-Benzoindole, 72 g, 0.43 mol) instead of indole (50.0 g, 0.43 mol), the same method as in Synthesis Example 3 was performed, the structural unit represented by Formula 2e and the structural unit represented by Formula 3c below Polymer 5 containing structural units to be obtained was obtained. The molar ratio of the structural unit represented by Chemical Formula 2e and the structural unit represented by Chemical Formula 3c included in Polymer 5 is 7:3

The weight average molecular weight (Mw) of Polymer 5 obtained using gel permeation chromatography was 1,915, and the polydispersity was 1.33.

[Formula 2e] [Formula 3c]

Synthesis Example 6

Structure represented by Chemical Formula 2f in the same manner as in Synthesis Example 3, except that 1-phenyl-1H-indole (1-Phenyl-1H-indole, 83 g, 0.43 mol) was used instead of indole (50.0 g, 0.43 mol). Polymer 6 including a unit and a structural unit represented by Formula 3c was obtained. The molar ratio of the structural unit represented by Chemical Formula 2f and the structural unit represented by Chemical Formula 3c included in Polymer 6 is 6:4

The weight average molecular weight (Mw) of polymer 6 obtained using gel permeation chromatography was 1,547, and the polydispersity was 1.32.

[Formula 2f] [Formula 3c]

Synthesis Example 7

Polymer 2 (31.0 g) and dimethylformamide (200 g) obtained in Synthesis Example 2 were put in a 500 ml two-necked flask equipped with a mechanical stirrer and stirred. After confirming that the polymer is completely dissolved, potassium hydroxide (7g) is slowly added dropwise to the stirring flask. After stirring for 30 minutes, propargyl bromide (19g) was slowly added, and the temperature inside the flask was raised to 60°C. After reaching the temperature, the reaction is carried out while stirring for 8 hours. After completion of the reaction, it is cooled to room temperature. Thereafter, ethanol (50ml) was slowly added to the flask, and after 10 minutes, it was slowly added to 1.5L of water being stirred in a 2L beaker. After completely adding, stir for 2 hours. After filtering the precipitated solid to remove water, the process of washing with a mixed solution of water (500ml) and tetrahydrofuran (200ml) is repeated three or more times. Thereafter, the solid is dried to obtain a polymer 7 including a structural unit represented by 2g below and a structural unit represented by Chemical Formula 3g below. The molar ratio of the structural unit represented by Chemical Formula 2g and the structural unit represented by Chemical Formula 3g included in Polymer 7 is 6:4

The weight average molecular weight (Mw) of Polymer 7 obtained using gel permeation chromatography was 1,880, and the polydispersity was 1.34.

[Formula 2g] [Formula 3g]

Synthesis Example 8

Diethyl bromomalonate (2.4 g) and C ₆₀ fullerene (4 g) were mixed with monochlorobenzene: dimethyl sulfoxide in a 2:1 volume ratio in a 100 mL three-necked flask equipped with a mechanical stirrer and cooling tube. (C ₆ H ₅ Cl:DMSO) was added together with 50 g, and stirred at 20° C. for 30 minutes. Then, sarcosine (2 g) is added, and the reaction is carried out with further stirring for 2 hours. After completion of the reaction, it was washed three times with monochlorobenzene and distilled water, and the solvent was evaporated under reduced pressure to obtain 4.3 g of a reddish-brown solid. Using silica gel chromatography, the obtained solid was fractionated with a mixed solvent of n-hexane:ethyl acetate in a volume ratio of 1:1.5 to obtain a fullerene derivative represented by the following formula (1c).

[Formula 1c]

Comparative Synthesis Example 1

Indole (50.0 g, 0.43 mol), 6-hydroxypyrene-1-carbaldehyde (6-hydroxypyrene-1-carbaldehyde, 110 g, 0.43 mol), and methane were placed in a 500 ml two-necked flask equipped with a mechanical stirrer and cooling tube. Sulfonilic acid (20.5 g, 0.21 mol) was added to 1,4-dioxane (160 g), and after stirring well, the reaction was performed at 100° C. for 24 hours with stirring. After completion of the reaction, the internal temperature is cooled to 60 to 70 ° C., and tetrahydrofuran (300 g) is added so as not to harden. Thereafter, a 7% sodium bicarbonate aqueous solution was added to adjust the pH to 5 to 6, ethyl acetate (1000ml) was added, stirring was continued, and only the organic layer was extracted using a separatory funnel. After adding water (500ml) to the separatory funnel and shaking to remove remaining acid and sodium salt, the organic layer was finally extracted after repeating the process three or more times. After concentrating the extracted organic solution with an evaporator, adding tetrahydrofuran (1L) thereto to dissolve it, and slowly adding it dropwise to a beaker containing hexane (5L) being stirred, to include a structural unit represented by Formula 2h Comparative Polymer 1 is obtained.

The weight average molecular weight (Mw) of Comparative Polymer 1 obtained using gel permeation chromatography (GPC) was 1,711 and the polydispersity was 1.33.

[Formula 2h]

Comparative Synthesis Example 2

Indole (50.0 g, 0.43 mol) was replaced with 1-hydroxypyrene (94 g, 0.43 mol), and 6-hydroxypyrene-1-carbaldehyde (110 g, 0.43 mol) was replaced with pyrene-1-carbaldehyde ( 99 g, 0.43 mol), was obtained in the same manner as Comparative Synthesis Example 1, except that Comparative Polymer 2 including a structural unit represented by Chemical Formula 3c was used.

[Formula 3c]

The weight average molecular weight (Mw) of Comparative Polymer 2 obtained using gel permeation chromatography (GPC) was 1,638 and the polydispersity was 1.37.

Comparative Synthesis Example 3

Benzoperylene (28 g, 0.1 mol), 2-naphthoyl chloride (76 g, 0.4 mol), and trichloro aluminum were added to a 1 L three-necked flask equipped with a mechanical stirrer and cooling tube , 79.8 g, 0.6 mol) into toluene (Toluene, 1,000 g) and dissolved. Thereafter, the flask is immersed in an oil thermostat at 90° C. and the reaction is performed while stirring for 10 hours. After completion of the reaction, trichloroaluminum was removed using water, sodium borohydride (37.8g, 1.0mol) was added, and the reaction was carried out for 17 hours. After completion of the reaction, reaction by-products are removed using a mixture of water and methanol, and the organic solution is concentrated with an evaporator. After adding and dissolving tetrahydrofuran (1L) to the concentrated solution, it is slowly added dropwise to a beaker containing hexane (5L) being stirred and precipitates are formed to obtain Comparative Compound 1 represented by Formula B below. The molecular weight of Comparative Compound 1 represented by Chemical Formula B is 900.

[Formula B]

Comparative Synthesis Example 4

Pyrene (28.32 g, 0.14 mol), 1-naphthol (28.83 g, 0.2 mol) and paraformaldehyde ( p -Formaldehyde, 12.08 g, 0.4 mol) were mixed in a 1 L three-necked flask equipped with a mechanical stirrer and a cooling tube. After adding a solution of p -toluene sulfonic acid monohydrate (0.57 g, 0.003 mol) dissolved in propylene glycol monomethyl ether acetate (PGMEA, 163 g), at 60 ° C. Polymerize by stirring for 18 hours. After completion of the polymerization reaction, put in distilled water (40g) and methanol (400g), vigorously stirred, and left to stand (first process). After removing the supernatant and dissolving the precipitate in 80 g of PGMEA, 320 g of methanol was added, vigorously stirred, and allowed to stand (second process). Performing the second process once after the first process is referred to as a single purification process, and the purification process is repeated two more times. After the purification process, the polymer was dissolved in 80 g of PGMEA and concentrated under reduced pressure to remove residual methanol and distilled water. After adding and dissolving tetrahydrofuran (1L) to the obtained concentrate, it was slowly added dropwise to a beaker containing hexane (1L) being stirred and precipitated to form Comparative Polymer 3 containing a structural unit represented by Formula A below get

[Formula A]

Comparative Polymer 3 obtained using gel permeation chromatography (GPC) had a weight average molecular weight (Mw) of 4,000 and a polydispersity of 1.75.

Formation of Hardmask Composition

Example 1

Polymer 1 (1g) obtained in Synthesis Example 1 and C ₆₀ PCBM (Phenyl-C ₆₁ -butyric acid methyl ester, MST, 1g) represented by Formula 1a below were mixed with o -dichlorobenzene ( o -Dichlorobenzene, 20g) After mixing, the mixture was dispersed for 20 minutes using an ultrasonic grinder, and filtered through a 0.45 μm Teflon filter to prepare a hard mask composition of Example 1.

[Formula 1a]

Example 2

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

Example 3

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

Example 4

A hardmask composition of Example 4 was prepared in the same manner as in Example 1, except that Polymer 4 (1g) obtained in Synthesis Example 4 was used instead of Polymer 1 (1g) obtained in Synthesis Example 1.

Example 5

A hardmask composition of Example 5 was prepared in the same manner as in Example 1, except that Polymer 5 (1g) obtained in Synthesis Example 5 was used instead of Polymer 1 (1g) obtained in Synthesis Example 1.

Example 6

A hardmask composition of Example 6 was prepared in the same manner as in Example 1, except that Polymer 6 (1g) obtained in Synthesis Example 6 was used instead of Polymer 1 (1g) obtained in Synthesis Example 1.

Example 7

A hardmask composition of Example 7 was prepared in the same manner as in Example 1, except that Polymer 7 (1g) obtained in Synthesis Example 7 was used instead of Polymer 1 (1g) obtained in Synthesis Example 1.

Example 8

The hardmask composition of Example 8 was prepared in the same manner as in Example 3, except that a fullerene derivative (1g, TCI) represented by Formula 1b was used instead of C ₆₀ PCBM (1g).

[Formula 1b]

Example 9

The hardmask composition of Example 9 was prepared in the same manner as in Example 3, except that the fullerene derivative (1g) represented by Formula 1c obtained in Synthesis Example 8 was used instead of C ₆₀ PCBM (1g).

[Formula 1c]

Comparative Example 1

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

Comparative Example 2

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

Comparative Example 3

A hardmask composition of Comparative Example 3 was prepared in the same manner as in Example 1, except that Comparative Compound 1 (1g) obtained in Comparative Synthesis Example 3 was used instead of Polymer 1 (1g) obtained in Synthesis Example 1.

Comparative Example 4

A hardmask composition of Comparative Example 4 was prepared in the same manner as in Example 1, except that Comparative Polymer 3 (1g) obtained in Comparative Synthesis Example 4 was used instead of Polymer 1 (1g) obtained in Synthesis Example 1.

Comparative Example 5

Instead of Polymer 1 (1g) obtained in Synthesis Example 1, a compound (1g) represented by Formula C, pyridinium p-toluenesulfonate (0.1g) as a thermal acid generator, and C ₆₀ PCBM (1g) were added Mix with o -dichlorobenzene (15 g) and Anisole (5 g). Thereafter, the hardmask composition of Comparative Example 5 was prepared by dispersing for 20 minutes using an ultrasonic mill and filtering with a 0.45 μm Teflon filter.

[Formula C]

Comparative Example 6

Polymer 3 (2 g) obtained in Synthesis Example 3 was mixed with o -dichlorobenzene (20 g), dispersed for 20 minutes using an ultrasonic mill, and filtered through a 0.45 μm Teflon filter to obtain a hard mask of Comparative Example 6. composition was prepared

Evaluation 1: Dispersion stability

The hard mask compositions according to Examples 1 to 9 and Comparative Examples 1 to 4 were stored at room temperature, and then, after 72 hours, precipitation was visually confirmed.

The results are shown in Table 1.

dispersion stability Example 1 O Example 2 O Example 3 O Example 4 O Example 5 O Example 6 O Example 7 O Example 8 O Example 9 O Comparative Example 1 X Comparative Example 2 X Comparative Example 3 X Comparative Example 4 X

O: When not precipitated and dispersion stability is maintained

X: When precipitated

Referring to Table 1, in the hardmask compositions of Examples 1 to 9, compared to the hardmask compositions of Comparative Examples 1 to 4, since the fullerene derivative and the polymer included in the hardmask composition have compatibility with each other, they do not precipitate. It can be confirmed that it has excellent dispersion stability. Accordingly, compared to the hardmask compositions according to Comparative Examples 1 to 4, it can be confirmed that the hardmask compositions according to Examples 1 to 9 are suitable for forming a film by a solution process, for example, spin coating.

Hereinafter, the etching resistance and heat resistance of the organic film formed by spin-coating the hard mask composition according to Examples and Comparative Examples on a silicon wafer are evaluated. However, as described above, since the hardmask compositions of Comparative Examples 1 to 4 have low dispersion stability and it is difficult to form a film by spin coating, the evaluation of etching resistance, heat resistance, and film formation of Comparative Examples 1 to 4 is omitted.

Evaluation 2: Erosion resistance 1

After spin-coating the hard mask composition according to Examples 1 to 9, Comparative Example 5, and Comparative Example 6 on a silicon wafer, heat treatment at 550 ° C. for 2 minutes in a nitrogen atmosphere to form an organic film, and then a thin film thickness meter (K-MAC Co.) to measure the thickness of the organic film. next. After dry etching the thin film for 30 seconds using a N ₂ /O ₂ mixed gas, the thickness of the organic film was measured again. A bulk etch rate (BER) was calculated from the difference in thickness of the organic film before and after dry etching and the etching time by Equation 1 below.

[Calculation 1]

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

The results are shown in Table 2.

Etch rate (Å/s) Example 1 17.5 Example 2 16.8 Example 3 15.9 Example 4 15.1 Example 5 15.5 Example 6 15.3 Example 7 16.2 Example 8 16.3 Example 9 15.8 Comparative Example 5 22.8 Comparative Example 6 20.0

Referring to Table 2, the organic films according to Examples 1 to 9 were compared with the organic films according to Comparative Example 5 containing the compound represented by Formula C instead of the polymer and Comparative Example 6 not containing the fullerene derivative, thereby reducing etching gas. It can be confirmed that the corrosion resistance is improved because there is sufficient corrosion resistance to the

Evaluation 3: film formation and heat resistance

The hard mask composition according to Example 3 and Comparative Example 6 was spin-coated on a silicon wafer, respectively, and then heat-treated under the four conditions in Tables 3 and 4 to form an organic film, and the thickness of the formed organic film was varied. Each was measured 51 times. The organic film formation and measurement were repeated for two silicon wafers for each condition.

The average value of the thickness of the organic film coated on each silicon wafer is shown in Table 3, and the difference between the thickest film thickness and the thinnest film thickness in each coated organic film is shown in Table 4.

Air_400℃/1min _{N2_550} ℃/2min Air_400℃/1min+
_{N2_550} ℃/2min Air_400℃/1min+
_{N2_550} ℃/5min Example 3_#1 2038 1139 1920 1915 Example 3_#2 2039 1128 1928 1919 Comparative Example 6_#1 1973 984 1709 1651 Comparative Example 6_#2 1977 931 1713 1646

Air_400℃/1min _{N2_550} ℃/2min Air_400℃/1min+
_{N2_550} ℃/2min Air_400℃/1min+
_{N2_550} ℃/5min Example 3_#1 20 156 15 13 Example 3_#2 24 158 16 16 Comparative Example 6_#1 18 279 97 80 Comparative Example 6_#2 20 221 100 76

Referring to Tables 3 and 4, compared to Comparative Example 6 not containing a fullerene derivative under all film formation conditions, Example 3 had a larger film thickness average value and a smaller film thickness deviation on the same silicon wafer, so Comparative Example 6 Compared to that of Example 3, it can be confirmed that the heat resistance and film formation properties are excellent.

In addition, referring to Tables 3 and 4, when a film is formed by curing only in an N ₂ atmosphere, compared to the case where a film is formed in the air or additionally cured under a N ₂ atmosphere after forming a film in the air, Example 3 and It can be confirmed that all of Comparative Example 6 had poor heat resistance and poor film formation. Furthermore, it can be seen that when the film is formed in the air and then calcined at a high temperature of 550° C. or higher under an N ₂ atmosphere, the difference between the film thickness average value and the film thickness deviation between Example 3 and Comparative Example 6 is more obvious.

While not wishing to be bound by any particular theory, it is believed that crosslinking between polymers proceeds upon curing under air, but crosslinking of polymers does not proceed under N ₂ atmosphere. Therefore, in both Example 3 and Comparative Example 6, when a film was formed by curing only in an N ₂ atmosphere, heat resistance and film formation were the most poor, and in the case of Example 3, a film was formed in the atmosphere and then further cured in an N ₂ atmosphere. It is considered to have the best heat resistance and film formation properties.

Evaluation 4: Erosion resistance 2

After spin-coating the hardmask composition according to Example 3 and Comparative Example 6 on a silicon wafer, heat treatment was performed at 400° C. for 1 minute in an air atmosphere, and then heat treatment was performed at 550° C. for 2 minutes or 5 minutes under a nitrogen atmosphere. After forming the film, the thickness of the formed organic film was measured with a thin film thickness meter (K-MAC Co.). next. After dry etching the thin film for 30 seconds using a N ₂ /O ₂ mixed gas, the thickness of the organic film was measured again. A bulk etch rate (BER) was calculated from the difference in thickness of the organic film before and after dry etching and the etching time by Equation 1 above.

The results are shown in Table 5.

Etch rate (Å/s) Air_400℃/1min + _N2 _550℃/2min Air_400℃/1min + _N2 _550℃/5min Example 3 15.5 15.3 Comparative Example 6 19.7 19.2

Referring to Table 5, even when the film is formed in the air and then calcined at a high temperature of 550° C. or more under an N ₂ atmosphere, as in Table 2, the organic film according to Example 3 is obtained according to Comparative Example 6 without a fullerene derivative. Compared to the organic film, it can be confirmed that it has sufficient etching resistance to etching gas.

In summary, it is impossible to form an organic layer sufficient to be applied as a hard mask layer through spin-coating with the fullerene derivative alone. However, since the fullerene derivatives represented by Chemical Formulas 1a to 1c and the polymers of Synthesis Examples 1 to 7 are compatible with each other, the hardmask compositions of Examples 1 to 9 including a combination thereof can be obtained by spin-coating. An organic film can be formed, and the formed organic film can have a sufficient film thickness and a small film thickness deviation. Furthermore, the organic layer formed with the hard mask compositions of Examples 1 to 9 may have excellent heat resistance while maintaining excellent etching resistance of the fullerene derivative. In addition, when an organic film is formed by forming a film in the air and then firing at a high temperature of 550° C. or more under an N ₂ atmosphere, the organic film formed from the hard mask compositions of Examples 1 to 9 by crosslinking between polymers has excellent film formation and corrosion resistance. It can show arousal and heat resistance.

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 (16)

A fullerene derivative containing at least one substituent represented by Formula 1 below, and
A hard mask composition comprising a polymer including a first structural unit represented by Formula 2 below and a second structural unit represented by Formula 3 below:
[Formula 1]

In Formula 1,
X and Y are each independently hydrogen, halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, -OR ^a , -NR ^b R ^c , -L ¹ -C(=O )OR ^d , -L ² -C(=0)NR ^e R ^f , -L ³ -C(=0)N(-R ^g )C(=0)R ^h , or a combination thereof;
at least one of X and Y is -OR ^a ; -NR ^b R ^c ; -L ¹ -C(=O)OR ^d ; -L ² -C(=O)NR ^e R ^f ; -L ³ -C(=0)N(-R ^g )C(=0)R ^h ; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) a C6 to C30 aryl group substituted with C(=0)R ^h or a combination thereof; or a combination thereof;
L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, or a substituted or unsubstituted C1 to C30 alkenylene group;
R ^a to R ^h are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, or a substituted or unsubstituted C1 to C30 alkynyl group. A C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof;
* is the point of connection with the fullerene core:
[Formula 2] [Formula 3]

In Formulas 2 and 3,
A ¹ is a moiety represented by Formula 4 below;
A ² is a substituted or unsubstituted C6 to C40 aromatic ring;
B ¹ and B ² are each independently a substituted or unsubstituted C6 to C40 aryl group:
[Formula 4]

In Formula 4,
C is a substituted or unsubstituted tetragonal ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, a substituted or unsubstituted heptagonal ring or a fused ring thereof,
Z ¹ is hydrogen, a hydroxyl group, a halogen, 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, or a substituted or unsubstituted C2 to C30 alkoxy group. A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof ego,
Z ² is a hydroxy group, a halogen, a substituted or unsubstituted C1 to C20 alkoxy group, 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 C30 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof ,
n is 0 or 1;
In paragraph 1,
at least one of X and Y is -OR ^a ; -NR ^b R ^c ; -L ¹ -C(=O)OR ^d ; -L ² -C(=O)NR ^e R ^f ; -L ³ -C(=0)N(-R ^g )C(=0)R ^h ; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a phenyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=0)R ^h or a naphthyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) Anthracenyl group substituted with C(=0)R ^h or a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a phenanthrenyl group substituted with a combination thereof; -OR ^a , -NR ^b R ^c , -L ¹ -C(=O)OR ^d , -L ² -C(=O)NR ^e R ^f , -L ³ -C(=O)N(-R ^g ) C(=O)R ^h or a pyrenyl group substituted with a combination thereof; Or a hard mask composition that is a combination thereof.
In paragraph 1,
L ¹ to L ³ are each independently a single bond, 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 substituted or unsubstituted pentyl group; A hard mask composition comprising a rene group, a substituted or unsubstituted hexylene group, or a combination thereof.
In paragraph 1,
R ^a to R ^h are each independently hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, or a substituted group. Or an unsubstituted hexyl group, a substituted or unsubstituted ethenyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, a substituted or unsubstituted pentenyl group, a substituted or unsubstituted hexenyl group, a substituted or A hard mask composition comprising an unsubstituted ethynyl group, a substituted or unsubstituted propynyl group, a substituted or unsubstituted butynyl group, a substituted or unsubstituted pentynyl group, a substituted or unsubstituted hexynyl group, or a combination thereof.
In paragraph 1,
The hard mask composition of claim 1 , wherein the fullerene derivative includes 1 to 6 substituents represented by Chemical Formula 1.
In paragraph 1,
The hard mask composition of claim 1, wherein the fullerene core is C60, C70, C74, C76, C78, C80, C82 or C84.
In paragraph 1,
The hard mask composition of claim 1, wherein the fullerene derivative is included in an amount of 0.1 to 30% by weight based on the total content of the hard mask composition.
In paragraph 1,
A hardmask composition in which A ¹ is any one of substituted or unsubstituted selected from Group 1 below:
[Group 1]

In the group 1 above,
Z ¹ is hydrogen, a hydroxyl group, a halogen, 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, or a substituted or unsubstituted C2 to C30 alkoxy group. A substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof am.
In paragraph 1,
Z ¹ is hydrogen, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted Unsubstituted ethenyl group, substituted or unsubstituted propenyl group, substituted or unsubstituted butenyl group, substituted or unsubstituted pentenyl group, substituted or unsubstituted hexenyl group, substituted or unsubstituted ethynyl group, substituted or unsubstituted Substituted propynyl group, substituted or unsubstituted butynyl group, substituted or unsubstituted pentynyl group, substituted or unsubstituted hexynyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthrayl group A hard mask composition comprising a cenyl group, a substituted or unsubstituted pyrenyl group, or a combination thereof.
In paragraph 1,
A ² is a substituted or unsubstituted hardmask composition selected from Group 2 below:
[Group 2]

In paragraph 1,
A ² is substituted with at least one -OR ⁱ ;
R ⁱ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heteroalkyl group, A hard mask composition comprising an unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.
In paragraph 1,
B ¹ and B ² are each independently a substituted or unsubstituted hardmask composition selected from Group 3 below:
[Group 3]
.
In paragraph 1,
B ¹ and B ² are the same hardmask composition.
In paragraph 1,
A hardmask composition wherein at least one of A ² , B ¹ and B ² includes a condensed ring.
In paragraph 1,
The hard mask composition of claim 1, wherein the polymer is included in an amount of 0.1% to 30% by weight based on the total amount of the hardmask composition.
Forming an organic hard mask layer by applying a hard mask composition according to any one of claims 1 to 15 on a material layer and heat-treating;
forming an inorganic hardmask layer on the organic hardmask layer;
Forming a photoresist layer on the inorganic hard mask layer;
Exposing and developing the photoresist layer to form a photoresist pattern;
forming an inorganic hard mask pattern by selectively removing the inorganic hard mask layer using the photoresist pattern;
selectively removing an organic hard mask layer using the inorganic hard mask pattern and exposing a portion of the material layer; and
Etching the exposed portion of the material layer
Pattern forming method comprising a.