TWI694092B - Polymer, organic layer composition, and method of forming patterns - Google Patents

Abstract

The present disclosure is related to a polymer including a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2 or Chemical Formula 3, an organic layer composition including the polymer, and a method of forming patterns using the organic layer composition.

Description

Polymer, organic layer composition and method for forming pattern

The present disclosure relates to a novel polymer, an organic layer composition containing the polymer, and a method for forming a pattern using the organic layer composition.

Recently, the semiconductor industry has developed to ultra-fine technology with patterns of a few nanometers to tens of nanometers. Such ultrafine technology essentially requires effective lithographic techniques.

Typical lithography techniques include: providing a material layer on a semiconductor substrate; coating a photoresist layer thereon; exposing and developing the photoresist layer to provide a photoresist pattern; and using the photoresist pattern as a mask pair The material layer is etched.

At present, according to the miniaturization of the pattern to be formed, it is difficult to provide a fine pattern with an excellent outline only by the above-mentioned typical lithography technique. Therefore, a layer called a hard mask layer may be formed between the material layer and the photoresist layer to provide a fine pattern.

The hard mask layer functions as an intermediate layer to transfer the fine pattern of photoresist to the material layer through the selective etching process. Therefore, the hard mask layer needs to have characteristics such as heat resistance and etching resistance in order to withstand multiple etching processes.

On the other hand, a spin-on coating method has recently been proposed to replace the chemical vapor deposition (CVD) method to form a hard mask layer. The spin coating method can not only be easily performed but can also improve gap filling characteristics and planarization characteristics.

The hard mask composition applied to the spin coating method may generally include a resin having a maximized carbon content to increase etching selectivity. In this case, since the resin does not dissolve due to the reduced solubility in the solvent mainly used for semiconductors, the hard mask composition may be difficult to apply in the spin coating method. To solve this problem, another solvent with better solubility has been conventionally proposed, but the solvent may have a bad smell or deteriorate coating uniformity. In addition, when the carbon content is reduced to increase the solubility, there is a problem of reducing the etching resistance. Therefore, there is a need for an organic layer composition material that improves storage stability, enhances solubility to use solvents mainly used in semiconductor processes, and maximizes carbon content.

The embodiment provides a novel polymer having improved etching resistance and layer density while ensuring solubility and storage stability.

Another embodiment provides an organic layer composition including the polymer.

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

[化學式2]

[化學式3]

在化學式1至化學式3中， A為由化學式X表示的部分， B為經取代或未經取代的C6至C30芳族環基團， Ar¹ 及Ar² 獨立地為經取代或未經取代的苯環或其稠環， m為介於0至5範圍內的整數，且 *為連接點， [化學式X]

其中，在化學式X中， Ar³ 為經取代或未經取代的四角環、經取代或未經取代的五角環、經取代或未經取代的六角環或其稠環， R^a 為氫、羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合， Z^a 獨立地為羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合，且 n為介於0至2範圍內的整數。According to an embodiment, there is provided a polymer including a structural unit represented by Chemical Formula 1, and a structural unit represented by Chemical Formula 2 or Chemical Formula 3. [Chemical Formula 1]

[Chemical Formula 2]

[Chemical Formula 3]

In Chemical Formulas 1 to 3, A is a moiety represented by Chemical Formula X, B is a substituted or unsubstituted C6 to C30 aromatic ring group, and Ar ¹ and Ar ^{2 are} independently substituted or unsubstituted Benzene ring or its condensed ring, m is an integer ranging from 0 to 5, and * is the point of attachment, [Chemical Formula X]

Wherein, in the chemical formula X, Ar ³ is a substituted or unsubstituted quadrangular ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring or a condensed ring, R ^a is hydrogen, hydroxy , Halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof, Z ^{a is} independently hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, Substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 hetero Aryl or a combination thereof, and n is an integer ranging from 0 to 2.

In Chemical Formula 1, B may be one of the substituted or unsubstituted portions of Group 1. [Group 1]

在群組2中， R¹ 及R² 獨立地為氫、羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合， 條件是在群組2中，每一部分的氫可獨立地由以下置換或未經置換：羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合。In Chemical Formula 1 to Chemical Formula 3, A may be one of the parts of Group 2. [Group 2]

In Group 2, R ¹ and R ^{2 are} independently hydrogen, hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or Unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, Substituted or unsubstituted C2 to C30 heteroaryl or a combination thereof, provided that in Group 2, each part of the hydrogen can be independently substituted or unsubstituted by the following: hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or Unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof.

In Chemical Formula 2 or Chemical Formula 3, Ar ¹ and Ar ² may independently be substituted or unsubstituted benzene moieties, substituted or unsubstituted naphthalene moieties, substituted or unsubstituted Anthracene part, substituted or unsubstituted phenanthrene part, substituted or unsubstituted fused tetracene part, substituted or unsubstituted chrysene part, substituted or Unsubstituted triphenylene part, substituted or unsubstituted pyrene part, substituted or unsubstituted perylene part, substituted or unsubstituted benzoperylene ) Part or substituted or unsubstituted coronene part.

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

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

The polymer may be included in an amount of 0.1% to 30% by weight based on the total amount of the organic layer composition.

According to another embodiment, a method for forming a pattern includes: forming a material layer on a substrate, applying an organic layer composition including a polymer and a solvent on the material layer, and heat-treating the organic layer composition to form a hard mask Layer, forming a silicon-containing thin layer on the hard mask layer, forming a photoresist layer on the silicon-containing thin layer, exposing and developing the photoresist layer to form a photoresist pattern, and using the photoresist pattern to selectively remove the The thin silicon layer and the hard mask layer expose a portion of the material layer and etch the exposed portion of the material layer.

The organic layer composition can be applied by spin coating.

The method may further include forming a bottom antireflective coating (BARC) before forming the photoresist layer.

The polymer according to the embodiment may include a combination of the following groups: a heterocyclic group including an indole structure, a ring group having a third-order carbon bond, and a ring group having a fourth-order carbon bond. Therefore, when the polymer is used as an organic layer material, an organic layer having etching resistance and layer density and ensuring solubility and storage stability can be provided.

Exemplary embodiments of the present invention will be described in detail below, and can be easily performed by those skilled in the art. However, the present invention can be implemented in many different forms and should not be interpreted as being limited to the exemplary embodiments described herein.

In this specification, when a definition is not provided otherwise, "substituted" may mean that the hydrogen atom of the compound is replaced by a substituent selected from the group consisting of a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, and a cyano group , Amine, azido, amidino group, hydrazine group, hydrazono, carbonyl group, carbamoyl group, thiol group, ester group, carboxyl group or its salt, sulfonate group Or its salt, phosphoric acid or its salt, C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 aralkyl, C1 to C30 alkoxy, C1 to C20 Heteroalkyl, C3 to C20 heteroaralkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C3 to C30 heterocycloalkyl, and combinations thereof.

In this specification, when no definition is provided otherwise, "hetero" refers to containing 1 to 3 heteroatoms selected from N, O, S, and P.

In this specification, when a definition is not provided otherwise, "*" refers to a connection point of a compound or a compound part.

In the following, the polymers according to the examples are explained.

[化學式2]

[化學式3]

在化學式1至化學式3中， A為由化學式X表示的部分， B為經取代或未經取代的C6至C30芳族環基團， Ar¹ 及Ar² 獨立地為經取代或未經取代的苯環或其稠環， m為介於0至5範圍內的整數，且 *為連接點： [化學式X]

其中，在化學式X中， Ar³ 為經取代或未經取代的四角環、經取代或未經取代的五角環、經取代或未經取代的六角環或其稠環， R^a 為氫、羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合， Z^a 獨立地為羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合，且 n為介於0至2範圍內的整數。The polymer according to the embodiment includes the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 or Chemical Formula 3. [Chemical Formula 1]

[Chemical Formula 2]

[Chemical Formula 3]

In Chemical Formulas 1 to 3, A is a moiety represented by Chemical Formula X, B is a substituted or unsubstituted C6 to C30 aromatic ring group, and Ar ¹ and Ar ^{2 are} independently substituted or unsubstituted Benzene ring or its condensed ring, m is an integer in the range of 0 to 5, and * is the point of attachment: [Chemical Formula X]

Wherein, in the chemical formula X, Ar ³ is a substituted or unsubstituted quadrangular ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring or a condensed ring, R ^a is hydrogen, hydroxy , Halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof, Z ^{a is} independently hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, Substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 hetero Aryl or a combination thereof, and n is an integer ranging from 0 to 2.

The polymer includes a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2 or Chemical Formula 3, wherein the number and arrangement of the resulting units are not limited.

The structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 or Chemical Formula 3 include the indole compound represented by A or a derivative thereof (indole structural part), and may be specifically represented by Chemical Formula X.

In Chemical Formula X, Ar ³ is a substituted or unsubstituted tetragonal ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring, or a fused ring thereof, and the fused ring may be, for example 2. The condensed form of 2, 3 or 4 benzene rings is not limited to this.

在群組2中， R¹ 及R² 獨立地為氫、羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合， 條件是在群組2中，每一部分的氫可獨立地由以下置換或未經置換：羥基、鹵素、經取代或未經取代的C1至C30烷氧基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C2至C30烯基、經取代或未經取代的C2至C30炔基、經取代或未經取代的C6至C30芳基、經取代或未經取代的C1至C30雜烷基、經取代或未經取代的C2至C30雜芳基或其組合。The chemical formula X may specifically be one of the parts of the group 2, but it is not limited to this. [Group 2]

In Group 2, R ¹ and R ^{2 are} independently hydrogen, hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or Unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, Substituted or unsubstituted C2 to C30 heteroaryl or a combination thereof, provided that in Group 2, each part of the hydrogen can be independently substituted or unsubstituted by the following: hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or Unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof.

In Group 2, the position where each part is connected to another part is not particularly limited.

The structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 or Chemical Formula 3 include the indole structure represented by A, and in the indole structure, the side of the pentagonal ring portion including the nitrogen atom (N) is represented by The ring is closed (fused), and the other side is not fused by the ring but open (ie, one side of the pentagonal ring in formula X is fused with Ar ³ , but the other side is not fused), compared to For carbazole-based structural units that have a pentacyclic ring portion including a nitrogen atom partially closed in this structure, this can relatively promote bonding within the polymer or between multiple polymers during baking, and thus increase carbon Content and correspondingly greatly improve the etching resistance.

In addition to the indole structure represented by A, the structural unit represented by Chemical Formula 1 also includes a hydrogen-containing portion, carbon, and an aromatic ring group represented by B (that is, a ring group portion having a tertiary carbon bond) . Further, in addition to the indole structure represented by A, the structural unit represented by Chemical Formula 2 or Chemical Formula 3 also includes carbon and a portion represented by Ar ¹ and Ar ² (that is, a portion having a quaternary carbon bond).

In this context, tertiary carbon indicates carbon in which three of the four hydrogens bonded to it are replaced with groups other than hydrogen, and quaternary carbon indicates that the four hydrogens bonded to it are removed in addition to hydrogen The carbon is replaced by other groups.

The polymer includes tertiary carbon having a structural unit represented by Chemical Formula 1, and thereby may have maximized ring parameters and enhance etching resistance. In addition, the polymer includes a quaternary carbon having a structural unit represented by Chemical Formula 2 or Chemical Formula 3, and therefore, the solubility with respect to the solvent can be improved due to a steric effect generated by the structural characteristics of the quaternary carbon bond. The conventional composition inevitably uses a solvent having high solubility, but will deteriorate storage stability or coating uniformity, but the polymer according to the embodiment itself has high solid solubility and is not limited in selecting a solvent, and Therefore, the storage stability and coating uniformity of the organic layer composition may not be impaired.

The polymer includes both tertiary carbon and quaternary carbon, and therefore simultaneously ensures layer density and solubility, and accordingly can minimize the addition of other functional groups and ultimately improve solubility and etch resistance.

For example, the aromatic ring group (B) connected to the tertiary carbon in Chemical Formula 1 may be one of the substituted or unsubstituted portions in Group 1, but it is not limited thereto. [Group 1]

On the other hand, Ar ¹ and Ar ² forming a ring group portion having a quaternary carbon in Chemical Formula 2 or Chemical Formula 3 are independently a substituted or unsubstituted benzene moiety, a substituted or unsubstituted naphthalene moiety, Substituted or unsubstituted anthracene moieties, substituted or unsubstituted phenanthrene moieties, substituted or unsubstituted fused tetraphenyl moieties, substituted or unsubstituted molybdenum moieties, substituted or unsubstituted moieties Triphenylene moieties, substituted or unsubstituted pyrene moieties, substituted or unsubstituted perylene moieties, substituted or unsubstituted benzoperylene moieties, or substituted or unsubstituted molybdenum moieties, but not limited to this. Ar1 and Ar in Chemical Formula 2 or Chemical Formula 3 ^may be the same or different from each other.

In Chemical Formula 3, m is an integer ranging from 0 to 5, which means that there is no bond between Ar ¹ and Ar ² or it is connected by an alkylene group having 1 to 5 carbons. In other words, when m is 0, there is no corresponding key. The polymer can be obtained, for example, by ternary copolymerization. In the polymer, a tertiary carbon structure can be formed, for example, by introducing an aldehyde compound or its derivative as an electrophilie during polymer synthesis.

The polymer may have a weight average molecular weight of about 500 to 200,000. More specifically, the polymer may have a weight average molecular weight of about 1,000 to 20,000. When the polymer has a weight average molecular weight within the above range, the organic layer composition (for example, hard mask composition) containing the polymer can be optimized by adjusting the carbon content and the solubility in the solvent.

When the polymer is used as an organic layer material, not only a uniform thin layer can be achieved during the baking process without forming pin-holes or voids and the thickness distribution is not deteriorated, and when the lower substrate (or layer ) With step or patterning, excellent gap filling characteristics and flattening characteristics can be achieved.

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

The solvent may be any solvent having sufficient solubility or dispersibility for the polymer, and may include, for example, at least one selected from propylene glycol, propylene glycol diacetate, methoxy propylene glycol, diethylene glycol, 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-dimethylformamide Amine, N,N dimethylacetamide, methylpyrrolidone (methyl pyrrolidone), methylpyrrolidone (methyl pyrrolidinone), acetone acetone and ethyl 3-ethoxypropionate.

The polymer may be included in an amount of about 0.1% by weight to 50% by weight, about 0.1% by weight to 30% by weight, or about 0.1% by weight to 15% by weight based on the total amount of the organic layer composition. When a 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 contain the following additives: surfactant, crosslinking agent, thermal acid generator or plasticizer.

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

The crosslinking agent may be, for example, a melamine-based crosslinking agent, a substituted urea-based crosslinking agent, or a polymer-based crosslinking agent. Preferably, it may be a cross-linking agent having at least two cross-links to form a substituent, for example, for example, methoxymethylated glycoluril, butoxymethylated glycoluril ), methoxymethylated melamine, butoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine Amine (butoxymethylated benzoguanamine), methoxymethylated urea (methoxymethylatedurea), butoxymethylated urea (butoxymethylatedurea), methoxymethylated thiourea (methoxymethylated thiourea) and butoxymethylated thiourea (butoxymethylated thiourea) butoxymethylated thiourea) and other compounds.

The cross-linking agent may be a cross-linking agent with high heat resistance. The cross-linking agent having high heat resistance may be a compound containing a cross-linking substituent containing an aromatic ring (for example, 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 Formic acid and/or 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, other organic sulfonic acid alkyl esters, etc., but not Only this.

The additive may be present in an amount of 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 without changing the optical characteristics of the organic layer composition.

According to another embodiment, an organic layer manufactured using the 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 for an electronic device, a planarization layer, a sacrificial layer, a filler Wait.

Hereinafter, a method of forming a pattern using an organic layer composition will be explained with reference to FIG. 1.

FIG. 1 is a flowchart of a method for forming a pattern according to an embodiment.

A method for forming a pattern according to an embodiment includes: forming a material layer on a substrate (S1), applying the organic layer composition including the polymer and a solvent on the material layer (S2), and forming the organic layer Heat treatment to form a hard mask layer (S3), a silicon-containing thin layer (S4) on the hard mask layer, a photoresist layer (S5) on the silicon-containing thin layer, and exposure and development of the photoresist layer To form a photoresist pattern (S6), the photoresist pattern is used to selectively remove the silicon-containing thin layer and the hard mask layer to expose a portion of the material layer (S7), and to etch the exposed portion of the material layer (S7) S8).

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

The material layer is a material to be finally patterned, for example, a metal layer such as an aluminum layer and a copper layer, a semiconductor layer such as a silicon layer, or an insulating layer such as a silicon oxide layer and a silicon 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 in the form of a solution by spin coating. Here, the thickness of the organic layer composition is not particularly limited, but may be, for example, about 50 angstroms to 200,000 angstroms or about 50 angstroms to 10,000 angstroms.

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

The silicon-containing thin layer may be formed of materials such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and/or SiN.

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

The photoresist layer may be exposed using, for example, ArF, KrF, or EUV. After the exposure, heat treatment may be performed at about 100°C to 700°C.

The etching process may be performed on the exposed portion of the material layer by a dry etching process using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and mixed gas thereof, but is not limited.

The etched material layer may be formed into a plurality of patterns, and the plurality of patterns may be metal patterns, semiconductor patterns, insulating patterns, etc., such as various patterns of semiconductor integrated circuit devices.

Hereinafter, the present disclosure will be described in more detail with reference to examples. However, these examples are exemplary, and the present disclosure is not limited to this. Synthesis Example Synthesis Example 1

Combine 50 g (0.43 mol) indole, 34.1 g (0.21 mol) 1-naphthaldehyde, 38.5 g (0.49 mol) 9-fluorenone and 24.4 g (0.14 mol) Ear) p-toluene sulfonic acid (p-toluene sulfonic acide) was added to a 500-ml double-necked flask equipped with a mechanical stirrer and cooling tube 180 g 1,4-dioxane, and the resulting mixture was stirred and then After raising the temperature of the flask to 110°C, the mixture was stirred for 17 hours. When the reaction was completed, the internal temperature of the flask was lowered to 60°C to 70°C, 300 grams of tetrahydrofuran was added to the flask to prevent the hardening of the compound, and the pH of the compound was adjusted to 5 to 5 with a 7% sodium bicarbonate aqueous solution 6. Then, 1000 ml of ethyl acetate was poured into the flask and the resulting mixture was continuously stirred, and the mixture was treated with a separatory funnel to extract only the organic layer. By pouring 500 ml of water into a separatory funnel, this operation was repeated three times or repeatedly to remove the acid and sodium salt remaining therein, and the organic layer was finally extracted. Subsequently, the organic solution was concentrated using an evaporator, and 700 g of tetrahydrofuran was added to the compound thus obtained to obtain a solution. The solution was slowly added dropwise to a beaker containing 3000 ml of hexane to form a precipitate and obtain a polymer including the structural unit represented by Chemical Formula 1a.

合成例 2 When the polymer was processed by gel permeation chromatography (GPC), the weight average molecular weight (Mw) of the polymer was 1,230, and the polydispersity (PD) of the polymer was 1.21. [Chemical Formula 1a]

Synthesis Example 2

Except that 1-pyrenecarboxaldehyde was used instead of 1-naphthaldehyde, a polymer including a structural unit represented by Chemical Formula 2a was obtained according to the same method as Synthesis Example 1.

合成例 3 The weight average molecular weight (Mw) of the polymer was 1,445, and the polydispersity (PD) of the polymer was 1.28. [Chemical Formula 2a]

Synthesis Example 3

Except that 1H-benzo[g]indole (1H-benzo[g]indole) was used instead of indole, a polymer including a structural unit represented by Chemical Formula 3a was obtained according to the same method as in Synthesis Example 2.

合成例 4 The weight average molecular weight (Mw) of the polymer was 1,710, and the polydispersity (PD) of the polymer was 1.31. [Chemical Formula 3a]

Synthesis Example 4

Except that 1-coronenecarboxaldehyde was used instead of 1-pyrene formaldehyde, a polymer including a structural unit represented by Chemical Formula 4a was obtained according to the same method as Synthesis Example 3.

合成例 5 The weight average molecular weight (Mw) of the polymer was 2,100, and the polydispersity (PD) of the polymer was 1.33. [Chemical Formula 4a]

Synthesis Example 5

Except for using 9H-Indeno[1,2-I]phenanthrene-9-one (9H-Indeno[1,2-I]phenanthren-9-one]) instead of 9-stilbionone, according to the same as Synthesis Example 3 The method obtains a polymer including the structural unit represented by the chemical formula 5a.

合成例 6 The weight average molecular weight (Mw) of the polymer was 1,890, and the polydispersity (PD) of the polymer was 1.36. [Chemical Formula 5a]

Synthesis Example 6

Same as in Synthesis Example 3 except that 1H-dibenzo[e,g]indole (1H-dibenzo[e,g]indole) was used instead of indole and benzophenone was used instead of 9-stilbrone The method of obtaining a polymer including the structural unit represented by the chemical formula 6a.

比較合成例 1 The weight average molecular weight (Mw) of the polymer was 2,660, and the polydispersity (PD) of the polymer was 1.41. [Chemical Formula 6a]

Comparative Synthesis Example 1

Put 20 g (0.103 mol) of 1-hydroxyanthracene (1-hydroxyanthracene) and 3.08 g (0.103 mol) of paraformaldehyde in a 500 ml flask and dissolve in 42 g of propylene glycol monomethyl ether ether To the ester (propylene glycol monomethyl ether acetate, PGMEA), 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 sample extracted from the polymerization reactant per hour has a weight average molecular weight of 3,000 to 4,200, the reaction is completed to obtain a polymer including the structural unit represented by Chemical Formula A.

比較合成例 2 The weight average molecular weight (Mw) of the polymer was 3,200, and the polydispersity (PD) of the polymer was 1.85. [Chemical Formula A]

Comparative Synthesis Example 2

33 g (0.23 mol) of indole and 35.9 g (0.23 mol) of 1-naphthalene formaldehyde were placed in a 500 ml flask in sequence, and then dissolved in 200 g of propylene glycol monomethyl ether acetate (PGMEA). 1 g (0.005 mol) of p-toluenesulfonic acid was added thereto, and the mixture was stirred at 90°C to 120°C for about 12 hours. When the sample extracted from the polymerization reactant per hour has a weight average molecular weight of 2,000 to 3,000, the reaction is completed to obtain a polymer including a structural unit represented by Chemical Formula B.

比較合成例 3 The weight average molecular weight (Mw) of the polymer was 2,620, and the polydispersity (PD) of the polymer was 1.51. [Chemical Formula B]

Comparative Synthesis Example 3

Put 28.5 g (0.17 mol) of carbazole and 30.8 g (0.17 mol) of 9- stilbene in sequence into a 500 mL flask, then dissolve in 250 g of 1,4-dioxane and add to it 32.5 grams (0.17 mole) of p-toluenesulfonic acid, and the mixture was stirred at 90°C to 120°C for 30 hours. Then, when the sample extracted from the polymerization reactant per hour has a weight average molecular weight of 2,000 to 4,000, the reaction is completed to obtain a polymer including the structural unit represented by the chemical formula C.

比較合成例 4 The weight average molecular weight (Mw) of the polymer was 3,730, and the polydispersity (PD) of the polymer was 1.38. [Chemical Formula C]

Comparative Synthesis Example 4

Place 30 g (0.18 mol) of carbazole, 14 g (0.09 mol) of 1-naphthaldehyde, and 16.2 g (0.09 mol) of 9- stilbene in this order into a 500-mL flask, then dissolve in 70 g To 1,4-dioxane, 8.6 g (0.09 mol) of p-toluenesulfonic acid was added thereto, and the mixture was stirred at 95°C to 100°C for 28 hours. Then, when the sample extracted from the polymerization reactant per hour has a weight average molecular weight of 2,000 to 4,000, the reaction is completed to obtain a polymer including the structural unit represented by the chemical formula D.

比較合成例 5 The weight average molecular weight (Mw) of the polymer was 3,760, and the polydispersity (PD) of the polymer was 1.81. [Chemical Formula D]

Comparative Synthesis Example 5

The polymer structural unit represented by the chemical formula E was obtained according to the same method as Synthesis Example 1, except that 1-anthracarbaldehyde was used instead of 9-stilbionone.

比較合成例 6 The weight average molecular weight (Mw) of the polymer was 1,320, and the polydispersity (PD) of the polymer was 1.19. [Chemical Formula E]

Comparative Synthesis Example 6

The polymer structural unit represented by the chemical formula F was obtained according to the same method as Synthesis Example 1 except that benzophenone was used instead of 1-naphthaldehyde.

比較合成例 7 The weight average molecular weight (Mw) of the polymer was 2,890, and the polydispersity (PD) of the polymer was 1.42. [Chemical Formula F]

Comparative Synthesis Example 7

硬遮罩組成物的製備 實例 1 Combine 9-stilbene (18.02 g, 0.1 mol), indole (11.72 g, 0.1 mol), and N-phenylnaphthalen-1-amine (21.53 g, 0.1 mol) ), p-toluenesulfonic acid monohydrate (19.04 g, 0.1 mol) and PGMEA (281.20 g) were placed in a 500-ml flask equipped with a temperature sensor, condenser and mechanical stirrer at 120°C Stirring. Then, the reaction is completed when the sample extracted from the polymerization reactant per hour has a weight average molecular weight of 1,000 to 3,000. 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 was repeated three times. Then, the organic solvent layer was extracted therefrom, and the organic solvent layer was processed under reduced pressure. Then, 50 g of tetrahydrofuran was added thereto, 300 g of hexane was used to form a precipitate, and then PGMEA and monomer remaining therein were removed to obtain a polymer (Mw: 1,587) containing a structural unit represented by Chemical Formula G. [Chemical Formula G]

Preparation Example 1 of Hard Mask Composition

1.2 g of the polymer according to Synthesis Example 1 was dissolved in a mixed solvent of 10 g of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3 (v/v)), and A Teflon (tetrafluoroethylene) filter filtered the solution to prepare a hard mask composition. Example 2

A hard mask composition was prepared according to the same method as 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 according to the same method as 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 according to the same method as 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 according to the same method as 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 according to the same method as Example 1, except that the polymer of Synthesis Example 6 was used instead of the polymer of Synthesis Example 1. Comparative example 1

A hard mask composition was prepared according to the same method as 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 according to the same method as Example 1, except that the polymer of Comparative Synthesis Example 2 was used instead of the polymer of Synthesis Example 1. Comparative Example 3

A hard mask composition was prepared according to the same method as Example 1, except that the polymer of Comparative Synthesis Example 3 was used instead of the polymer of Synthesis Example 1. Comparative Example 4

A hard mask composition was prepared according to the same method as Example 1, except that the polymer of Comparative Synthesis Example 4 was used instead of the polymer of Synthesis Example 1. Comparative example 5

A hard mask composition was prepared according to the same method as Example 1, except that the polymer of Comparative Synthesis Example 5 was used instead of the polymer of Synthesis Example 1. Comparative Example 6

A hard mask composition was prepared according to the same method as Example 1, except that the polymer of Comparative Synthesis Example 6 was used instead of the polymer of Synthesis Example 1. Comparative Example 7

A hard mask composition was prepared according to the same method as Example 1, except that the polymer of Comparative Synthesis Example 7 was used instead of the polymer of Synthesis Example 1. Evaluation Evaluation 1 : Etching resistance

Each hard mask composition according to Examples 1 to 6 and Comparative Examples 1 to 7 was spin-coated on a silicon wafer and heat-treated on a hot plate at 240°C for 1 minute to form Each film having a thickness of 4,000 Angstroms, and the thickness of each film was measured. Then, each thin film was dry-etched with CHF ₃ /CF ₄ mixed gas and N ₂ /O ₂ mixed gas for 100 seconds and 60 seconds, respectively, and the thickness of the film was measured again. The thickness of the thin film before and after dry etching and the etching time of the thin film are used to calculate the bulk etch rate (BER) according to the calculation equation 1. [Calculation Equation 1] Etching rate (bulk etching rate, BER) = (initial film thickness-film thickness after etching)/etching time (Angstroms/sec)

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

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, compared to the films formed from the hard mask compositions according to Comparative Examples 1 to 7, the films formed from the hard mask compositions according to Examples 1 to 6 respectively have resistance due to The etching gas has sufficient etching resistance and exhibits improved bulk etching characteristics. Evaluation 2 : Solubility and storage stability

Each polymer according to Examples 1 to 6 and Comparative Examples 1 to 7 was added to 20 grams of ethyl lactate (EL), 20 grams of propylene glycol monomethyl ether acetate (PGMEA), and 20 grams of propylene glycol, respectively Monomethyl ether (PGME) to test solubility.

The solubility can be obtained by measuring the mass of each compound dissolved in 20 grams of solvent and converting the mass to a percentage as shown in the calculation equation 2. [Calculation Equation 2] Solubility (%) = mass of polymer dissolved in solvent (g) / mass of solvent (20 g)

On the other hand, the storage stability was evaluated by: dissolving each polymer of Examples 1 to 6 and Comparative Examples 1 to 7 at 10% by weight in ethyl lactate, and storing the solution in a Cut off the extreme ultraviolet (UV) in a clean room at 23°C for one month, and then measure its gel permeation chromatography to test whether the trend curve changes to "X" or "O".

The results are shown in Table 3. [table 3]

Referring to Table 3, compared to the polymers according to Comparative Examples 1 to 7, the polymers according to Examples 1 to 6 showed excellent solubility with respect to the solvent and showed excellent storage stability. Evaluation 3 : Layer density

Each hard mask composition according to Examples 1 to 6 and Comparative Examples 1 to 7 was spin-coated on a silicon wafer and heat-treated on a hot plate at 240°C for 1 minute to form Each film having a thickness of 1,000 Angstroms.

The layer density of each film was measured using X-ray diffraction analysis equipment of PANalytical, Inc.

The results are shown in Table 4. [Table 4]

Referring to Table 4, each film formed by the hard mask composition according to Examples 1 to 6 shows a high layer compared to the film formed by the hard mask composition according to Comparative Examples 1 to 7. density.

Although the present invention has been described in conjunction with exemplary embodiments that are currently considered to be practical, it should be understood that the present invention is not limited to the disclosed embodiments, but instead is intended to cover the spirit and scope of the scope of the accompanying patent application Various retouches and equivalent configurations.

S1, S2, S3, S4, S5, S6, S7, S8

FIG. 1 is a flowchart illustrating a method of forming a pattern according to an embodiment.

S1, S2, S3, S4, S5, S6, S7, S8

Claims (14)

A polymer including a structural unit represented by Chemical Formula 1, and a structural unit represented by Chemical Formula 2 or Chemical Formula 3:

Among them, in Chemical Formula 1 to Chemical Formula 3, A is a portion represented by Chemical Formula X, B is a substituted or unsubstituted C6 to C30 aromatic ring group, and Ar ¹ and Ar ^{2 are} independently substituted or unsubstituted Substituted benzene ring or its condensed ring, m is an integer in the range of 0 to 5, when m is 0, there is no corresponding bond, and * is the connection point, [Chemical Formula X]

Wherein, in the chemical formula X, Ar ³ is a substituted or unsubstituted quadrangular ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring or a condensed ring, R ^a is hydrogen, hydroxy , Halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof, Z ^{a is} independently hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, Substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 hetero Aryl or a combination thereof, and n is 0 or 1. The polymer as described in item 1 of the patent application scope, wherein in Chemical Formula 1, B is one of the substituted or unsubstituted portions of Group 1: [Group 1]

The polymer as described in item 1 of the patent application scope, wherein in Chemical Formula 1, A is one of the parts of Group 2: [Group 2]

Among them, in Group 2, R ¹ and R ^{2 are} independently hydrogen, hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, Substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkane Group, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof, provided that in Group 2, each part of the hydrogen is independently substituted or unsubstituted by the following: hydroxyl, halogen, substituted or unsubstituted Substituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted Or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof. The polymer according to item 1 of the patent application scope, wherein in Chemical Formula 2, Ar ¹ and Ar ^{2 are} independently a substituted or unsubstituted benzene moiety, a substituted or unsubstituted naphthalene moiety, a substituted or Unsubstituted anthracene moiety, substituted or unsubstituted phenanthrene moiety, substituted or unsubstituted fused tetraphenyl moiety, substituted or unsubstituted

Moieties, substituted or unsubstituted biphenyl triphenyl moieties, substituted or unsubstituted pyrene moieties, substituted or unsubstituted perylene moieties, substituted or unsubstituted benzoperylene moieties, or substituted or unsubstituted Replaced Kobe part. The polymer according to item 1 of the patent application range, wherein the weight average molecular weight of the polymer is in the range of 1,000 to 200,000. An organic layer composition, including: a polymer, including a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2 or Chemical Formula 3; and a solvent: [Chemical Formula 1]

Among them, in Chemical Formula 1 to Chemical Formula 3, A is a portion represented by Chemical Formula X, B is a substituted or unsubstituted C6 to C30 aromatic ring group, and Ar ¹ and Ar ^{2 are} independently substituted or unsubstituted Substituted benzene ring or its condensed ring, m is an integer in the range of 0 to 5, when m is 0, there is no corresponding bond, and * is the connection point,

Wherein, in the chemical formula X, Ar ³ is a substituted or unsubstituted quadrangular ring, a substituted or unsubstituted pentagonal ring, a substituted or unsubstituted hexagonal ring or a condensed ring, R ^a is hydrogen, hydroxy , Halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof, Z ^{a is} independently hydroxy, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, Substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 hetero Aryl or a combination thereof, and n is 0 or 1. The organic layer composition as described in item 6 of the patent application scope, wherein in Chemical Formula 1, B is one of the substituted or unsubstituted portions of Group 1: [Group 1]

The organic layer composition as described in Item 6 of the patent application scope, wherein in Chemical Formula 1, A is one of the parts of Group 2: [Group 2]

Among them, in Group 2, R ¹ and R ^{2 are} independently hydrogen, hydroxyl, halogen, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, Substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkane Group, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof, provided that in Group 2, each part of the hydrogen is independently substituted or unsubstituted by the following: hydroxyl, halogen, substituted or unsubstituted Substituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted Or unsubstituted C6 to C30 aryl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heteroaryl, or a combination thereof. The organic layer composition as described in item 6 of the patent application scope, wherein in Chemical Formula 2, Ar ¹ and Ar ^{2 are} independently a substituted or unsubstituted benzene moiety, a substituted or unsubstituted naphthalene moiety, a Substituted or unsubstituted anthracene moiety, substituted or unsubstituted phenanthrene moiety, substituted or unsubstituted fused tetraphenyl moiety, substituted or unsubstituted

Moieties, substituted or unsubstituted biphenyl triphenyl moieties, substituted or unsubstituted pyrene moieties, substituted or unsubstituted perylene moieties, substituted or unsubstituted benzoperylene moieties, or substituted or unsubstituted Replaced Kobe part. The organic layer composition as described in item 6 of the patent application range, wherein the weight average molecular weight of the polymer is in the range of 1,000 to 200,000. The organic layer composition as described in item 6 of the patent application range, wherein the amount of the polymer is 0.1% by weight to 30% by weight based on the total amount of the organic layer composition. A method for forming a pattern, including forming a material layer on a substrate, and combining the organic layer group as described in any one of patent application items 6 to 11 The product is coated on the material layer, the organic layer composition is heat-treated to form a hard mask layer, a silicon-containing thin layer is formed on the hard mask layer, and is formed on the silicon-containing thin layer A photoresist layer, exposing and developing the photoresist layer to form a photoresist pattern, and using the photoresist pattern to selectively remove the silicon-containing thin layer and the hard mask layer to expose the The portion of the material layer, and the exposed portion of the material layer is etched. The method for forming a pattern as described in item 12 of the patent application range, wherein the organic layer composition is applied by spin coating. The method for forming a pattern as described in item 12 of the patent application range, wherein the method for forming a pattern further includes forming a bottom anti-reflective coating (BARC) before forming the photoresist layer.

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