KR20220034364A - Composition for hard mask - Google Patents

Abstract

The present invention relates to a composition for a hard mask comprising a polymer comprising a repeating unit having a specific structure. The composition for a hard mask according to the present invention comprises an amide group which is thermally stable and has excellent solubility, thereby improving etch resistance and heat resistance.

Description

Composition for hard mask {COMPOSITION FOR HARD MASK}

The present invention relates to a composition for a hard mask.

Recently, high-integration design due to miniaturization and complexity of electronic devices is accelerating the development of more advanced materials and related processes. Accordingly, lithography using existing photoresists also requires new patterning materials and techniques. became

In the case of the existing lithography patterning process, a photoresist (PR), a photosensitive liquid, is applied on the wafer to form a photoresist layer, and a metal photomask engraved with a design pattern is placed on the wafer using exposure equipment, and a circuit is engraved by passing light through it. After inserting, a method of forming a pattern by selectively removing exposed or unexposed areas while spraying a developer was used.

An anti-reflective coating (ARC) layer was formed between the wafer layer and the photoresist layer to suppress resolution degradation due to light reflection during the exposure process. In this case, etching of the ARC layer is added, and accordingly, consumption or etching amount of the photoresist layer or photoresist pattern may be increased, and the thickness of the etch target film may increase or the amount of etching required to form a desired pattern increases. There was a problem in that sufficient etching resistance of the photoresist layer or the photoresist pattern, which is required, was not secured. In addition, as the miniaturization of the pattern is required, in the case of the existing patterning method using only photoresist, it is difficult to form the miniaturized pattern.

Therefore, in the patterning process, in order to transfer the photoresist micropattern to the substrate to a sufficient depth without collapsing and to refine the pattern, an organic layer called a hard mask layer, which is a hard intermediate layer, is added between the wafer and the photoresist layer. method was introduced.

Such a hardmask layer requires properties such as heat resistance and etch resistance to withstand multiple etching processes. In order to form the hardmask layer by spin-on coating, it must have excellent solubility, and - Coating properties such as gap-fill properties and planarization properties are also required.

The conventional hardmask composition has a problem in that it is difficult to apply to a spin-on type because solubility is lowered as a polymer compound is included to ensure heat resistance and etch resistance. Therefore, there is a need for a hard mask composition that can satisfy all of the above characteristics.

In this regard, Korean Patent Application Laid-Open No. 10-2016-0008930 discloses a hard mask composition having improved heat resistance and gap-fill properties including a compound having a specific structure, but there is a problem in that the etch-resistance effect is not satisfied. there is.

In addition, Korean Patent Application Laid-Open No. 10-2016-0088763 discloses a technology related to a hard mask composition for spin coating, but as the graphene copolymer is included, the solubility is relatively significantly lowered, which is disadvantageous in terms of coatability. exist.

Republic of Korea Patent Publication No. 10-2016-0008930 (published on Jan. 1, 2016) Republic of Korea Patent Publication No. 10-2016-0088763 (published on July 26, 2016)

The present invention is thermally stable in order to solve the above-mentioned problems, and by including an amide group having excellent solubility as a constituent unit, etch resistance and heat resistance are improved by promoting intermolecular interaction through a hydrogen bond, and ,

Provided is a composition for a hard mask with improved solubility and coating properties by controlling the crystallinity of the molecular structure through a rotatable structure including a flexible linker or pendant group.

The present invention provides a composition for a hard mask comprising a structure represented by Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

(In Formulas 1 to 2,

R1 to R5 are each independently a substituted or unsubstituted C6 to C40 arylene group, a substituted or unsubstituted C3 to C40 heteroarylene group, or a combination thereof,

R6 is a substituted or unsubstituted C6 to C40 aryl group, a substituted or unsubstituted C3 to C40 heteroaryl group, or a combination thereof;

Wherein R1 to R6, each independently, may include one or more substituents,

The substituents are each independently a hydroxyl group (-OH), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof,

m to n are each independently an integer of 1 to 100,

* means a bonding hand.)

The composition for a hard mask according to the present invention is thermally stable, and by including an amide group having excellent solubility as a constituent unit, intermolecular interaction is promoted through a hydrogen bond, so that etch resistance and heat resistance can be improved, It has excellent solubility and can provide an advantageous effect on coating properties.

In addition, the composition for a hard mask according to the present invention includes a methylene linking group or pendant group having flexible properties, so that solubility is increased and crystallinity of molecular structure can be easily controlled, so that flatness and gap-fill properties Coating properties such as can also be improved.

Therefore, when the composition for a hard mask according to the present invention is used, an improved hard mask layer can be formed in a well-balanced overall in terms of etch resistance, heat resistance, chemical resistance, solubility and coating properties.

The present invention provides a composition for a hard mask capable of forming a hard mask layer with improved etch resistance, heat resistance, chemical resistance, solubility and coating properties in a balanced manner by including a repeating unit having a specific structure, and pattern formation using the hard mask composition provide a way

Hereinafter, the composition for a hard mask according to an embodiment of the present invention will be described in detail. However, this is only an example, and the present invention is not limited thereto.

In the present invention, when there is an isomer of the structure, repeating unit, or resin represented by the formula, the structure, repeating unit, or resin represented by the formula means a representative formula including the isomer.

Throughout this specification, 'substituted' or 'substituted' means substituted with a substituent, and the substituents may be each independently different or the same.

Throughout this specification, 'unsubstituted' generally means that hydrogen is bonded. In addition, when it is not represented by a substituent, it generally means that hydrogen is bonded.

Throughout this specification, the mark of '*' in the formula means a bond,

Throughout the present specification, the term 'bonding hand' refers to a point at which a moiety or compound represented by the chemical formula is connected to another moiety or compound.

<Composition for hard mask>

polymer

The composition for a hard mask according to the present invention may include a structure represented by Formula 1 or Formula 2, which includes a polymer having two or more repeating units.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

R1 to R5 are each independently a substituted or unsubstituted C6 to C40 arylene group, a substituted or unsubstituted C3 to C40 heteroarylene group, or a combination thereof,

R6 is a substituted or unsubstituted C6 to C40 aryl group, a substituted or unsubstituted C3 to C40 heteroaryl group, or a combination thereof;

Wherein R1 to R6, each independently, may include one or more substituents,

The substituents are preferably included in positions other than the main chain connection site, and are each independently a hydroxyl group (-OH), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, C3 to C20 of a heteroaryl group, or a combination thereof.

m to n are each independently an integer of 1 to 100,

* means a bonding hand.

On the other hand, the definition of each substituent in the above-described polymer structure is as follows.

The 'arylene group' refers to a divalent group derived from an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, or a biphenyl group, and the meaning of 'derived' in the present invention is a substituent formed by the departure of one or more hydrogen atoms included in the compound. it means.

The arylene group of the present invention includes those having a substituent and those not having a substituent. The arylene group is, for example, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 4,4′-biphenylrylene group, a 4,3′-biphenylrylene group, 3 , 3'-biphenylrylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group, etc. , but the present invention is not limited thereto.

A 'heteroarylene group' refers to one or more atoms other than carbon such as a pyridyl group, a quinolinyl group, a pyrimidinyl group, a pyrazinyl group, a naphthyridyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and a carbazolyl group. A divalent group introduced from an aromatic group in an open ring is shown, and includes those having a substituent and those not having a substituent.

The 'aryl group' may be a monocyclic ring or a polycyclic ring, and an aromatic hydrocarbon such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a triphenylenyl group, a terphenyl group, a pyrenyl group can be lifted

The term 'heteroaryl group' refers to an aryl group containing one or more hetero atoms other than carbon atoms among atoms constituting the ring, and may be a saturated ring or an unsaturated ring, and further may be a monocyclic or condensed ring, and the hetero atom may be at least one selected from oxygen, sulfur and nitrogen. The heteroaryl group is, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrrole, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole , thiadiazole, oxadiazole, quinoline, benzofuran, indole, morpholine, pyrrolidine, piperidine, tetrahydrofuran, and the like.

In the present invention, by including the above structure, a hard mask formed of the composition for a hard mask of the present invention can sufficiently secure solubility to exhibit excellent coating properties and, at the same time, exhibit excellent etch resistance and heat resistance.

In the present invention, the structure represented by R1 to R4 in Formula 1 or Formula 2 may include one or more compounds selected from the group consisting of structures represented by the following Formulas 3-1 to 3-11, Preferably, it may be a divalent group derived by desorption of one or more hydrogens from any one structure selected from the group consisting of structures represented by the following Chemical Formulas 3-1 to 3-11.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

Formulas 3-1 to 3-11 may each independently include one or more substituents at positions other than unsubstituted or bonding hands,

The substituents are each independently a hydroxyl group (-OH), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof,

R7 to R11 are each independently hydrogen, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof.

When R1 to R4 include a substituent, R1 to R4 may include at least one hydroxyl group as a substituent at a position excluding the bonding hand.

When a crosslinkable functional group such as a hydroxyl group is included as a substituent, it is advantageous in crosslinking properties and solubility, and coating properties such as flatness and gap-fill properties and chemical resistance can be improved.

For example, R1 to R4 may include the following structures, but are not limited thereto:

* means a bond hand.

The polymer according to the present invention includes R1 to R4 and an amide group connecting them in the constituent unit, thereby promoting intermolecular interaction through a hydrogen bond, thereby improving etch resistance. In addition, since the amide group is thermally stable, heat resistance may be improved, and solubility may also be excellent, thereby providing advantageous effects in coating properties.

When R1 to R4 do not include the arylene group or the heteroarylene group according to the present invention, the reaction site that can utilize the oxidative coupling that can be derived from the heterocycle is reduced, so that the etch resistance and chemical resistance properties are reduced. A relatively insufficient problem may occur, and when R1 to R4 are not connected with an amide group, a thermally stable amide group may not be included, which may be disadvantageous in terms of heat resistance, and a problem of relatively insufficient solubility and coating properties may occur.

On the other hand, when the substituent is outside the range according to the present invention, for example, a carboxy group, an ester group, an ether group, a halogen group or a -CF 3 group, if a reactive substituent outside the scope of the present invention is present at the same time, the target There may be a problem that unnecessary reactions other than the reaction with .

In addition, when the substituent is an acidic functional group such as a carboxyl group, the pH of the composition is lowered by acid during coating, and problems such as etch resistance, heat resistance, or solubility of the hard mask may be lowered, and if the substituent is In the case of an ester group, an ether group, a halogen group, or a -CF3 group, etching properties and heat resistance of the hard mask may be deteriorated due to insufficient carbon content in the molecule.

In the present invention, the structure represented by R5 in Formula 1 may include a structure represented by Formula 4 below.

[Formula 4]

In Formula 4,

X1 to X2 are each independently a substituted or unsubstituted heteroarylene group structure containing a nitrogen (N) atom, and at least one structure selected from the group consisting of structures represented by the following Chemical Formulas 4-1 to 4-3 may include,

The nitrogen is a structure directly linked to the main chain,

Z is a direct bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C40 arylene group, or a substituted or unsubstituted C3 to C40 heteroarylene group, or a combination thereof,

* means a bond hand.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

Formulas 4-1 to 4-3 may each independently include one or more substituents at positions other than unsubstituted or bonding hands,

The substituents are each independently a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof,

* means a bond hand.

For example, R5 may include the following structure, but is not limited thereto:

* means a bond hand.

The R5 structure represented by Chemical Formula 4 of the present invention includes an N-heteroarylene group structure of X ₁ and X ₂ , so that intermolecular interaction is promoted through oxidative coupling based on a high carbon content, It may be possible to improve packing properties, and as a result, etch resistance and heat resistance may be further improved. In addition, since both of X ₁ and X ₂ are connected with a flexible methylene group, it may be advantageous in terms of solubility.

In the present invention, the R6 structure of the polymer represented by Formula 2 may include one or more compounds selected from the group consisting of structures represented by Formulas 3-1 to 3-11, but Formula 3-1 to 3-11 is a monovalent group introduced by desorption of one hydrogen from any one of the structures selected from the group consisting of structures represented by 3-11.

In the present invention, when the polymer includes the R6 structural unit, etch resistance and solubility can be flexibly controlled by adjusting the crystallinity of the polymer according to the type of pendant group, and as a result, flatness and gap - Coating properties such as gap-fill properties can be improved.

The polymer according to the present invention may include, for example, at least one of repeating units represented by the following Chemical Formulas A-1 to A-7.

[Formula A-1]

[Formula A-2]

[Formula A-3]

[Formula A-4]

[Formula A-5]

[Formula A-6]

[Formula A-7]

In Formulas A-1 to A-7, n is an integer of 1 to 100.

In addition, the polymer of the present invention may have a weight average molecular weight of 1,000 to 20,000, preferably 1,500 to 5,000. When the above range is satisfied, the above-described effects of the present invention may be most excellent.

In addition, according to one embodiment of the present invention, the content of the polymer is not particularly limited as long as it can achieve the object of the present invention, but, for example, may be 1 to 30% by weight based on the total weight of the composition, preferably Preferably, it may be 5 to 15% by weight. When the above range is satisfied, the above-described effects of the present invention may be best exhibited.

The composition for a hard mask according to the present invention includes the polymer and the solvent, and may further include additional agents such as a crosslinking agent and a catalyst. The composition for a hard mask comprising the polymer according to the present invention may be performed according to a conventional hard mask manufacturing method in the art.

menstruum

The solvent used in the composition for a hard mask according to the present invention is not particularly limited, and may include an organic solvent having sufficient solubility in the above-described polymer, and may include one or more solvents as necessary. For example, the solvent is propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, cyclopentanone, ethyl lactate, gamma -Butyrolactone (γGBL), acetyl acetone, etc. may be included.

The content of the solvent is not particularly limited, and may be included in the remaining amount excluding the polymer of the present invention and additional agents to be described later, and the remaining amount means that the total weight of the hard mask composition is 100% by weight.

additive

The composition for a hard mask of the present invention may further include an additive.

The additive may further include a necessary component in terms of not affecting the properties of the composition for a hard mask, and specifically, may further include a crosslinking agent, a catalyst, a surfactant, and the like.

The crosslinking agent is one capable of crosslinking repeating units of a polymer by heating in a reaction catalyzed by the generated acid, and is particularly limited if it is a crosslinking agent that can be reacted with the polymer in a way that can be catalyzed by the generated acid doesn't happen As a representative example of such a crosslinking agent, any one selected from the group consisting of melamine, an amino resin, a glycoluryl compound and a bisepoxy compound may be used.

By further including the crosslinking agent, the curing properties of the composition for a hard mask may be further strengthened.

An acid catalyst or a basic catalyst may be used as the catalyst.

The acid catalyst may be a thermally activated acid catalyst. As an example of the acid catalyst, an organic acid such as p-toluene sulfonic acid monohydrate may be used, and a compound of a thermal acid generator (TAG) system that promotes storage stability may be mentioned. The thermal acid generator is an acid generator compound adapted to release an acid during heat treatment, for example, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadiene On, benzointosylate, 2-nitrobenzyltosylate, an alkyl ester of organic sulfonic acid, etc. can be used. As the basic catalyst, any one selected from ammonium hydroxide represented by NH4OH or NR4OH (R is an alkyl group) may be used, but is not limited thereto.

In addition, other photosensitive catalysts known in the field of resist technology can be used as long as they are compatible.

Examples of the surfactant include, but are not limited to, alkylbenzenesulfonate, alkylpyridinium salt, polyethylene glycol, tetraammonium salt, and the like. In this case, the content of the surfactant may be 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the polymer.

When the content of the surfactant is included in the above range, it is preferable because it is excellent in improving surface properties and adhesion without impairing the object of the present invention.

<Pattern Forming Method>

The pattern forming method using the hard mask composition according to the present invention may be performed according to a conventional pattern forming method in the art, and the method for forming a fine pattern will be described in detail below, but is not limited thereto.

For example, a fine pattern may be formed by the following method using the above-described composition for a hard mask of the present invention.

providing a layer of material over the substrate;

applying a hardmask composition according to the present invention over said material layer;

heat-treating the hardmask composition to form a hardmask layer;

forming a thin film layer on the hard mask layer;

forming a photoresist layer on the thin film layer;

exposing and developing the photoresist layer to form a photoresist pattern; and

It provides a pattern forming method comprising the step of selectively removing the thin film layer and the hard mask layer using the photoresist pattern.

The pattern forming method may implement a fine pattern, and the method may be performed a plurality of times. In addition, the hardmask composition of the present invention is applied to multiple patterning methods such as a conventional ArF lithography method, EUV or EBL lithography method, Self-Aligned Double Patterning (SADP) process, and Litho-Etch-Litho-Etch (LELE) Process. possible.

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are provided to illustrate the present invention, and the present invention is not limited by the following examples, and may be variously modified and changed. The scope of the present invention will be determined by the technical spirit of the claims to be described later.

Synthesis Example: Polymer Synthesis

Synthesis Example 1: Polymer A-1

A 1 L three-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel was installed in an oil container, and 3-hydroxy-N-(1-naphthyl)-2-naphthaamide 31.3 g (0.1 mol), 1, 16.6 g (0.1 mol) of 4-dimethoxymethylbenzene was added to the reactor and dissolved in 200 g of propylene glycol monomethyl ether acetate (PGEMA). Then, 0.38 g (0.002 mol) of para-toluenesulfonic acid hydrate was added. After polymerization by stirring for 12 hours while maintaining the temperature inside the reactor at 120° C., 0.45 g (0.003 mol) of triethanolamine as a neutralizing agent was added to the reactor, followed by stirring at room temperature for an additional hour. The reaction mixture obtained by cooling to room temperature was filtered using distilled water/methanol having a mass ratio of 3:7, and the precipitated polymer was filtered and distilled under reduced pressure to obtain a polymer A-1 represented by the following formula (A-1). The polymer had a weight average molecular weight (Mw) of 2500, and a degree of dispersion (Mw/Mn) of 1.8.

[Formula A-1]

Synthesis Example 2: Polymer A-2

31.3 g (0.1 mol) of 3-hydroxy-N-(1-naphthyl)-2-naphthaamide, 9,9'-bis[(1-methoxymethyl)indole-3-yl)]flu as a synthetic monomer Polymer A-2 represented by the following formula A-2 was obtained in the same manner as in Synthesis Example 1, except that 48.6 g (0.1 mol) of orene was used. The polymer had a weight average molecular weight (Mw) of 2100 and a degree of dispersion (Mw/Mn) of 1.6.

[Formula A-2]

Synthesis Example 3: Polymer A-3

Synthesis Example 1 except that 31.3 g (0.1 mol) of 3-hydroxy-N-(1-naphthyl)-2-naphthaamide and 23.0 g (0.1 mol) of 1-pyrenecarboxaldehyde were used as synthetic monomers Polymer A-3 represented by the following formula A-3 was obtained in the same manner as described above. The polymer had a weight average molecular weight (Mw) of 1900 and a degree of dispersion (Mw/Mn) of 1.5.

[Formula A-3]

Synthesis Example 4: Polymer A-4

31.3 g (0.1 mol) of 4-hydroxy-N-(1-naphthyl)-2-naphthaamide, 9,9'-bis[(1-methoxymethyl)indole-3-yl)]flu as a synthetic monomer Polymer A-4 represented by the following formula A-4 was obtained in the same manner as in Synthesis Example 1, except that 48.6 g (0.1 mol) of orene was used. The polymer had a weight average molecular weight (Mw) of 2200, and a degree of dispersion (Mw/Mn) of 1.8.

[Formula A-4]

Synthesis Example 5: Polymer A-5

Synthesis example except that 56.0 g (0.1 mol) of 4-hydroxy-N-(1-pyrenyl)-2-naphthaamide and 16.6 g (0.1 mol) of 1,4-dimethoxymethylbenzene were used as the synthetic monomer Polymer A-5 represented by the following formula (A-5) was obtained in the same manner as in 1. The polymer had a weight average molecular weight (Mw) of 3100 and a degree of dispersion (Mw/Mn) of 2.0.

[Formula A-5]

Synthesis Example 6: Polymer A-6

Synthesis Example 1 except that 56.0 g (0.1 mol) of 4-hydroxy-N-(1-pyrenyl)-2-naphthaamide and 23.0 g (0.1 mol) of 1-pyrenecarboxaldehyde were used as synthetic monomers Polymer A-6 represented by the following formula A-6 was obtained in the same manner as described above. The polymer had a weight average molecular weight (Mw) of 2000 and a degree of dispersion (Mw/Mn) of 1.5.

[Formula A-6]

Synthesis Example 7: Polymer A-7

Synthetic monomer 5-hydroxy-N-(1-pyrenyl)-2-naphthaamide 56.0 g (0.1 mol), 9,9'-bis[(1-methoxymethyl)indole-3-yl)]flu Polymer A-7 represented by the following formula A-7 was obtained in the same manner as in Synthesis Example 1 except that 48.6 g (0.1 mol) of orene was used. The polymer had a weight average molecular weight (Mw) of 2000 and a degree of dispersion (Mw/Mn) of 1.6.

[Formula A-7]

Synthesis Example 8: Polymer B-1

Synthesis example except that 39.6 g (0.1 mol) of 9,9'-bis (1H-indole-3-yl) fluorene and 12.2 g (0.1 mol) of 1-methoxy-4-methylbenzene were used as synthetic monomers Polymer A-8 represented by the following formula (A-8) was obtained in the same manner as in 1. The polymer had a weight average molecular weight (Mw) of 3300 and a degree of dispersion (Mw/Mn) of 1.9.

[Formula B-1]

Synthesis Example 9: Polymer B-2

3.6 g (0.01 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane and 14.6 g of N-methyl-2-pyrrolidone were placed in a reactor and stirred at room temperature. After the dissolution was completed, the reactor was cooled to 0 °C, and then 1.26 g (0.016 mol) of pyridine was added dropwise. Then, a solution of 2.4 g (0.008 mmol) of 4,4'-oxydibenzoyl chloride in 9.6 g of N-methyl-2-pyrrolidone was added dropwise to the stirring reactor at 0° C., followed by further stirring for 2 hours. After completion of the reaction, after the pyridine was completely removed, the obtained powder was dissolved in tetrahydrofuran, and then a precipitate was obtained in hexane and dried to obtain a polymer B-2 represented by the following Chemical Formula B-2. The polymer had a weight average molecular weight (Mw) of 5000 and a degree of dispersion (Mw/Mn) of 2.2.

[Formula B-2]

Synthesis Example 10: Polymer B-3

In a flask, 5.0 g (0.0215 mol) of 1,6-diaminopyrene, 13.83 g (0.0646 mol) of 4-hydroxy-1,8-naphthalenedicarboxylic anhydride and 1-methyl-2-pyrrolidinone After adding 75 g, the mixture was stirred for 12 hours. When the reaction was completed, methanol was added, and the precipitate was filtered and dried to obtain a polymer B-3 represented by the following Chemical Formula B-3.

[Formula B-3]

Examples and Comparative Examples: Preparation of a composition for a hard mask

A composition for a hard mask was prepared by a method commonly used with the composition and content (wt%) shown in Table 1 below.

weight% (a) polymer (b) solvent type content type content type content Example 1 A-1 10 C-1 90 C-2 10 Example 2 A-2 10 C-1 90 C-2 10 Example 3 A-3 10 C-1 90 C-2 10 Example 4 A-4 10 C-1 90 C-2 10 Example 5 A-5 10 C-1 90 C-2 10 Example 6 A-6 10 C-1 90 C-2 10 Example 7 A-7 10 C-1 90 C-2 10 Comparative Example 1 B-1 10 C-1 90 C-2 10 Comparative Example 2 B-2 10 C-1 90 C-2 10 Comparative Example 3 B-3 10 C-1 90 C-2 10

Polymers A-1 to A-7: Polymers prepared according to Synthesis Examples 1 to 7

Polymers B-1 to B-3: Polymers prepared according to Synthesis Examples 8 to 10

Solvent C-1: propylene glycol monomethyl ether acetate

Solvent C-2: cyclohexanone

<Experimental example>

Etching resistance, heat resistance, and solubility of the hard mask layer or hard mask formed of the composition of Table 1 were evaluated by the following method, and the results are shown in Table 2.

(1) Evaluation of etch resistance

Each of the compositions according to Examples and Comparative Examples was coated on a silicon wafer by spin-coating, heat treated at 400° C. for 90 seconds to form a thin film, and then the initial thin film thickness was measured. Each of the formed film-coated wafers was dry-etched using a dry etching equipment (Dielectric etcher) under CF ₄ /CHF ₃ mixed gas conditions, and the thin film thickness was measured. The etching rate (A/min) was calculated by dividing the difference between the initial thin film thickness (Å) and the post-etched thin film thickness (Å) by the etching time (min).

(2) Heat resistance evaluation

The compositions according to Examples and Comparative Examples were spin-coated and heat treated in the same manner as in etch resistance evaluation to form a thin film. After the thin film was collected, the temperature was increased to 400 °C at a rate of 10 °C/min using a thermogravimetric analysis (TGA) to measure wt% loss.

◎: less than 10 wt%

○: 10 wt% or more and less than 15 wt%

△: 15 wt% or more and less than 20 wt%

X: 20 wt% or more

(3) Solubility evaluation

The compositions according to Examples and Comparative Examples were diluted to a certain wt% concentration using propylene glycol monomethyl ether acetate (PGMEA) to determine completely soluble wt%.

◎: 15 wt% or more

○: 10 wt% or more and less than 15 wt%

△: 5 wt% or more and less than 10 wt%

X: less than 5 wt% or insoluble

Etch resistance (etch rate, Å/min) heat resistance solubility Example 1 790 ○ ◎ Example 2 730 ◎ ◎ Example 3 710 ◎ ◎ Example 4 730 ◎ ◎ Example 5 770 ○ ◎ Example 6 690 ◎ ○ Example 7 700 ◎ ◎ Comparative Example 1 1240 X ◎ Comparative Example 2 1150 X ◎ Comparative Example 3 1030 △ ○

Referring to Table 2, when the thin film formed from the composition for a hard mask according to the embodiment mentioned in the present invention is compared with the thin film formed from the composition for a hard mask according to the comparative example, overall in terms of etch resistance, heat resistance and solubility It was confirmed that the characteristics were improved in a balanced way.

On the other hand, in the case of Comparative Examples 1 to 2, the solubility is good, but it was very poor compared to the Example in terms of etch resistance and heat resistance. Overall, it was confirmed that the characteristics were not excellent.

Claims (6)

A composition for a hard mask comprising a structure represented by Formula 1 or Formula 2:
[Formula 1]

[Formula 2]

In Formulas 1 to 2,
R1 to R5 are each independently a substituted or unsubstituted C6 to C40 arylene group, a substituted or unsubstituted C3 to C40 heteroarylene group, or a combination thereof,
R6 is a substituted or unsubstituted C6 to C40 aryl group, a substituted or unsubstituted C3 to C40 heteroaryl group, or a combination thereof;
Wherein R1 to R6, each independently, may include one or more substituents,
The substituents are each independently a hydroxyl group (-OH), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof,
m to n are each independently an integer of 1 to 100,
* means a bonding hand.
According to claim 1,
The structure represented by R1 to R4 in Formula 1 or Formula 2 is,
A composition for a hard mask comprising a divalent group derived from at least one structure selected from the group consisting of structures represented by the following Chemical Formulas 3-1 to 3-11:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

Formulas 3-1 to 3-11, each independently, may be unsubstituted or include one or more substituents,
The substituents are each independently a hydroxyl group (-OH), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof,
R7 to R11 are each independently hydrogen, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof.
According to claim 1,
The structure represented by R5 in Formula 1 is,
A composition for a hard mask comprising a structure represented by the following formula (4):
[Formula 4]

In Formula 4,
X1 to X2 are each independently a substituted or unsubstituted heteroarylene group structure containing a nitrogen (N) atom, and at least one selected from the group consisting of structures represented by the following Chemical Formulas 4-1 to 4-3 It may include a structure,
The nitrogen is a structure directly connected to the main chain,
Z is a direct bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C40 arylene group, or a substituted or unsubstituted C3 to C40 heteroarylene group, or a combination thereof,
* means a bond hand.
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

Formulas 4-1 to 4-3 are each independently unsubstituted or may include one or more substituents,
The substituents are each independently a hydroxyl group (-OH), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof,
* means a bond hand.
According to claim 1,
The R6 structure of the polymer represented by Formula 2 is,
A composition for a hard mask comprising a monovalent group derived from at least one structure selected from the group consisting of structures represented by the following Chemical Formulas 3-1 to 3-11:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

Formulas 3-1 to 3-11 are each independently unsubstituted or may include one or more substituents,
The substituents are each independently a hydroxyl group (-OH), a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof,
R7 to R11 are each independently hydrogen, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof.
According to claim 1,
A composition for a hard mask, characterized in that it further comprises a solvent.
According to claim 1,
A composition for a hard mask, characterized in that it further comprises an additive.