TWI644999B - Polymer, organic layer composition, and method of forming patterns - Google Patents

Abstract

The present invention discloses an organic layer composition and a method of forming a pattern using the organic layer composition, the organic layer composition comprising: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent. In Chemical Formula 1 and Chemical Formula 3, A, B, A ⁰ , A ¹ , A ² , L ¹ , L ² , L ³ , L ⁴ , X ¹ , X ² , X ³ , X ⁴ , m and n The same as described in the manual.

Description

Polymer, organic layer composition and method of forming a pattern

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

Recently, high-integration designs based on miniaturization (micro-tilization) and complexity of electronic devices have accelerated the development of more advanced materials and related processes, and therefore, lithography using conventional photoresists is also required. New patterned materials and technologies.

In a patterning process, an organic layer, referred to as a hard mask layer, can be formed as a hard interlayer to transfer the fine pattern of photoresist down to a sufficient depth on the substrate without collapse.

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

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

In general, since heat resistance and etching resistance have a trade-off relationship with spin-on characteristics, an organic layer material satisfying all of the above characteristics is required.

Embodiments of the present invention provide an organic layer composition that can be applied by spin coating and has improved etching resistance.

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

According to an embodiment, an organic layer composition comprises: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent.

In Chemical Formula 1, A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and B is a divalent organic group, and A and B At least one of them is substituted with a functional group containing a moity represented by Chemical Formula 2: [Chemical Formula 2]

Wherein, in Chemical Formula 2, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and * is a point of attachment,

Wherein, in Chemical Formula 3, A ⁰ , A ¹ , and A ^{2 are} independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A ⁰ , A ¹ and A ² are in the structure. Containing substituted or unsubstituted amino, substituted or unsubstituted vinyl, substituted or unsubstituted ethynyl, azido or nitrile, L ¹ , L ² , L ³ and L ⁴ Independently 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, X ¹ , X ² , X ³ and X ⁴ independently a hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, wherein X ¹ and X ^{2 are} not hydrogen at the same time, and X ³ and X ^{4 are} not hydrogen at the same time, and m and n are Independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the constraint that when m is 0, at least one of A ⁰ and A ² is included in the structure. a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, in A ¹ and A ⁰ At least one of the packages in the structure A substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group.

The functional group containing a moiety represented by Chemical Formula 2 can be represented by Chemical Formula 2'.

In Chemical Formula 2', W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing Or a combination thereof, Z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C30 aryl, a is 0 or 1, and b is between 0 and 10 An integer in the range, and * is the join point.

In Chemical Formula 3, A ⁰ , A ¹ and A ² may independently comprise a substituted or unsubstituted moiety selected from Group 1.

In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO ₂ , CR ^f R ^g , NR ^h or a carbonyl group, wherein R ^f to R ^{h are} independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

In Chemical Formula 3, at least one of A ⁰ , A ¹ and A ² may be a polycyclic cyclic group.

In Chemical Formula 3, at least one of A ⁰ , A ¹ and A ² may contain at least one of the functional groups represented by Chemical Formula 4 in the structure.

[Chemical Formula 4]

In Chemical Formula 4, W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, halogen-containing group Or a combination thereof, Y is a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, a nitrile group or a combination thereof, a is 0 or 1, b is an integer ranging from 0 to 10, and * is a connection point.

When the monomer contains a substituted or unsubstituted ethynyl group, the monomer may be represented by one of Chemical Formula 3a to Chemical Formula 3d.

[Chemical Formula 3b]

In Chemical Formula 3a to Chemical Formula 3d, A ³ , A ⁴ and A ^{5 are} independently a substituted or unsubstituted aromatic ring-containing group, and W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

In Chemical Formula 1, the A may be a substituted or unsubstituted moiety selected from Group 1 and Group 2.

[Group 1]

In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO ₂ , CR ^f R ^g , NR ^h or a carbonyl group, wherein R ^f to R ^{h are} independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

In group 2, Z ¹ and Z ^{2 are} independently NR ^d , O, S, Te or Se, Z ³ to Z ⁵ are N, and R ^d and R ^{e are} independently hydrogen, hydroxyl, methoxy, An ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

The B may be represented by one of the chemical formula Z1 to the chemical formula Z4.

[Chemical Formula Z3]

In the chemical formula Z1 to the chemical formula Z4, e and f are independently 0 or 1, g is an integer of 1 to 5, and Y ¹ to Y ^{4 are} independently selected from the substituted or unsubstituted portion of Group 3. One, and * is the connection point: [Group 3]

In group 3, M, M 'and M "are independently a substituted or unsubstituted C1 to C10 _{alkylene, O, S, SO 2,} CR f R g, NR h or carbonyl, wherein R ^f To R ^{h is} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof, and L ¹ is a substituted or unsubstituted C6 to C50 extended aryl group, The substituted or unsubstituted C1 to C10 alkylene oxide-containing group or a combination thereof, r is an integer of 0 to 10, s is an integer of 0 to 10, and k is an integer of 0 to 3.

The polymer may further contain a structural unit represented by Chemical Formula 5.

In Chemical Formula 5, X ⁰ is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and L ⁰ is a divalent organic group, and * For the connection point.

In Chemical Formula 5, X ⁰ may be a substituted or unsubstituted moiety selected from Group 1 and Group 2.

[Group 1]

In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO ₂ , CR ^f R ^g , NR ^h or a carbonyl group, wherein R ^f to R ^{h are} independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof, in Group 2, Z ¹ and Z ^{2 are} independently NR ^d , O, S, Te or Se, Z ³ to Z ⁵ are N, and R ^d and R ^{e are} independently hydrogen, hydroxy, methoxy, ethoxy, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkyl group, Substituted or unsubstituted C6 to C30 aryl or a combination thereof.

The polymer may comprise at least one oxygen atom in the structural unit.

The monomer may have a molecular weight of 500 to 50,000.

The polymer may have a weight average molecular weight of from 500 to 200,000.

The weight ratio of the polymer to the monomer may range from 70:30 to 30:70.

In accordance with another embodiment, a method of forming a pattern includes: providing a layer of material on a substrate, applying the organic layer composition to the layer of material, and subjecting the organic layer composition to heat treatment to form a hard mask layer Forming a thin layer containing germanium on the hard mask layer, forming a photoresist layer on the thin layer containing germanium, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist The agent pattern selectively removes the tantalum-containing layer and the hard mask layer to expose a portion of the material layer and etch the exposed portions of the material layer.

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

The heat treatment may include performing a first heat treatment at 50 ° C to 250 ° C and performing a second heat treatment at 200 ° C to 500 ° C after the first heat treatment.

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

The present invention provides an organic layer composition having improved etching resistance while being coated by a spin coating method by containing a predetermined polymer and a predetermined additive. The organic layer produced from the organic layer composition has an improved film density and film flatness.

FIG. 1 is a view for explaining a method of evaluating a flattening feature (a step feature).

2 is a view for explaining a method of evaluating a thickness uniformity characteristic.

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

In the present specification, when no definition is provided, "substituted" means that the hydrogen of the compound is replaced by a halogen atom (F, Br, Cl or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, Amino, azide, sulfhydryl, fluorenyl, fluorenyl, carbonyl, amine carbhydryl, thiol, ester, carboxyl or a salt thereof, sulfonic acid or a salt thereof, 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 heteroaryl, 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 a definition is not additionally provided, "hetero" refers to one containing one to three hetero atoms selected from B, N, O, S, and P.

Hereinafter, the organic layer composition according to the embodiment will be explained.

The organic layer composition according to the embodiment comprises: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent.

In Chemical Formula 1, A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and B is a divalent organic group, and A and B At least one of them is substituted with a functional group containing a moiety represented by Chemical Formula 2: [Chemical Formula 2]

Wherein, in Chemical Formula 2, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and * is a point of attachment:

Wherein, in Chemical Formula 3, A ⁰ , A ¹ , and A ^{2 are} independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A ⁰ , A ¹ and A ² are in the The structure includes a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, L ¹ , L ² , L ³ , And L ^{4 is} independently 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, X ¹ , X ² , X ³ and X ^{4 is} independently hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, with the proviso that X ¹ and X ^{2 are} not hydrogen at the same time, and X ³ and X ^{4 are} not hydrogen at the same time, and m and n are independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the constraint that when m is 0, at least one of A ⁰ and A ² is in the The structure includes a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, A ¹ and at least one of a ⁰ Comprising a substituted or unsubstituted amino group in the structure, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl, azido or nitrile group.

In the present specification, "ethynyl" refers to a monovalent functional group which is produced by substitution of one hydrogen of an acetylene compound, and "azido" refers to a monovalent functional group produced by substitution of one hydrogen of an azide compound. base.

The organic layer composition contains a polymer having a predetermined structure and a monomer having a predetermined structure. First, the polymer is explained.

The polymer contains one or more of the structural units represented by Chemical Formula 1, and includes an aromatic ring-containing moiety represented by A and a linking moiety represented by B in the structural unit. .

For example, A may be a substituted or unsubstituted aromatic ring-containing group, for example, a substituted or unsubstituted moiety selected from Group 1, but is not limited thereto.

[Group 1]

In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO ₂ , CR ^f R ^g , NR ^h or a carbonyl group, wherein R ^f to R ^{h are} independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

By way of further example, the A may be a substituted or unsubstituted aromatic ring-containing group, such as, but not limited to, a substituted or unsubstituted moiety selected from Group 2.

[Group 2]

In group 2, Z ¹ and Z ^{2 are} independently NR ^d , O, S, Te or Se, Z ³ to Z ⁵ are N, and R ^d and R ^{e are} independently hydrogen, hydroxyl, methoxy, An ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

By way of further example, A can be a combination of substituted or unsubstituted aromatic ring-containing groups and substituted or unsubstituted heteroaromatic ring-containing groups. For example, in Chemical Formula 1, A may contain two or more substituted or unsubstituted benzene rings, for example, two to six substituted or unsubstituted benzene rings. In this paper, the benzene ring can be At least one hydroxyl group is substituted.

In Chemical Formula 1, the linking group represented by B may be a divalent organic linear group, a divalent organic cyclic group, or a combination thereof. For example, B may be represented by one of Chemical Formula Z1 to Chemical Formula Z4, but is not limited thereto.

In the chemical formula Z1 to the chemical formula Z4, e and f are independently 0 or 1, g is an integer of 1 to 5, and Y ¹ to Y ^{4 are} independently a substituted or unsubstituted moiety selected from Group 3 (moiety One of them, and * is the connection point:

In group 3, M, M 'and M "are independently a substituted or unsubstituted C1 to C10 _{alkylene, O, S, SO 2,} CR f R g, NR h or carbonyl, wherein R ^f To R ^{h is} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof, and L ¹ is a substituted or unsubstituted C6 to C50 extended aryl group, The substituted or unsubstituted C1 to C10 alkylene oxide-containing group or a combination thereof, r is an integer of 0 to 10, s is an integer of 0 to 10, and k is an integer of 0 to 3.

On the other hand, in Chemical Formula 1, at least one of A and B is substituted with an acetylene-containing group represented by Chemical Formula 2. For example, the aromatic ring-containing group or the heteroaromatic ring-containing group represented by A may be substituted with an acetylene-containing group, and the linking group represented by B may be substituted with an acetylene-containing group or a moiety (moiety). And part B (moiety) may be substituted by an acetylene-containing group. Herein, the number of substitutions is not particularly limited.

For example, the functional group containing a moiety represented by Chemical Formula 2 can be represented by Chemical Formula 2', but is not limited thereto.

In Chemical Formula 2', W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing Or a combination thereof, Z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C30 aryl, a is 0 or 1, and b is between 0 and 10 An integer in the range, and * is the join point.

For example, the functional group containing a moiety represented by Chemical Formula 2 may be represented by Chemical Formula 2", but is not limited thereto.

In Chemical Formula 2", W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C 1 to C 20 alkyl, halogen atom, halogen-containing Base or a combination thereof, a is 0 or 1, and * is a connection point.

For example, the polymer can comprise at least one oxygen in the structure atom.

The polymer can ensure etching resistance due to the aromatic ring-containing group or the heteroaromatic ring-containing group represented by A in the structural unit, and can ensure flexibility due to the organic group represented by B. In addition, when the polymer is cured, acetylene forms a ring structure by introducing at least one acetylene to A or B, and thus etching resistance can be further improved. Therefore, the organic layer formed using the polymer has an increased layer density. In addition, the organic layer formed using the polymer may have thickness uniformity.

The polymer may further contain, for example, a structural unit represented by Chemical Formula 5.

In Chemical Formula 5, X ⁰ is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and L ⁰ is a divalent organic group, and * For the connection point.

In Chemical Formula 5, X may be a substituted or unsubstituted moiety selected from Group 1 and Group 2, and L ^{0 is the} same as B which is a linking group in Chemical Formula 1. Essentially different from the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 5 does not contain an acetylene functional group.

Hereinafter, the monomer of the organic layer composition will be described.

The monomer is represented by Chemical Formula 3 as described above.

[Chemical Formula 3]

In Chemical Formula 3, A ⁰ , A ¹ and A ^{2 are} independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A ⁰ , A ¹ , and A ² are in the structure. Containing substituted or unsubstituted amino, substituted or unsubstituted vinyl, substituted or unsubstituted ethynyl, azido or nitrile, L ¹ , L ² , L ³ , and L ⁴ independently, 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, X ¹ , X ² , X ³ and X ^{4 are} independently The ground is hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, and the limitation is that X ¹ and X ^{2 are} not hydrogen at the same time, and X ³ and X ^{4 are} not hydrogen at the same time, and m and n is independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the proviso that when m is 0, at least one of A ⁰ and A ² comprises substituted or An unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, at least one of A ¹ and A ⁰ Contains replaced or not Substituted amine, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl, azido or nitrile group.

For example, in Chemical Formula 3, one or more of A ⁰ , A ¹ and A ² may include a functional group represented by Chemical Formula 4 in the structure.

In Chemical Formula 4, W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, halogen-containing group Or a combination thereof, Y is a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, a nitrile group or a combination thereof, a is 0 or 1, b is an integer ranging from 0 to 10, and * is a connection point.

The functional group represented by Chemical Formula 4 may include a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group.

The monomer may contain, for example, one or more of the functional groups represented by Chemical Formula 4 in the structure.

For example, in Chemical Formula 3 representing a monomer, A ⁰ , A ¹ and A ^{2 are} independently a substituted or unsubstituted moieties selected from Group 1, but are not limited thereto.

For example, in Chemical Formula 3 indicating a monomer, at least one of A ⁰ , A ¹ and A ² may be a polycyclic cyclic group.

For example, the monomer may be represented by one of Chemical Formula 3a to Chemical Formula 3d, but is not limited thereto.

[Chemical Formula 3d]

In Chemical Formula 3a to Chemical Formula 3d, A ³ , A ⁴ and A ^{5 are} independently a substituted or unsubstituted aromatic ring-containing group, and W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

As described above, the organic layer composition contains a polymer in which acetylene is introduced and a monomer as an aromatic ring-containing compound containing a substituted or unsubstituted amino group, substituted or unsubstituted At least one of a substituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, or a nitrile group.

As such, when the polymer and the monomer are simultaneously used to prepare the organic layer composition, the acetylene functional group introduced into the polymer reacts with the amine, acetylene, azide or the like introduced into the monomer and thus forms a ring, and Therefore, the carbon content in the organic layer composition can be relatively increased. Therefore, the etching resistance is improved, and thus the etching selectivity can be improved. Therefore, the organic layer formed using the organic layer composition can have excellent layer density and pattern forming ability.

For example, the polymer can have a weight average molecular weight of from about 500 to 200,000. When the polymer has a weight average molecular weight in the range, the organic layer composition (for example, a hard mask composition) containing the polymer can be optimized by adjusting the carbon content and the solubility in the solvent. In addition, for example, the monomer may have A molecular weight of about 500 to 50,000.

The solvent of the organic layer composition is not particularly limited as long as the solvent has sufficient solubility or dispersibility for 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, diethylene 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, methylpyrrolidinone, ethyl acetonide 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 monomer may be included in an amount of from about 0.1% by weight to 50% by weight, for example, from about 5% by weight to 50% by weight based on the total of the organic layer composition.

For example, the weight ratio of polymer to monomer can be controlled in the range of 70:30 to 30:70, but is not limited thereto.

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 may be, for example, a melamine-based, substituted urea-based or polymer-based crosslinking agent. Preferably, it may be a crosslinking agent having at least two crosslinks to form a substituent, such as, for example, methoxymethylated glycoluril, butoxymethylated glycoluril, methoxyl Melamine melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, A compound such as methoxymethylated thiourea or butoxymethylated thiourea.

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 (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 or the like and / and 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyltosylate, other alkyl sulfonate, etc., but not Limited to this.

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 and the optical properties of the organic layer composition are not changed.

According to another embodiment, an organic layer fabricated 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 described.

A method of forming a pattern according to an embodiment includes: providing a material layer on a substrate, applying an organic layer composition containing a polymer and a solvent to the material layer, and heat treating the organic layer composition to form a hard mask layer, Formed on the hard mask layer a thin layer containing germanium, forming a photoresist layer on the thin layer containing germanium, exposing and developing the photoresist layer to form a photoresist pattern, and using a photoresist pattern to selectively remove the thin layer containing germanium The layer and the hard mask layer expose a portion of the material layer and etch the exposed portions of the material layer.

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, and examples thereof include 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 or a tantalum nitride layer. The material layer can be formed by a method such as a chemical vapor deposition (CVD) process.

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

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

For example, the heat treatment may include a first heat treatment performed at 50 ° C to 250 ° C and a second heat treatment performed after the first heat treatment and at 200 ° C to 500 ° C.

The thin layer containing germanium may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, and/or SiN.

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

Exposure can be performed on the photoresist layer using, for example, ArF, KrF, or EUV. in After the exposure, the heat treatment may be performed at about 100 ° C to 500 ° 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 a mixed gas thereof, but is not limited.

The etched 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, or the like, such as various patterns of the semiconductor integrated circuit device.

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

Polymer synthesis

Polymerization example 1

Resin polymerization

Naphthalen-1-ol (14.2 g), paraformaldehyde (6 g), and p-toluene sulfonic acid hydrate (1.9 g) were placed in the flask. And propylene glycol monomethyl ether acetate (PGMEA, 33 g), and stirred at 80 ° C to carry out polymerization. When the molecular weight was observed by gel permeation chromatography (GPC) during the reaction and the weight average molecular weight reached 2,000 to 3,500, the polymerization was completed. After the completion of the polymerization, the reactant was slowly cooled to room temperature, hexane (100 g) was added thereto to extract propylene glycol monomethyl ether acetate, and hexane was removed using distilled water and methanol to obtain inclusion. Polymer of structural unit represented by Chemical Formula 1a' (weight average molecular weight) (Mw) = 3,000).

Acetylation reaction

The polymer (10 g) containing the structural unit represented by the chemical formula 1a' was dissolved in N,N-dimethylformamide (DMF) (40 ml) in a flask, and The solution was stirred in ice water. After stirring it for 10 minutes, NaH (1 g) was slowly added dropwise thereto, and the mixture was stirred in ice water for 30 minutes, and propargyl bromide was added thereto (in toluene) 80%, 5.5 grams). After the reaction was completed, ethyl acetate (ethyl acetate, EtOAc) (100 ml) was added thereto to dilute the reaction solution, and the diluted reaction solution was washed several times with water to remove N,N-dimethylformamidine. amine. After the N,N-dimethylformamide was completely removed, the remaining EtOAc was removed to obtain a polymer 1a containing the structural unit represented by Chemical Formula 1a.

Polymerization example 2

Resin polymerization

Polymerization of the same resin as in Polymerization Example 1 gave 4,4'-(9H-fluorene-9,9-diyl)diphenol (14 g), 1,3-bis(4-(methoxymethyl)benzene (6.6 g), propylene glycol monomethyl ether acetate (PGMEA, 20 g) and diethyl sulfate (0.25 g) were reacted at 100 ° C to obtain a formula represented by the formula 1b' Polymer of structural unit (weight average molecular weight (Mw) = 3,700).

Acetylation reaction

According to the same oximation as in Polymerization Example 1, a polymer (9 g) containing the structural unit represented by Chemical Formula 1b', N,N-dimethylformamide (45 ml), NaH (0.9 g) was used. And propargyl bromide (80% in toluene, 3.5 g) to obtain a polymer 1b containing the structural unit represented by Chemical Formula 1b.

[Chemical Formula 1b]

Polymerization example 3

Resin polymerization

Polymerization according to the same resin as in Polymerization Example 1 and using 6,6'-(9H-fluorene-9,9-diyl)dinaphthyl-2-ol (18 g), 1,3-bis(methoxymethyl) Benzene (6.6 g), propylene glycol monomethyl ether acetate (PGMEA, 25 g) and diethyl sulfate (0.2 g) obtained a polymer comprising a structural unit represented by the chemical formula 1c' at 110 °C. (weight average molecular weight (Mw) = 3,800).

Acetylation reaction

According to the same oximation as in Polymerization Example 1, a polymer (10 g) containing the structural unit represented by Chemical Formula 1c', N,N-dimethylformamide (45 ml), NaH (0.7 g) was used. And propargyl bromide (80% in toluene, 2.5 g) to obtain the package A polymer 1c containing a structural unit represented by Chemical Formula 1c.

Comparison of polymerization example 1

Polymerization was carried out according to the same resin as in Polymerization Example 1 and using naphthalen-1-ol (14 g), 1,4-bis(methoxymethyl)benzene (17 g), and propylene glycol monomethyl ether acetate (PGMEA, 64)克), and diethyl sulfate (0.3 g) obtained a polymer 1k containing a structural unit represented by the chemical formula 1k at 100 °C. (weight average molecular weight (Mw) = 3,000).

Monomer synthesis

Synthesis Example 1

In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, hydrazine (30 g, 0.1 mol), bromonaphthoquinone chloride (27 g, 0.1 mol) and 1,2-dichloroethane were placed. The alkane (150 g) was thoroughly stirred. After 15 minutes, to Aluminum trichloride (14.67 g, 0.11 mol) was slowly added, and the mixture was allowed to react at room temperature for 1 hour. After the hydrazine was completely removed, the reactants were added to methanol, and trichloroaluminum was removed by filtering the precipitate therein. A powder obtained by filtration was placed in a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, and 1-dodecanethiol (44 g, 0.45 mol), potassium hydroxide (15) was added thereto. G, 0.54 mol), and N,N-dimethylformamide (262 g), and the mixture was stirred at 100 ° C for 5 hours. After the reaction was completed, the reactant was cooled and adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and the precipitate was filtered. The filtrate obtained was then dried in a vacuum oven to remove moisture.

The powder obtained therefrom was added to tetrahydrofuran (THF) (160 g) to obtain a solution. Then, an aqueous solution of sodium borohydride (8 g, 0.21 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the solution was adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure.

The synthesized polymer (10 g, 0.02 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh ₃ ) ₂ Cl ₂ , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Subsequently, ethynyl trimethyl decane (3.5 g) was added thereto, and the mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) solution (250 ml), and potassium carbonate (20 g, 7 eq.) was added thereto at room temperature. The mixture was stirred for 6 hours. After the completion of the reaction, the resultant was subjected to extraction with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-1.

Synthesis Example 2

In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, hydrazine (10 g, 0.05 mol), bromonaphthoquinone chloride (27 g, 0.1 mol) and 1,2-dichloroethane were placed. The alkane (150 g) was then thoroughly stirred. After 15 minutes, trichloroaluminum (14.67 g, 0.11 mol) was slowly added thereto, and the obtained mixture was allowed to react at room temperature for 1 hour. After all the hydrazine was removed, the reactants were added to methanol and the precipitate was filtered to remove the aluminum trichloride. A powder obtained by filtration was placed in a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, and 1-dodecanethiol (44 g, 0.22 mol) and potassium hydroxide were added thereto. 15 g, 0.25 mol), and N,N-dimethylformamide (262 g), and the mixture was stirred at 100 ° C for 5 hours. After the reaction was completed, the reactant was cooled and adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and the precipitate formed therein was filtered. The filtrate obtained was then dried in a vacuum oven to remove moisture.

Then, tetrahydrofuran (160 g) was again added to the obtained powder to obtain a solution. An aqueous solution of sodium borohydride (8 g, 0.21 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction solution was adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure.

The synthesized polymer (10 g, 0.018 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh ₃ ) ₂ Cl ₂ , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Then, ethynyl trimethyl decane (3.5 g) was added thereto, and the obtained mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) (250 mL), and potassium carbonate (20 g, 7 eq. The mixture was stirred for 6 hours. After completion of the reaction, the resultant was extracted with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-2.

Synthesis Example 3

In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, hydrazine (10 g, 0.05 mol), 4-methoxybenzhydryl chloride (8.43 g, 0.05 mol) and 1,2 were placed. Dichloroethane (100.11 g) was used to prepare a solution. Subsequently, aluminum chloride (6.59 g, 0.0494 mol) was slowly added to the solution, and the obtained mixture was stirred at room temperature for 2 hours. After the reaction was completed, methanol was added to the solution, and the precipitate formed therein was filtered and dried.

Subsequently, a compound (15.46 g, 0.0460 mol), 1,3,5-benzenetrimethylsulfonium chloride (4.07 g, 0.0153 mol), and 1,2-dichloroethane (102.62 g) were placed in the flask. To prepare a solution. Subsequently, aluminum chloride (6.13 g, 0.0460 mol) was slowly added to the solution, and the obtained mixture was stirred at room temperature for 6 hours. After the reaction was completed, the precipitate formed by adding methanol to the solution was filtered and dried.

Compound (15.17 g, 0.0130 mol), 1-dodecanethiol (13.18 g, 0.0651 mol), potassium hydroxide (4.38 g, 0.0781 mol), and N,N-dimethyl were placed in the flask. Baseamidine (76.37 g) was stirred at 120 ° C for 3 hours. Subsequently, the mixture was cooled and neutralized with a 5% hydrogen chloride solution to have a pH of 6 to pH 7, and the precipitate formed therein was filtered and dried.

A compound (11.84 g, 0.0105 mol) and tetrahydrofuran (40 g) were placed in a flask to prepare a solution. Subsequently, an aqueous solution of sodium borohydride (7.98 g, 0.2108 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 24 times. hour. After the reaction was completed, the resultant was neutralized to have pH 7 with a 5% hydrogen chloride solution, and then extracted with ethyl acetate and dried to obtain Compound 8.

The synthesized polymer (10 g, 0.012 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh ₃ ) ₂ Cl ₂ , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Then, ethynyl trimethyl decane (3.5 g) was added thereto, and the obtained mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) (250 mL), and potassium carbonate (20 g, 7 eq. The mixture was stirred for 6 hours. After completion of the reaction, the resultant was extracted with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-3.

Synthesis Example 4

In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, methoxy hydrazine (40 g, 0.172 mol), p-xylylene chloride (17.48 g, 0.086 mol) and 1, 2 were placed. Dichloroethane (300 g) was thoroughly stirred. After 15 minutes, trichloroaluminum (25.26 g, 0.189 mol) was slowly added thereto, and the obtained mixture was allowed to react at room temperature for 5 hours. After the reaction was completed, the resultant was concentrated by an evaporator after removing trichloroaluminum using water.

Subsequently, the compound (40.96 g, 0.068 mol), 1-dodecanethiol (41.78 g, 0.21 mol), potassium hydroxide (15.46 g, 0.27 mol) and N,N-di were placed in the flask. Methylformamide (230 g) was stirred at 120 ° C for 8 hours. The mixture was cooled, neutralized with a 5% hydrogen chloride solution to have pH 7, and then extracted with ethyl acetate and dried.

Then, tetrahydrofuran (160 g) was added to the compound to obtain a solution. An aqueous solution of sodium borohydride (32 g, 0.84 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the resultant was acidified to have a pH < 5 using a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure.

The synthesized polymer (10 g, 0.017 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh ₃ ) ₂ Cl ₂ , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Then, ethynyl trimethyl decane (3.5 g) was added thereto, and the mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) (250 mL), and potassium carbonate (20 g, 7 eq. The mixture was stirred for 6 hours. After the completion of the reaction, the resultant was subjected to extraction with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-4.

Synthesis Example 5

In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, bismuth (20 g, 0.1 mol), methoxybenzamide chloride (34 g, 0.2 mol) and 1,2-two were placed. Ethyl chloride (312 g) was thoroughly stirred. After 15 minutes, trichloroaluminum (29.2 g, 0.22 mol) was slowly added thereto, and the mixture was allowed to react at room temperature for 3 hours. After the reaction was completed, a reaction solution was added to methanol, and the precipitate therein was filtered to remove aluminum trichloride. A filtered powder was placed in a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, and 1-dodecanethiol (91 g, 0.45 m) and potassium hydroxide (30 g, 0.54) were added thereto. Mohr), and N,N-dimethylformamide (262 g), and the mixture was stirred at 100 ° C for 5 hours. After the reaction was completed, the reaction was cooled and 7% The hydrogen chloride solution was neutralized to have a pH < 5, and the precipitate formed therein was filtered. The filtered material was dried in a vacuum oven to remove moisture.

The powder obtained was dissolved in tetrahydrofuran (160 g) to obtain a solution. An aqueous solution of sodium borohydride (16 g, 0.42 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the resultant was acidified to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure to obtain a compound, and acetonitrile was added to the compound. NMP (CH ₃ CN/NMP = 1/1, 15 g) was obtained. Then, potassium hydrogencarbonate (3 g, 0.022 mol) and 4-nitrophthalonitrile (3.8 g, 0.022 mol) were added to the solution, and the mixture was stirred at 85 ° C for 5 hours.

After the reaction was completed, the resultant was neutralized to have a pH < 5 with a 7% hydrogen chloride solution, and the precipitate formed therein was filtered. The filtered powder was dried in a vacuum oven to remove moisture. The obtained powder was redissolved in tetrahydrofuran (16 g) to obtain a solution. An aqueous solution of sodium borohydride (0.8 g, 0.021 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the solution was acidified to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent was reduced under pressure to obtain a compound represented by Chemical Formula 3-5.

Preparation of hard mask composition

Example 1 to Example 9 and Comparative Example 1

The polymer and monomer were dissolved in propylene glycol monomethyl ether acetate (PGMEA) solvent and filtered to obtain a hard mask composition.

The composition of the polymer and monomer is shown in Table 1.

Assessment 1 : Flattening Features

On the patterned tantalum wafer (groove width: 10 μm, groove depth: 100 nm), the compositions in Table 1 were spin-coated, respectively, baked to form a film, and vertical scanning electrons were used. Vertical scanning electron The microscope, V-SEM) equipment was examined for its cross section.

The solid content in the hard mask composition was adjusted to first form a 2000 angstrom thick film on the bare wafer after first heat treatment at 180 ° C for 120 seconds and then heat treatment at 400 ° C for 120 seconds. The hard mask compositions were spin-coated separately, and then the film formed therefrom was first heat treated at 180 ° C for 120 seconds and then heat treated at 400 ° C for 120 seconds.

The planarization characteristics of the film were evaluated by measuring the difference (i.e., the step difference) between the region having the pores in the resist underlayer and the non-porous region. 1 is a cross-sectional view showing an enlarged view of any pattern in a germanium wafer to which a coating liquid is applied. In Fig. 1, the thickness indicated by the arrow is a step.

The more excellent the planarization feature, the smaller the difference (step difference) between the patterned region and the unpatterned region, and therefore, the smaller the value, the more excellent the planarization feature. The results are shown in Table 2.

Referring to Table 2, the film formed of the hard mask compositions according to Examples 1 to 9, respectively, exhibited excellent planarization characteristics as compared with the film formed of the hard mask composition according to Comparative Example 1.

Evaluation 2 : Thickness uniformity

The hard mask compositions according to Examples 1 to 9 and Comparative Example 1 were spin-coated on a 12-inch wafer, respectively, and then the obtained film was first heat-treated at 180 ° C for 120 seconds and then at 400. Heat treated at °C for 120 seconds. The solids content of the hard mask composition was adjusted to form a 2,000 angstrom thick film after the second heat treatment.

Uniformity was evaluated according to Equation 2 by using 19 points, measuring each film thickness at 19 points as shown in FIG. 2, and using the film thickness. The thickness of the film was measured using a K-MAC device. The results are shown in Table 3.

[Calculation Equation 2] Uniformity (%) = (Maximum thickness of 19 points of the film - Minimum thickness of 19 points of the film) / (Average thickness of 19 points of the film) × 100

Referring to Table 3, the film formed of the hard mask compositions according to Examples 1 to 9, respectively, showed excellent thickness uniformity as compared with the film formed of the hard mask composition according to Comparative Example 1.

Assessment 3 : Coating properties

The hard mask compositions according to Examples 1 to 9 and Comparative Example 1 were spin-coated on a 12-inch wafer, respectively, and then the obtained film was first heat-treated at 180 ° C for 120 seconds and then at 400. Heat treated at °C for 120 seconds. The solids content of the hard mask composition was adjusted to form a 2,000 angstrom thick film after the second heat treatment.

The surface of the film was examined with an electron microscope. The results are shown in Table 4.

[Table 4]

As shown in Table 4, the films formed by the hard mask compositions according to Examples 1 to 9, respectively, exhibited excellent coating properties as compared with the film formed of the hard mask composition according to Comparative Example 1.

Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not to be construed as limited Various finishes and equivalent configurations.

Claims (18)

An organic layer composition comprising: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent, Wherein, in Chemical Formula 1, A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and B is a divalent organic group, and A And at least one of B and B is substituted with a functional group containing a moity represented by Chemical Formula 2, Wherein, in Chemical Formula 2, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and * is a point of attachment, Wherein, in Chemical Formula 3, A ⁰ , A ¹ and A ^{2 are} independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A ⁰ , A ¹ and A ² are in the structure. A substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and L ¹ , L ² , L ³ and L ^{4 are} independently Is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 extended aryl group, or a combination thereof, X ¹ , X ² , X ³ , and X ⁴ independently a hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, wherein X ¹ and X ^{2 are} not hydrogen at the same time, and X ³ and X ^{4 are} not hydrogen at the same time, and m and n are Independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the constraint that when m is 0, at least one of A ⁰ and A ² is in the structure A substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, A ¹ and A ⁰ At least one of the The structure includes a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group. The organic layer composition according to claim 1, wherein the functional group including the moiety represented by Chemical Formula 2 is represented by Chemical Formula 2', Wherein, in the chemical formula 2', W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, A halogen group or a combination thereof, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, a is 0 or 1, and b is 0. An integer up to the range of 10, and * is the join point. The organic layer composition according to claim 1, wherein in Chemical Formula 3, A ⁰ , A ¹ and A ² independently comprise a substituted or unsubstituted portion selected from Group 1: [Group 1] Wherein, in group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO ₂ , CR ^f R ^g , NR ^h or a carbonyl group, wherein R ^f to R ^{h are} independently Hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen containing group or a combination thereof. The organic layer composition according to claim 1, wherein in Chemical Formula 3, at least one of A ⁰ , A ¹ and A ² is a polycyclic cyclic group. The organic layer composition according to claim 1, wherein in Chemical Formula 3, at least one of A ⁰ , A ¹ , and A ² contains the functional group represented by Chemical Formula 4 in the structure. At least one: [Chemical Formula 4] Wherein, in Chemical Formula 4, W is O, S, NR ^a or CR ^b R ^c , wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, halogen-containing Or a combination thereof, Y is a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, a nitrile group or a combination thereof, a is 0 or 1, b is an integer ranging from 0 to 10, and * is a connection point. The organic layer composition according to claim 1, wherein when the monomer comprises a substituted or unsubstituted ethynyl group, the monomer is represented by one of Chemical Formula 3a to Chemical Formula 3d: [Chemical Formula 3b] Wherein, in Chemical Formula 3a to Chemical Formula 3d, A ³ , A ⁴ , and A ^{5 are} independently a substituted or unsubstituted aromatic ring-containing group, and W is O, S, NR ^a or CR ^b R ^c Wherein R ^a to R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof. The organic layer composition according to claim 1, wherein in Chemical Formula 1, A is a substituted or unsubstituted moiety selected from Group 1 and Group 2, [Group 1] [Group 2] Wherein, in group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO ₂ , CR ^f R ^g , NR ^h or a carbonyl group, wherein R ^f to R ^{h are} independently a hydrogen, substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof, wherein, in Group 2, Z ¹ and Z ^{2 are} independently NR ^d , O, S, Te Or Se, Z ³ to Z ⁵ are N, and R ^d and R ^{e are} independently hydrogen, hydroxy, methoxy, ethoxy, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 Alkyl, substituted or unsubstituted C6 to C30 aryl or a combination thereof. The organic layer composition as described in claim 1, wherein B is represented by one of chemical formula Z1 to chemical formula Z4: Wherein, in the chemical formula Z1 to the chemical formula Z4, e and f are independently 0 or 1, g is an integer of 1 to 5, and Y ¹ to Y ^{4 are} independently a substituted or unsubstituted portion selected from the group 3 One of (moiety), and * is the connection point, Wherein in the group 3, M, M 'and M "are independently a substituted or unsubstituted C1 to C10 _{alkylene, O, S, SO 2,} CR f R g, NR h or a carbonyl group, wherein R ^f to R ^{h are} independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof, and L ¹ is a substituted or unsubstituted C6 to C50 extended aryl group, The substituted or unsubstituted C1 to C10 alkylene oxide-containing group or a combination thereof, r is an integer of 0 to 10, s is an integer of 0 to 10, and k is an integer of 0 to 3. The organic layer composition according to claim 1, wherein the polymer further comprises a structural unit represented by Chemical Formula 5: Wherein in Chemical Formula 5, X ⁰ is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and L ⁰ is a divalent organic group, and * is the connection point. The organic layer composition according to claim 9, wherein in Chemical Formula 5, X ⁰ is a substituted or unsubstituted portion selected from Group 1 and Group 2, [Group 1] Wherein in group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO ₂ , CR ^f R ^g , NR ^h or a carbonyl group, wherein R ^f to R ^{h are} independently hydrogen a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof, wherein in Group 2, Z ¹ and Z ^{2 are} independently NR ^d , O, S, Te or Se Z ³ to Z ⁵ are N, and R ^d and R ^{e are} independently hydrogen, hydroxy, methoxy, ethoxy, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkyl group A substituted or unsubstituted C6 to C30 aryl group or a combination thereof. The organic layer composition of claim 1, wherein the polymer comprises at least one oxygen atom in the structural unit. The organic layer composition according to claim 1, wherein the monomer has a molecular weight of 500 to 50,000. The organic layer composition of claim 1, wherein the polymer has a weight average molecular weight of 500 to 200,000. The organic layer composition of claim 1, wherein the weight ratio of the polymer to the monomer is from 70:3 to 30:70. A method of forming a pattern, comprising providing a material layer on a substrate, the organic layer group according to any one of claims 1 to 14. An object is applied to the layer of material, the organic layer composition is heat treated to form a hard mask layer, and a thin layer containing germanium is formed on the hard mask layer, on the thin layer containing germanium Forming a photoresist layer, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern to selectively remove the germanium-containing thin layer and the hard mask The layer exposes a portion of the layer of material and etches the exposed portion of the layer of material. The method of forming a pattern according to claim 15, wherein the organic layer composition is applied by a spin coating method. The method of forming a pattern according to claim 15, wherein the heat treatment comprises performing a first heat treatment at 50 ° C to 250 ° C and performing a second heat treatment at 200 ° C to 500 ° C after the first heat treatment. . The method of forming a pattern according to claim 15, wherein the method of forming a pattern further comprises forming a bottom anti-reflective coating (BARC) prior to forming the photoresist layer.