TW201727376A - Polymer, organic layer composition, and method of forming patterns - Google Patents

Abstract

Disclosed are a polymer including a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2, an organic layer composition including the polymer, and a method of forming patterns using the organic layer composition. The Chemical Formulae 1 and 2 are the same as defined in the detailed description.

Description

Polymer, organic layer composition and pattern forming method

The present invention discloses a polymer, an organic layer composition comprising the polymer, and a method of forming a pattern using the organic layer composition.

In recent years, the semiconductor industry has advanced toward ultra-fine technology with patterns of several to several tens of nanometer sizes. Such ultra-fine technology basically requires effective lithography. A typical lithography technique includes providing a layer of material on a semiconductor substrate; coating a photoresist layer thereon; exposing and developing it to provide a photoresist pattern; and etching the layer of material using the photoresist pattern as a mask. Nowadays, according to a pattern to form a small size, it is difficult to provide a fine pattern having an excellent outline by only the typical lithography technique mentioned above. Thus, a layer called a hard mask layer can be formed between the material layer and the photoresist layer to provide a fine pattern. The hard mask layer acts as an intermediate layer to transfer the fine pattern of photoresist to the material layer via a selective etching process. Therefore, the hard mask layer needs to have characteristics such as heat resistance and etching resistance to withstand during a plurality of etching processes. On the other hand, in recent years, it has been shown that a spin coating method can replace a chemical vapor deposition (CVD) method to form a hard mask layer. The spin coating method can be easily performed not only, but also the planarization characteristics can be improved. Herein, it is necessary to fill the pattern to make it free of voids, because the fine pattern may have to be realized by forming a plurality of patterns. In addition, when the substrate has a step, or when the region close to the pattern and the unpatterned region are present together on the wafer, the surface of the hard mask layer needs to be planarized by the underlayer. There is a need for an organic layer material that satisfies the desired characteristics of a hard mask layer.

One embodiment of the present invention provides a polymer having both etch resistance, solubility, and storage stability.

Another embodiment of the present invention provides an organic layer composition that provides an organic layer having mechanical characteristics and film planarization characteristics.

Another embodiment of the present invention provides a method of forming a pattern using an organic layer composition.

According to an embodiment, the polymer comprises the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2. [Chemical Formula 1] [Chemical Formula 2] In Chemical Formula 1 and Chemical Formula 2, A ¹ and A ^{2 are} independently a divalent group containing at least one of a substituted or unsubstituted benzene ring, and A ³ is a divalent cyclic group containing a quaternary carbon. And * is the connection point.

A ³ may be one of the groups of group 1. [Group 1] In Group 1, Ar ¹ to Ar ^{4 are} independently a substituted or unsubstituted C6 to C30 aryl group, and R ¹¹ to R ^{14 are} independently a hydroxyl group, a sulfinyl group, a thiol group, a cyano group, or a substituted group. Or unsubstituted amino group, halogen atom, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 alkoxy group , substituted or unsubstituted C3 to C30 cycloalkenyl, substituted or unsubstituted C1 to C20 alkylamino, substituted or unsubstituted C7 to C20 arylalkyl, substituted or unsubstituted 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 alkyl Ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group or a combination thereof, o, p, q and r are independently 0 to 3 An integer wherein 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, and m is an integer in the range of 1 to 3, And * is Junction.

At least one of A ¹ and A ² may be a divalent cyclic group containing at least two rings in its structure.

A ¹ and A ² may independently be a divalent group derived from one of the compounds of Group 2 and Group 3, wherein at least one hydrogen of the divalent group is substituted or unsubstituted. [Group 2] [Group 3] In group 3, R ¹ , R ² and R ^{3 are} independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted Substituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkane A substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom, a halogen-containing group Group or a combination thereof.

A ¹ and A ² may be different from each other.

The weight average molecular weight of the polymer can range from 1,000 to 200,000.

According to another embodiment, the organic layer composition comprises a polymer comprising a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2; and a solvent.

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

According to another embodiment, a pattern forming method includes: providing a material layer on a substrate; coating an organic layer composition on the material layer; heat treating the organic layer composition to form a hard mask layer; and forming the hard mask layer on the hard mask layer a thin layer; a photoresist layer formed on the germanium-containing thin layer; the photoresist layer is exposed and developed to form a photoresist pattern; and the photoresist pattern is used to selectively remove the germanium-containing thin layer and the hard mask layer to expose the material layer a portion; and etching the exposed portion of the material layer.

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

The pattern forming method may further include forming a bottom anti-reflective coating (BARC) before forming the photoresist layer.

The present invention provides an organic layer material having film planarization characteristics as well as mechanical characteristics such as etching resistance and film density.

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

In the present specification, the term "substituted" may be substituted when the group is substituted with a substituent selected from the group: a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, a cyano group, when a definition is not otherwise provided. , an amine group, an azido group, a decyl group, a fluorenyl group, a fluorenylene group, a carbonyl group, an amine carbaryl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 arylalkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C2 to C20 Aryl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocycloalkyl, and combinations thereof.

In the present specification, when no definition is provided, "hetero" refers to a group containing 1 to 3 hetero atoms selected from N, O, S and P.

In the present specification, when no definition is provided, "*" means a point of attachment of a compound or a moiety of a compound.

Further, the "monovalent group" derived from the compound A is formed by substituting one hydrogen in the compound A. For example, the monovalent group of a group derived from benzene becomes a phenyl group. Further, the "divalent group" derived from the compound A is a divalent group obtained by replacing two hydrogens in the compound A and forming two connection points. For example, the divalent group of the group derived from benzene becomes a phenyl group.

In the following, a polymer according to an embodiment is described.

The polymer according to an embodiment includes the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2. [Chemical Formula 1] [Chemical Formula 2]

In Chemical Formula 1 and Chemical Formula 2, A ¹ and A ^{2 are} independently a divalent group containing at least one of a substituted or unsubstituted benzene ring, and A ³ is a divalent cyclic group containing a quaternary carbon. And * is the connection point.

The polymer can be synthesized by trimerization. The polymer includes the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2, and for example, in Chemical Formula 1 and Chemical Formula 2, A ¹ and A ² may be different from each other.

The structural unit represented by Chemical Formula 1 contains a compound moiety including a benzene ring and represented by A ¹ and a cyclic group moiety containing a quaternary carbon represented by A ³ . The structural unit represented by Chemical Formula 2 contains a compound moiety including a benzene ring and represented by A ² and a cyclic group moiety containing a quaternary carbon represented by A ³ .

Due to the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2, the polymer according to an embodiment can ensure planarization characteristics as well as film density and etching resistance.

In the present specification, a quaternary carbon refers to a carbon which is substituted with a hydrogen at another four sites bonded to carbon by another group.

In Chemical Formula 1 and Chemical Formula 2, the divalent cyclic group containing a quaternary carbon represented by A ³ may be, for example, a group selected from the group of Group 1, but is not limited thereto. [Group 1]

In Group 1, Ar ¹ to Ar ^{4 are} independently a substituted or unsubstituted C6 to C30 aryl group, and R ¹¹ to R ^{14 are} independently a hydroxyl group, a sulfinyl group, a thiol group, a cyano group, or a substituted group. Or unsubstituted amino group, halogen atom, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 alkoxy group , substituted or unsubstituted C3 to C30 cycloalkenyl, substituted or unsubstituted C1 to C20 alkylamino, substituted or unsubstituted C7 to C20 arylalkyl, substituted or unsubstituted 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 alkyl Ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group or a combination thereof, o, p, q and r are independently 0 to 3 An integer wherein 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, and m is an integer in the range of 1 to 3, And * is Junction.

For example, in Chemical Formula 1 and Chemical Formula 2, at least one of A ¹ and A ² may be a divalent cyclic group containing at least two rings in the structure. In particular, at least one of A ¹ and A ² may be, for example, a divalent group derived from one of the compounds of Group 2 and Group 3, wherein at least one hydrogen of the divalent group may be substituted or not Replaced, but not limited to. [Group 2] [Group 3]

In group 3, R ¹ , R ² and R ^{3 are} independently hydrogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted Substituted C6 to C30 aryl, substituted or unsubstituted C7 to C30 arylalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkane A substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxyl group, a halogen atom, a halogen-containing group Group or a combination thereof. In the group 3, R ¹ , R ² and R ³ representing a functional group bonded to a nitrogen (N) atom may independently be, for example, hydrogen or a substituted or unsubstituted phenyl group, but are not limited thereto.

For example, A ¹ and A ² may independently be a substituted or unsubstituted divalent group derived from one of the compounds of Group 2, and for another example, A ¹ and A ² may independently be a substituted or unsubstituted divalent group derived from one of the compounds of Group 3, and for yet another example, any of A ¹ and A ² may be one of the compounds derived from Group 2 The substituted or unsubstituted divalent group of the person, and the other may be a substituted or unsubstituted divalent group derived from one of the compounds of the group 3.

The point of attachment of each of the compound of the group 2 and the group 3 to the chemical formula 1 and the chemical formula 2 is not particularly limited. Further, each of the compounds of Group 2 and Group 3 is represented in an unsubstituted form, but any hydrogen of each compound may be substituted with another substituent, and the kind and number of the substituents are not particularly limited.

For example, at least one of A ¹ and A ² is a divalent group derived from one of the compounds of Group 2 and Group 3, wherein at least one hydrogen of the divalent group can be replaced, for example, by the following group: Hydroxy, sulfinyl, thiol, cyano, substituted or unsubstituted amine, 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 C30 cycloalkenyl, substituted or unsubstituted C1 to C20 alkylamino, substituted or not Substituted C7 to C20 arylalkyl, substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 a heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 aryl alkyl ether group, a substituted or unsubstituted C1 to C30 haloalkyl group or Combinations thereof, and the type and number of substituents, should be selected by those of ordinary skill in the art in view of the characteristics of the polymer.

For example, when at least one of A ¹ and A ² is substituted, for example, by a hydrophilic functional group such as a hydroxyl group, the polymer may have an increased affinity for the lower layer, and thus the organic layer produced therefrom may have a modified nature. Film flattening characteristics.

The polymer may respectively contain a plurality of structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2. A plurality of structural units represented by Chemical Formula 1 may have the same structure or different structures, and likewise, a plurality of structural units represented by Chemical Formula 2 may have the same structure or different structures.

The polymer can be substantially rigid in character attributable to the carbocyclic group in the structure, and the solubility and storage stability can be improved, and therefore, the spin coating method is advantageously attributed to the quaternary carbon in the above structure. use. In addition, the quaternary carbon minimizes the benzyl hydrogen and maximizes the ring parameters, thus ensuring excellent thermal resistance.

For example, the polymer may have a weight average molecular weight of from about 1,000 to 20,000. When the weight average molecular weight of the polymer is within the range, the organic layer composition comprising the polymer (e.g., the hard mask composition) can be optimized by adjusting the amount of carbon and the solubility in the solvent.

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

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

The polymer may be included in an amount of from about 0.1% by weight to 50% by weight based on the total of the organic layer composition. When the polymer in the range is included, the thickness, surface roughness and planarization of the organic layer can be controlled.

The organic layer composition may further comprise the following additives: a surfactant, a crosslinking agent, a thermal acid generator or a plasticizer.

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

The crosslinking agent can be, for example, a melamine, a substituted urea or a polymeric crosslinking agent. Preferably, it may be a crosslinking agent having at least two crosslinking groups to form a substituent, such as a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethyl Melamine melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, Methoxymethylated thiourea or butoxymethylated thiourea and analogs thereof.

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 substituent containing an aromatic ring such as a benzene ring or a naphthalene ring in the molecule.

The thermal acid generator may be, 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, Naphthalene carbonate and its analogs or/and 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyltoluenesulfonate, organic sulfoorganosulfonylalkyl Esters and their analogs, but are not limited thereto.

The additive may be present 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. Within the above range, the solubility can be improved while the optical properties of the organic layer composition are not changed.

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, and may include, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filling layer, and the like for an electronic device. .

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

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

The substrate can be, for example, a germanium 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 a spin coating method. Herein, the thickness of the organic layer composition is not particularly limited, but may be, for example, about 50 to 10,000 angstroms.

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

The tantalum-containing layer may be formed of, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiN, and/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, for example, using ArF, KrF or EUV. After the exposure, the heat treatment may be performed at about 100 ° C to 500 ° C.

The etching process of the exposed portion of the material layer can be performed via a dry etching process using an etching gas, and the etching gas can be, for example, but not limited to, CHF ₃ , CF ₄ , Cl ₂ , BCl _{3 ,} and a mixed gas thereof.

The etch material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulating pattern, and the like, such as different patterns of the semiconductor integrated circuit device.

The invention is described in more detail below with reference to examples. However, these examples are illustrative and the invention is not limited thereto. Synthesis example synthesis example 1

100 g (0.46 mol) 1-hydroxyindole, 16.5 g (0.11 mol) 1-naphthol, 87.7 g (0.49 mol) 9-fluorenone, 55 g (0.57 mol) methanesulfonic acid, 30.4 g (0.29 mol) 3-mercaptopropionic acid and 86.4 g of 1,4-dioxane were placed in a 500 ml 2-neck flask equipped with a mechanical stirrer and a condenser, and stirred and then heated to 105 ° C and Stir for 12 hours. Upon completion of the reaction, the resultant was cooled to 60 ° C - 70 ° C, and 300 g of tetrahydrofuran was added thereto so that the compound did not harden. The compound was treated with a 7% aqueous solution of sodium bicarbonate to give a pH of about 5-6. Subsequently, 1000 ml of ethyl acetate was poured thereto, and the mixture was further stirred, and only the organic layer was extracted with a separating funnel. Subsequently, the organic layer was finally extracted by repeatedly placing 500 ml of water in a separatory funnel three times and shaking the separatory funnel to remove acid and sodium salts therefrom.

Subsequently, the obtained organic solution was concentrated with an evaporator to obtain a compound, and 500 g of tetrahydrofuran was added thereto to obtain a solution. The solution was slowly added dropwise to 2500 ml of hexane in a beaker, stirred to form a precipitate and a polymer was obtained.

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured by gel permeation chromatography (GPC) (Mw: 1,780, PD: 1.76).

The polymer has the structural unit shown in Chemical Formula 1a. [Chemical Formula 1a] Synthesis example 2

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

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using gel permeation chromatography (GPC). (Mw: 2,400, PD: 1.75)

The polymer has the structural unit shown in Chemical Formula 1b. [Chemical Formula 1b] Synthesis example 3

A polymer was obtained in the same manner as in Synthesis Example 1, except that 1,6-dihydroxyindole was used instead of 1-hydroxyindole.

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using gel permeation chromatography (GPC). (Mw: 1,900, PD: 1.65)

The polymer has the structural unit shown in Chemical Formula 1c. [Chemical Formula 1c] Synthesis example 4

A polymer was obtained in the same manner as in Synthesis Example 1, except that 1-hydroxyacetophene was used instead of 1-hydroxyindole.

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using gel permeation chromatography (GPC). (Mw: 1,600, PD: 1.51)

The polymer has the structural unit shown in Chemical Formula 1d. [Chemical Formula 1d] Synthesis example 5

A polymer was obtained in the same manner as in Synthesis Example 4 except that 1-hydroxyindole was used instead of 1-naphthol.

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using gel permeation chromatography (GPC). (Mw: 1,910, PD: 1.57)

The polymer has the structural unit shown in Chemical Formula 1e. [Chemical Formula 1e] Synthesis example 6

A polymer was obtained in the same manner as in Synthesis Example 1, except that 1,6-dihydroxyindole was used instead of 1-naphthol.

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using gel permeation chromatography (GPC). (Mw: 1,900, PD: 1.5)

The polymer has the structural unit shown in Chemical Formula 1f. [Chemical Formula 1f] Synthesis example 7

1,1'-binaphthyl-2,2'-diol (22.9 g, 0.08 mol), anthrone (18.0 g, 0.1 mol), p-toluenesulfonic acid monohydrate (19.04 g, 0.1 mol) And PGMEA (313.23 g) were placed in a 500 ml flask equipped with a thermometer, a condenser and a mechanical stirrer and stirred at 120 °C. When the weight average molecular weight of the sample obtained from the polymerization agent per hour was 1,000, 1-phenyl-1H-indole (3.6 g, 0.02 mol) was added thereto. When the weight average molecular weight of the sample obtained from the polymerization reactant per hour was 1,200 to 2,000, the reaction was completed. When the reaction was completed, the process of removing the acid catalyst with distilled water after adding a small amount of tetrahydrofuran and ethyl acetate thereto was repeated three times. Subsequently, an organic solvent layer was extracted therefrom and treated under reduced pressure, and 50 g of tetrahydrofuran was added thereto, followed by formation of a precipitate in 300 g of hexane and filtration to obtain a polymer.

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using gel permeation chromatography (GPC). (Mw: 2, 154, PD: 1.67)

The polymer has the structural unit shown in Chemical Formula 1g. [Chemical Formula 1g] Synthesis example 8

Phenanthrene-2-ol (15.5 g, 0.08 mol), anthrone (23.03 g, 0.1 mol), methanesulfonic acid (9.61 g, 0.1 mol), mercaptopropionic acid (5.31 g, 0.05 mmol) PGMEA (313.23 g) was placed in a 500 ml flask equipped with a thermometer, a condenser and a mechanical stirrer and stirred at 120 °C. When the weight average molecular weight of the sample obtained from the polymerization per hour was 1,000, 1-phenyl-1H-indole (19.04 g, 0.1 mol) was added thereto. When the weight average molecular weight of the sample obtained from the polymerization per hour was 1,200 to 2,000, the reaction was completed. When the reaction was completed, the process of removing the acid catalyst with distilled water after adding a small amount of tetrahydrofuran and ethyl acetate thereto was repeated three times. Subsequently, an organic solvent layer was extracted therefrom and treated under reduced pressure, and 50 g of tetrahydrofuran was added thereto, followed by formation of a precipitate in 300 g of hexane and filtration to obtain a polymer.

The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer were measured using gel permeation chromatography (GPC). (Mw: 2,500, PD: 1.78)

The obtained polymer has the structural unit shown in Chemical Formula 1h. [Chemical Formula 1h] Comparative Synthesis Example 1

20 g (0.103 mol) of 1-hydroxyindole and 3.08 g (0.103 mol) of paraformaldehyde were sequentially placed in a 500 ml flask and dissolved in 42 g of propylene glycol monomethyl ether acetate (PGMEA). Into this, 0.4 g (0.002 mol) of p-toluenesulfonic acid was added thereto, and the mixture was stirred at 90 ° C to 120 ° C for 5 to 10 hours. When the weight average molecular weight of the sample obtained from the polymerization per hour was 3,000 to 4,200, the reaction was completed, and a polymer represented by Chemical Formula A (Mw = 3,200, PD = 1.85) was obtained. [Chemical Formula A] Comparative Synthesis Example 2

50 g (0.23 mol) of 1-hydroxyindole and 35.9 g (0.23 mol) of 1-naphthaldehyde were sequentially placed in a 500 ml flask and dissolved in 200 g of propylene glycol monomethyl ether acetate (PGMEA). 1 g (0.005 mol) of p-toluenesulfonic acid was added, and the mixture was stirred at 90 ° C to 120 ° C for about 8 hours. When the weight average molecular weight of the sample obtained from the polymerization per hour was 3,000 to 4,000, the reaction was completed, and a polymer represented by Chemical Formula B (Mw = 3,540, PD = 2.12) was obtained. [Chemical Formula B] Comparative Synthesis Example 3

Anthrone (2.3 g, 0.01 mol), carbazole (1.67 g, 0.01 mol), p-toluenesulfonic acid monohydrate (1.9 g, 0.01 mol) and 1,4-dioxane (25 g) It was placed in a flask and stirred at 120 °C. When the weight average molecular weight of the sample obtained from the polymerization per hour is from 2,500 to 3,500, the reaction is completed. When the reaction was completed, hexane (100 g) was added thereto for extraction, 1,4-dioxane, water and methanol were added thereto to form a precipitate, and the precipitate was filtered by removing it with methanol. The remaining monomer gave the polymer represented by Chemical Formula C (MW: 3, 100, PD = 1.75). [Chemical Formula C] Preparation of Hard Mask Composition Example 1

The polymer of Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3 (v/v)) and the solution was filtered to obtain a hard mask composition. The amount of the polymer is adjusted in the range of from 3% by weight to 15% by weight based on the total thickness of the hard masking 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. Comparative example 1

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

A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Comparative Synthesis Example 1 was used instead of the polymer of Synthesis Example 2. Comparative example 3

A hard mask composition was prepared in the same manner as in Example 1 except that the polymer of Comparative Synthesis Example 1 was used instead of the polymer of Synthesis Example 3. Evaluation Evaluation 1 : Resistance to etching

Each of the hard mask compositions according to Examples 1 to 8 and Comparative Examples 1 to 3 was spin-coated on a tantalum wafer and heat-treated at 240 ° C for 1 minute on a hot plate to form a thickness of 4,000 Å. Each film. Subsequently, the thickness of the film was measured using a film thickness measuring device manufactured by K-MAC. Subsequently, the film was subjected to dry etching for 60 seconds and 100 seconds, respectively, by using a mixed gas of N ₂ /O ₂ and CF _x gas, respectively, and the weight thereof was measured again. The bulk etch rate (BER) was calculated according to Equation 1 using the film thickness before and after dry etching and its etching time. [Calculation Equation 1] Body etching rate (BER) = (initial film thickness - film thickness after etching) / etching time (angstroms per second)

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

On the other hand, the etching rate was calculated by changing the heat treatment temperature and time to 400 ° C and 2 minutes, respectively. The results are shown in Table 2. [Table 2]

Referring to Tables 1 and 2, each of the films formed of the hard mask compositions according to Examples 1 to 8 was treated with an etching gas as compared with the films formed of the hard mask compositions according to Comparative Example 1 to Comparative Example 3. It has sufficient etch resistance to exhibit improved body etch characteristics. Assessment 2 : Solubility and storage stability

The polymers according to Synthesis Example 1 to Synthesis Example 8 and Comparative Synthesis Example 1 and Comparative Synthesis Example 2 were dissolved in 20 g of ethyl lactate (EL) solvent to visually examine the solubility thereof. Solubility was evaluated by measuring the mass of the polymer in 20 grams of ethyl lactate solvent and converting the mass to a percentage.

Subsequently, the solvent was changed to propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the solubility of the polymer was evaluated in the same manner as above.

On the other hand, a solution was prepared by dissolving the polymers of Synthesis Example 1 to Synthesis Example 8 and Comparative Synthesis Example 1 and Comparative Synthesis Example 2, respectively, in ethyl lactate (EL) to prepare a solution (polymer content: 10% by weight). To evaluate storage stability, the solution was stored in a clean room sealed with ultraviolet (UV) and placed at 23 ° C for one month, and its trend curve was examined by using gel permeation chromatography (GPC). Variety. When there is no trend curve change, no storage stability ("X") is given, and when there is a trend curve change, storage stability ("O") is given. The results are shown in Tables 3 and 4. [table 3] [Table 4]

Referring to Tables 3 and 4, the polymers of Synthesis Examples 1 to 8 exhibited satisfactory storage stability and excellent solubility in each solvent as compared with the polymers of Comparative Synthesis Example 1 and Comparative Synthesis Example 2.

Although the present invention has been described in connection with what is presently considered as a practical illustrative embodiment, it is understood that the invention is not limited to the disclosed embodiments, but rather, the invention is intended to cover the spirit of the appended claims Various modifications and equivalent configurations within the scope.

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Claims (16)

A polymer comprising: a structural unit represented by Chemical Formula 1; and a structural unit represented by Chemical Formula 2, [Chemical Formula 1] [Chemical Formula 2] Wherein, in the chemical formula 1 and the chemical formula 2, A ¹ and A ^{2 are} independently a divalent group comprising at least one of a substituted or unsubstituted benzene ring, and A ³ is a four-stage A divalent cyclic group of carbon, and * is a point of attachment. The polymer of claim 1, wherein A ³ is one of the groups of group 1: [Group 1] Wherein, in the group 1, Ar ¹ to Ar ^{4 are} independently a substituted or unsubstituted C6 to C30 aryl group, and R ¹¹ to R ^{14 are} independently a hydroxyl group, a sulfinyl group, a thiol group, a cyanogen group. A substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C3 to C30 cycloalkenyl, substituted or unsubstituted C1 to C20 alkylamino, substituted or unsubstituted C7 to C20 arylalkyl, Substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C1 To a C4 alkyl ether group, a substituted or unsubstituted C7 to C20 aryl alkyl ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof, o, p, q and r independently An integer from 0 to 3, 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 in the range of 1 to 3 Inside Integer, and * is the join point. The polymer of claim 1, wherein at least one of A ¹ and A ² is a divalent cyclic group comprising at least two rings in the structure. The polymer of claim 3, wherein A ¹ and A ^{2 are} independently a divalent group derived from one of the compounds of Group 2 and Group 3, wherein at least the divalent group One hydrogen is replaced or unsubstituted, [Group 2] [Group 3] Wherein, in the group 3, R ¹ , R ² and R ^{3 are} independently 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, hydroxyl group, halogen atom , halogen-containing groups or a combination thereof. The polymer of claim 1, wherein A ¹ and A ² are different from each other. The polymer of claim 1, wherein the weight average molecular weight is in the range of 1,000 to 200,000. An organic layer composition comprising: a polymer comprising: a structural unit represented by Chemical Formula 1; and a structural unit represented by Chemical Formula 2; and a solvent: [Chemical Formula 1] [Chemical Formula 2] Wherein, in the chemical formula 1 and the chemical formula 2, A ¹ and A ^{2 are} independently a divalent group comprising at least one of a substituted or unsubstituted benzene ring, and A ³ is a four-stage A divalent cyclic group of carbon, and * is a point of attachment. The organic layer composition as described in claim 7, wherein A ³ is one of the groups of the group 1: [group 1] Wherein, in the group 1, Ar ¹ to Ar ^{4 are} independently a substituted or unsubstituted C6 to C30 aryl group, and R ¹¹ to R ^{14 are} independently a hydroxyl group, a sulfinyl group, a thiol group, a cyanogen group. A substituted or unsubstituted amino group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C3 to C30 cycloalkenyl, substituted or unsubstituted C1 to C20 alkylamino, substituted or unsubstituted C7 to C20 arylalkyl, Substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 heteroaryl, substituted or unsubstituted C1 To a C4 alkyl ether group, a substituted or unsubstituted C7 to C20 aryl alkyl ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof, o, p, q and r independently An integer from 0 to 3, 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 in the range of 1 to 3 Inside Number and * is the point of attachment. The organic layer composition of claim 7, wherein at least one of A ¹ and A ² is a divalent cyclic group having at least two rings in the structure. The organic layer composition according to claim 9, wherein A ¹ and A ^{2 are} independently a divalent group derived from one of the group 2 and the compound of the group 3, wherein the divalent group At least one hydrogen is replaced or unsubstituted: [Group 2] [Group 3] Wherein, in the group 3, R ¹ , R ² and R ^{3 are} independently 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, hydroxyl group, halogen atom , halogen-containing groups or a combination thereof. The organic layer composition as described in claim 7, wherein A ¹ and A ² are different from each other. The organic layer composition of claim 7, wherein the weight average molecular weight is in the range of 1,000 to 200,000. The organic layer composition according to claim 7, 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. A pattern forming method comprising: providing a material layer on a substrate; and coating, on the material layer, an organic layer composition according to any one of claim 7 to claim 13; The layer composition is heat-treated to form a hard mask layer, a thin layer containing tantalum is formed on the hard mask layer; a photoresist layer is formed on the tantalum-containing layer; and the photoresist layer is exposed and developed to form a photoresist pattern; the photoresist pattern is used to selectively remove the tantalum-containing layer and the hard mask layer to expose a portion of the material layer; and etch the exposed portion of the material layer. The pattern forming method according to claim 14, wherein the organic layer composition is applied by a spin coating method. The pattern forming method of claim 14, further comprising forming a bottom anti-reflective coating layer before forming the photoresist layer.