TWI602845B - Polymer, organic layer composition, organic layer, and method of forming patterns - Google Patents

Description

Polymer, organic layer composition, organic layer, and method of forming a pattern

A novel polymer, an organic layer composition comprising the polymer, an organic layer made using the organic layer composition, and a method of forming a pattern using the organic layer composition are disclosed.

Recently, highly integrated designs based on downsizing (miniaturization) and complexity of electronic devices have accelerated the development of more advanced materials and their associated processes, and therefore, photolithography using conventional photoresist also requires new patterning. Materials and technology. In a patterning process, an organic layer, referred to as a hard mask layer, can be formed as a hard interlayer to transfer a fine pattern of photoresist to a sufficient depth on the substrate without causing the pattern to collapse. The hard mask layer functions as an intermediate layer for transferring a fine pattern of photoresist to the material layer via a selective etching process. Therefore, the hard mask layer is required to have characteristics such as etching resistance to be tolerated during the multi-etching process. On the other hand, it has recently been proposed to form a hard mask layer by a spin coating method instead of chemical vapor deposition. In general, since heat resistance and etching resistance have a trade-off relationship with spin coating characteristics, an organic layer material satisfying all the characteristics is required.

One embodiment provides a polymer having improved etch resistance and at the same time having good solubility characteristics.

Another embodiment provides an organic layer composition comprising the polymer.

Yet another embodiment provides an organic layer that simultaneously satisfies mechanical characteristics and film flatness.

Yet another embodiment provides a method of forming a pattern using the organic layer composition.

According to one embodiment, there is provided a polymer comprising the structural unit represented by Chemical Formula 1. [Chemical Formula 1]

In Chemical Formula 1, A is a carbon cyclic group containing at least one hetero atom, B is one of the groups in Group 1, and * is a point of attachment.

When the carbocyclic group contains a pentagonal ring portion and the pentagonal ring portion contains a nitrogen atom (N) as a hetero atom, the carbocyclic group contains at least two hetero atoms.

[Group 1] In Group 1, Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group, and R ¹¹ to R ¹⁴ are each independently a hydroxyl group, a thionyl group, a thiol group. , cyano, substituted or unsubstituted amino, halogen atom, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 To a C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, Substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted a C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 aryl alkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof, and g to j are each independently An integer in the range of 0 to 2, L is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 extended aryl group, or a combination thereof , m is an integer between 1 and 3, and * is the join point.

In Chemical Formula 1, the hetero atom may be N, O, S, Te or Se.

In Chemical Formula 1, A may be a substituted or unsubstituted cyclic group selected from Group 2. [Group 2]

In group 2, Z ¹ and Z ¹² are O, S, Te or Se, Z ² , Z ⁵ , Z ⁶ and Z ⁹ are NR ^a , O, S, Te or Se, Z ³ to Z ⁴ , Z ⁷ To Z ⁸ , Z ¹⁰ to Z ¹¹ and Z ¹³ to Z ²³ are N, and R ^a is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl , substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, hydroxy group, A halogen atom or a combination thereof.

In community 2, the connection points are not limited.

In Group 1, Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted ring group selected from Group 3. [Group 3]

In group 3, the connection points are not limited.

The polymer may contain one of the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-8. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 1-7] [Chemical Formula 1-8]

In Chemical Formula 1-1 to Chemical Formula 1-8, Z ¹⁰¹ and Z ¹⁰⁴ are N, Z ¹⁰² is O, S, Te or Se, and Z ¹⁰³ is NR ^a , O, S, Te or Se, R ^a and R ¹⁰¹ Is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heterocyclic A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom or a combination thereof, and * is a point of attachment.

The polymer may have a weight average molecular weight of from about 500 to about 20,000.

According to another embodiment, an organic layer composition comprising the polymer and a solvent is provided.

The polymer may be included in an amount of from about 0.1% by weight to about 50% by weight based on the total of the organic layer composition.

According to still another embodiment, an organic layer obtained by curing the organic layer composition is provided.

The organic layer may comprise a hard mask layer.

In accordance with another embodiment, a method of forming a pattern includes providing a layer of material on a substrate, coating the layer of organic layer on the layer of material, and thermally treating the layer of the layer to form a hard mask layer, Forming a thin layer containing germanium on the hard mask layer, forming a photoresist layer on the thin layer containing germanium, exposing and developing the photoresist layer to form a photoresist pattern, and selectively using the photoresist pattern The tantalum containing layer and the hard mask layer are removed to expose a portion of the material layer, and the exposed portions of the material layer are etched.

The organic layer composition can be applied using a spin coating method.

The method may further comprise forming a bottom antireflective coating (BARC) prior to forming the photoresist layer.

The heat treatment can be carried out at a temperature of from about 100 ° C to about 500 ° C.

A novel polymer having excellent etch resistance and heat resistance while having satisfactory solubility characteristics and thus being applicable to a spin coating method is provided.

Exemplary embodiments of the present invention will be described in detail below, and the embodiments can be easily performed by those having common knowledge in the related art. However, the invention may be embodied in many different forms and should not be construed as being limited to the exemplary embodiments set forth herein.

As used herein, when a definition is not otherwise provided, the term 'substituted' may mean that a compound is substituted with a substituent selected from the following to replace the hydrogen atom of the compound: a halogen atom (F, Br, Cl or I), a hydroxyl group. , alkoxy, nitro, cyano, amino, azido, indolyl, fluorenyl, fluorenylene, carbonyl, carbamoyl, thiol, ester, carboxyl or its salt, sulfonate Or a salt thereof, phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl, C2 to C20 heteroaryl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocycloalkyl, and Its combination.

As used herein, when a definition is not otherwise provided, the term 'hetero' refers to a compound comprising from 1 to 3 heteroatoms selected from N, O, S, Se, Te, and P.

Hereinafter, a polymer according to one embodiment will be described.

The polymer according to one embodiment contains the structural unit represented by Chemical Formula 1. [Chemical Formula 1]

In Chemical Formula 1, A is a carbocyclic group containing at least one hetero atom, B is one of the groups in Group 1, and * is a point of attachment.

When the carbocyclic group contains a pentagonal ring portion and the pentagonal ring portion contains a nitrogen atom (N) as a hetero atom, the carbocyclic group contains at least two hetero atoms. [Group 1]

In Group 1, Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group, and R ¹¹ to R ¹⁴ are each independently a hydroxyl group, a sulfinyl group, a thiol group, a cyano group, Substituted or unsubstituted amino, halogen atom, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 alkoxy A substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, substituted or not Substituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C1 to C4 alkane Alkyl ether, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group or a combination thereof, g to j are each independently from 0 to 2 An integer in the range, L is a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 extended aryl group, or a combination thereof, m is between 1 and 3 An integer in the range, and * is the join point.

The polymer contains a carbocyclic group (A) containing a hetero atom and an aromatic ring group (B) having a high carbon content, and can ensure a rigidity characteristic.

In addition, the polymer contains a tertiary carbon or a quaternary carbon in the structural unit (B in Chemical Formula 1), and thus the benzylic hydrogen can be minimized but the ring parameter is maximized, and thus the etching resistance is further enhanced. Sex.

In the present specification, the tertiary carbon indicates that three of the four hydrogens connected thereto are replaced by carbon other than hydrogen, and the quaternary carbon indicates four of the four hydrogens connected thereto. A carbon in which hydrogen is replaced by a group other than hydrogen.

When an organic layer composition is prepared using a polymer containing these carbons, a spin coating method can be advantageously applied due to improved solubility. The moiety containing a tertiary or quaternary carbon in the compound is the same as the group in the group 1.

In Chemical Formula 1, A is a carbocyclic group containing a hetero atom, and herein, the hetero atom indicates all atoms except carbon or hydrogen. A may contain, for example, the following hetero atom such as N, O, S, Te or Se, but is not limited thereto. In Chemical Formula 1, A may contain, for example, 1, 2, 3 or 4 hetero atoms, but is not limited thereto. However, the carbocyclic group A contains, for example, a pentagonal cyclic moiety, and when the nitrogen atom (N) is contained as a hetero atom in the pentagonal ring, the carbocyclic group A contains at least two hetero atoms.

For example, when a plurality of heteroatoms are contained in A, the heteroatoms are the same or different. For example, when the carbocyclic group A contains a pentagonal ring, the carbocyclic group may contain, for example, two nitrogen atoms.

The polymer contains heteroatoms in the structural unit, and thus the solubility and gap filling characteristics can be improved.

In Chemical Formula 1, A may contain, for example, at least one substituted or unsubstituted benzene ring. For example, A may be a substituted or unsubstituted ring group selected from Group 2, but is not limited thereto. [Group 2]

In group 2, Z ¹ and Z ¹² are O, S, Te or Se, Z ² , Z ⁵ , Z ⁶ and Z ⁹ are NR ^a , O, S, Te or Se, Z ³ to Z ⁴ , Z ⁷ To Z ⁸ , Z ¹⁰ to Z ¹¹ and Z ¹³ to Z ²³ are N, and R ^a is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl , substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, hydroxy group, A halogen atom or a combination thereof.

In community 2, the connection points are not limited.

In Chemical Formula 1, Ar ¹ to Ar ^{4 of the} group 1 may each independently be a substituted or unsubstituted ring group selected from the group 3, but is not limited thereto. [Group 3]

In group 3, the connection points are not limited.

For example, when the compound arranged in Group 2 and Group 3 is in a substituted form, one hydrogen in the compound may be substituted by a hydroxyl group, a substituted or unsubstituted C1 to C30 alkyl group, or not The substituted C1 to C30 alkoxy group or a combination thereof is substituted, but the invention is not limited thereto.

For example, the polymer may include one of the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-8, but is not limited thereto. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 1-7] [Chemical Formula 1-8]

In Chemical Formula 1-1 to Chemical Formula 1-8, Z ¹⁰¹ and Z ¹⁰⁴ are N, Z ¹⁰² is O, S, Te or Se, and Z ¹⁰³ is NR ^a , O, S, Te or Se, R ^a and R ¹⁰¹ Is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heterocyclic A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom or a combination thereof, and * is a point of attachment.

For example, the polymer may have a weight average molecular weight of from about 500 to about 20,000. When the weight average molecular weight of the polymer is within the range, the organic layer composition containing the polymer (for example, a hard mask composition) can be optimized by adjusting the amount of carbon and the solubility in a solvent.

When the polymer is an organic layer material, not only a uniform film can be formed during the baking process without forming pinholes and voids or the thickness distribution is deteriorated, but also a step or a step can be present in the lower substrate (or layer). Excellent gap fill and planarization features are obtained when patterning.

According to another embodiment, an organic layer composition comprising the polymer and a solvent is provided.

The solvent may be any solvent having sufficient solubility or dispersibility for the polymer and may be, for example, at least one solvent selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, and diethylene glycol. Alcohol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N, N-di Methylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidone, acetamidineacetone and ethyl 3-ethoxypropionate.

The polymer may be included in an amount of from about 0.1% by weight to about 30% by weight based on the total of the organic layer composition. When the polymer within the range is included, the thickness, surface roughness and planarization of the organic layer can be controlled.

The organic layer composition may further comprise an additive such as a surfactant, a crosslinking agent, a thermal acid generator, a plasticizer or the like.

The surfactant may contain, for example, an alkylbenzenesulfonate, an alkyl pyridinium salt, a polyethylene glycol or a quaternary ammonium salt, but is not limited thereto.

The crosslinking agent may be, for example, a melamine-based reagent, a substituted urea-based reagent, or a polymer-based reagent thereof. Preferably, the crosslinking agent having at least two crosslinking to form a substituent may be, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butyl Oxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethyl Thiourea or butoxymethylated thiourea and the like.

Further, the crosslinking agent may be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance may be a compound containing a crosslinking group having an aromatic ring (for example, a benzene ring or a naphthalene ring) to form a substituent in the molecule.

The thermal acid generator may be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, Naphthalenecarbonic acid, etc. or/and 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-toluenesulfonic acid-nitrobenzyl ester, other organic sulfonate An acid alkyl ester or the like, but is not limited thereto.

The additive may be included in an amount of from about 0.001 part by weight to 40 parts by weight based on 100 parts by weight of the organic layer composition. When the additives in the range are included, the solubility can be improved without changing the optical properties of the organic layer composition.

According to another embodiment, an organic layer made using an organic layer composition is provided. The organic layer may be formed, for example, by coating an organic layer composition on a substrate and heat-treating it to cure, and may include, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, or the like for use in an electronic device.

A method of forming a pattern by using an organic layer composition is described below.

A method of forming a pattern according to another embodiment includes providing a layer of material on a substrate, coating an organic layer composition comprising a polymer and a solvent, and heat treating the organic layer composition to form a hard mask layer, Forming a thin layer containing germanium on the hard mask layer, forming a photoresist layer on the thin layer containing germanium, exposing and developing the photoresist layer to form a photoresist pattern, and selectively removing the photoresist pattern The tantalum-containing layer and the hard mask layer expose a portion of the material layer and etch an exposed portion of the material layer.

The substrate can be, for example, a tantalum wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be finally patterned, such as a metal layer such as an aluminum layer and a copper layer; a semiconductor layer such as a germanium layer; or an insulating layer such as a hafnium oxide layer and a tantalum nitride layer. The material layer can be formed by a method such as a chemical vapor deposition (CVD) process.

The organic layer composition is the same as described above, and can be applied as a solution by spin coating. Herein, the thickness of the organic layer composition is not particularly limited, but may be, for example, about 50 angstroms to about 10,000 angstroms.

The heat treatment of the organic layer composition may be carried out, for example, at about 100 ° C to about 500 ° C for about 10 seconds to 1 hour.

The tantalum-containing layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, and/or SiN or the like.

The method may further comprise forming a bottom anti-reflective coating (BARC) prior to forming the photoresist layer on the tantalum-containing layer.

Exposure of the photoresist layer can be performed using, for example, ArF, KrF, or EUV. After the exposure, the heat treatment may be performed at about 100 ° C to about 500 ° C.

The etching process of the exposed portion of the material layer may be performed by an etching process using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl _{3 ,} and a mixed gas thereof.

The etched material layer may be formed in a variety of patterns, and the various patterns may be metal patterns, semiconductor patterns, insulating patterns, and the like, such as different patterns of semiconductor integrated circuit devices.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are exemplary, and the invention is not limited thereto.

Synthesis example

Synthesis Example 1 Quinoline (12.9 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-dioxin Alkane (94 g) was placed in a flask and then stirred at 100 ° C for 8 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, a precipitate produced by adding methanol thereto was filtered, and residual monomers were removed by using methanol. A polymer represented by Chemical Formula 1a. [Chemical Formula 1a]

Synthesis Example 2 9-methyl acridine (19.3 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1, 4-Dioxane (98 g) was placed in a flask and then stirred at 100 ° C for 12 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and the residual monomer was removed by recrystallization using acetonitrile and methanol by using acetonitrile and methanol to obtain a chemical formula. The polymer represented by 2a. [Chemical Formula 2a]

Synthesis Example 3 9-methyl acridine (19.3 g, 0.1 mol), benzophenone (18.2 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1, 4-Dioxane (98 g) was placed in a flask and then stirred at 100 ° C for 12 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and by using acetonitrile and methanol to remove residual monomers after recrystallization by using acetonitrile and methanol, The polymer represented by Chemical Formula 3a. [Chemical Formula 3a]

Synthesis Example 4 Thiianaphthene (13.4 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4 Dioxane (92 g) was placed in a flask and then stirred at 100 ° C for 8 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and the monomer remaining after filtration of the precipitate formed by adding methanol thereto was removed, and the compound represented by Chemical Formula 4a was obtained. polymer. [Chemical Formula 4a]

Synthesis Example 5 benzothiazole (13.5 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-two Oxane (91 g) was placed in a flask and then stirred at 100 ° C for 14 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and the monomer remaining after filtration of the precipitate formed by adding methanol thereto was removed, and the compound represented by Chemical Formula 5a was obtained. polymer. [Chemical Formula 5a]

Synthesis Example 6 benzoxazole (11.9 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4- Dioxane (91 g) was placed in a flask and then stirred at 100 ° C for 14 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and the residual monomer after the precipitation formed by filtering the methanol added thereto was removed by using methanol. A polymer represented by Chemical Formula 6a. [Chemical Formula 6a]

Synthesis Example 7 carbazole (11.8 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-dioxin Alkane (91 g) was placed in a flask and then stirred at 100 ° C for 14 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and the residual monomer after the precipitation formed by filtering the methanol added thereto was removed by using methanol. A polymer represented by Chemical Formula 7a. [Chemical Formula 7a]

Synthesis Example 8 7-azaindole (11.8 g, 0.1 mol), 9-fluorenone (18 g, 0.1 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1, 4-Dioxane (92 g) was placed in a flask and stirred at 100 ° C for 8 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and the residual monomer after the precipitation formed by filtering the methanol added thereto was removed by using methanol. A polymer represented by Chemical Formula 8a. [Chemical Formula 8a]

Synthesis Example 9 thiazide (20.1 g, 0.15 mol), anthrone (17.5 g, 0.09 mol), p-toluenesulfonic acid monohydrate (9.5 g, 0.05 mol) and 1,4-dioxane ( 152 g) was placed in a flask and then stirred at 100 ° C for 8 hours. When the reaction was completed, hexane (100 g) was added thereto to extract 1,4-dioxane, and the residual monomer after the precipitation formed by filtering the methanol added thereto was removed by using methanol. A polymer represented by Chemical Formula 9a. [Chemical Formula 9a]

Synthesis of Comparative Example 1 9,9'-bis(4-hydroxyphenyl)anthracene (50.0 g, 0.143 mol), 1,4-bis(methoxymethyl)benzene (23.7 g, 0.143 mol) and Propylene glycol monomethyl ether acetate (50 g) was placed in a flask to prepare a solution. Next, diethyl sulfate (1.10 g, 7.13 mmol) was added to the solution, and the mixture was stirred at 100 ° C for 24 hours. When the polymerization is completed, the resultant is precipitated in methanol to remove the monomer and the low molecular weight substance, and the polymer represented by Chemical Formula 10a is obtained. [Chemical Formula 10a]

Preparing a hard mask Composition

Example 1 The polymer according to Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethylether acetate (PGMEA) and cyclohexanone (7:3 (v/v)), and the solution was filtered. Prepare a hard mask composition. The weight of the polymer is adjusted in the range of 5.0% by weight to 15.0% by weight based on the total weight of the hard mask composition, depending on the desired thickness.

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

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

Example 4 A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Synthesis Example 4 was used instead of the polymer of Synthesis Example 1.

Example 5 A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Synthesis Example 5 was used instead of the polymer of Synthesis Example 1.

Example 6 A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Synthesis Example 6 was used instead of the polymer of Synthesis Example 1.

Example 7 A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Synthesis Example 7 was used instead of the polymer of Synthesis Example 1.

Example 8 A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Synthesis Example 8 was used instead of the polymer of Synthesis Example 1.

Example 9 A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Synthesis Example 9 was used instead of the polymer of Synthesis Example 1.

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

Evaluation 1 : Etch resistance

Each of the hard mask compositions (polymer content: 9.5%) according to Examples 1 to 9 and Comparative Example 1 was spin-coated on the patterned tantalum wafer. Subsequently, the coated wafer was subjected to heat treatment at 400 ° C for 120 seconds to form a film, and the thickness of the film was measured by using an ST5000 film thickness gauge manufactured by K-MAC.

Subsequently, the film was dry-etched by using a N ₂ /O ₂ mixed gas (50 mT / 300 W / 10O ₂ / 50 N ₂ ) for 60 seconds, and the thickness of the film was measured again. Next, the bulk etch rate (BER) was calculated according to the calculation formula 1 by using the film thickness and the etching time before and after the dry etching.

The film was dry etched using CFx gas (100 mT/600 W/42CF ₄ / 600Ar/15O ₂ ) instead of the N ₂ /O ₂ mixed gas for 120 seconds, and the etching rate was calculated according to Equation 1. [Calculation Equation 1] Block etching rate (BER) = (film initial thickness - film thickness after etching) / etching time (angstroms per second)

The results are provided in Table 1. [Table 1]

Referring to Table 1, each of the films formed by the hard mask compositions according to Examples 1 to 9 respectively exhibited a N ₂ /O ₂ mixed gas as compared with the film formed of the hard mask composition according to Comparative Example 1. And a lower etch rate of CFx gas.

Therefore, the hard mask compositions according to Examples 1 to 9 exhibited high etching resistance as compared with the film formed of the hard mask composition according to Comparative Example 1.

Evaluation 2 : Flattening feature

Each of the hard mask compositions (polymer content: 5%) according to Examples 1 to 9 and Comparative Example 1 was spin-coated on the patterned tantalum wafer, and then heat treated at 400 ° C for 120 seconds. And check the flattening characteristics of the film.

The flattening feature is digitized according to the calculation equation 2 by measuring the thickness of the hard mask layer from the cross-sectional image of the pattern observed by SEM, and the result is excellent because the height h1 and the height h2 in FIG. The smaller the difference, the better the flattening feature.

The results are provided in Table 2. [Table 2]

Referring to Table 2, each of the films formed by the hard mask compositions according to Examples 1 to 9, respectively, exhibited lower flatness according to Equation 2, as compared with the film formed of the hard mask composition according to Comparative Example 1. The feature measurements are taken, and thus the excellent flattening features are exhibited.

Evaluation 3 : Heat resistance

Each of the hard mask compositions (10.0% by weight) according to Examples 1 to 9 and Comparative Example 1 was spin-coated on a tantalum wafer, and then heat-treated at 240 ° C for 1 minute, and by using A film thickness gauge manufactured by K-MAC was used to measure the thickness of the film. The film was again heat treated at 400 ° C for 2 minutes, and the thickness of the film was measured again. The film thickness at two temperatures was used to calculate the thickness reduction rate of the film according to Equation 3, and thus the relative heat resistance of the hard mask film was digitized.

The results are provided in Table 3. [Calculation Equation 3] Thickness Reduction Rate of Film = (Thickness of Film Baked at 240 ° C - Thickness of Film Baked at 400 ° C) / (Thickness of Film Baked at 240 ° C) × 100 (%) [table 3]

Referring to Table 3, each of the films formed by the hard mask compositions according to Examples 1 to 9, respectively, was compared during the heat treatment at 400 ° C as compared with the film formed of the hard mask composition according to Comparative Example 1. Small thickness reduction rate.

Therefore, the hard mask compositions according to Examples 1 to 9 were highly crosslinked compared to the hard mask composition according to Comparative Example 1, and exhibited high heat resistance at 400 °C.

Although the present invention has been described in connection with what is presently considered as a practical exemplary embodiment, it is understood that the invention is not to be construed as Various modifications and equivalent arrangements.

H1, h2‧‧‧ height

FIG. 1 is a view illustrating evaluation of flattening features.

H1, h2‧‧‧ height

Claims (12)

An organic layer composition comprising: a polymer comprising the structural unit represented by Chemical Formula 1, and a solvent: Wherein in Chemical Formula 1, A is a carbocyclic group containing at least one hetero atom, B is one of the groups in Group 1, and * is a point of attachment, wherein when the carbocyclic group comprises a pentagonal ring portion and When the pentagonal cyclic moiety contains a nitrogen atom as a hetero atom, the carbocyclic group contains at least two heteroatoms: Wherein in Group 1, Ar ¹ to Ar ⁴ are each independently a substituted or unsubstituted ring group selected from Group 3: Wherein in Group 3, the point of attachment of the ring group is not limited, and R ¹¹ to R ¹⁴ are each independently a hydroxyl group, a sulfinyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a halogen. Atom, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C3 To a C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamino group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, Substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C1 to C4 alkyl ether, substituted or unsubstituted a C7 to C20 arylalkyl ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof, wherein g to j are each independently an integer ranging from 0 to 2, and L is a single bond, Substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C30 extended aryl or a combination thereof, m is an integer in the range of 1 to 3, and * is Contacts. The organic layer composition of claim 1, wherein the hetero atom is nitrogen, oxygen, sulfur, ruthenium or selenium. The organic layer composition of claim 1, wherein the A is a substituted or unsubstituted ring group selected from the group 2: Wherein in Group 2, Z ¹ and Z ¹² are oxygen, sulfur, antimony or selenium, Z ² , Z ⁵ , Z ⁶ and Z ⁹ are NR ^a , oxygen, sulfur, antimony or selenium, Z ³ to Z ⁴ , Z ⁷ to Z ⁸ , Z ¹⁰ to Z ¹¹ and Z ¹³ to Z ²³ are nitrogen, and R ^a is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 naphthenic , substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heterocyclic, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, hydroxy A halogen atom or a combination thereof, wherein in Group 2, the point of attachment of the ring group is not limited. The organic layer composition according to claim 1, wherein the polymer includes one of the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-8: [Chemical Formula 1-1] [Chemical Formula 1-7] Wherein in Chemical Formula 1-1 to Chemical Formula 1-8, Z ¹⁰¹ and Z ¹⁰⁴ are nitrogen, Z ¹⁰² is oxygen, sulfur, ruthenium or selenium, and Z ¹⁰³ is NR ^a , oxygen, sulfur, ruthenium or selenium, R ^a and R ¹⁰¹ is hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heterocyclic A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom or a combination thereof, and * is a point of attachment. The organic layer composition according to claim 1, wherein the polymer has a weight average molecular weight of 500 to 20,000. The organic layer composition according to claim 1, wherein the polymer is contained in an amount of from 0.1% by weight to 50% by weight based on the total of the organic layer composition. An organic layer obtained by curing the organic layer composition as described in claim 1 of the patent application. The organic layer of claim 7, wherein the organic layer comprises a hard mask layer. A method of forming a pattern, comprising: providing a material layer on a substrate, coating an organic layer composition as described in claim 1 on the material layer, and heat treating the organic layer composition to form a hard mask a curtain layer, a thin layer containing germanium is formed on the hard mask layer, a photoresist layer is formed on the thin layer containing germanium, and the photoresist layer is exposed and developed to form a photoresist pattern, and the photoresist is used. A pattern selectively removes the tantalum containing layer and the hard mask layer to expose a portion of the material layer and etch an exposed portion of the material layer. The method of forming a pattern according to claim 9, wherein the organic layer composition is applied using a spin coating method. The method of forming a pattern according to claim 9, wherein the pattern forming method further comprises forming a bottom anti-reflective coating layer before forming the photoresist layer. The method of forming a pattern according to claim 9, wherein the heat treatment is performed at 100 ° C to 500 ° C.