Hardmask composition, hardmask layer, and method of forming patterns

Abstract

To provide a hardmask composition that can be effectively applied to a hardmask layer.SOLUTION: The present invention provides: a hard mask composition that comprises a polymer with a structural unit represented by the following formula 1, and a solvent; a hard mask layer comprising a cured product of the hard mask composition; and a pattern formation method using the hard mask composition. The definition of the formula 1 is as set forth in the specification.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a hardmask composition, a hardmask layer including a cured product of the hardmask composition, and a pattern forming method using the hardmask composition. [Background technology]

[0002] Recently, the semiconductor industry has been evolving from patterns of hundreds of nanometers to ultrafine technologies with patterns of several to tens of nanometers. To realize such ultrafine technologies, effective lithographic methods are essential.

[0003] A typical lithographic process includes the steps of forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing to form a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask.

[0004] In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile using only the above-mentioned typical lithographic method. In response to this, a technology has been developed to form a fine pattern by forming an auxiliary layer, called a hard mask layer, between a material layer to be etched and a photoresist layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2016-0061865 Summary of the Invention [Problem to be solved by the invention]

[0006] It is an object of the present invention to provide a hardmask composition that can be effectively applied to a hardmask layer.

[0007] Another object of the present invention is to provide a hard mask layer comprising a cured product of the above hard mask composition.

[0008] It is still another object of the present invention to provide a pattern forming method using the above hard mask composition. [Means for solving the problem]

[0009] The hard mask composition according to one embodiment of the present invention includes a polymer having a structural unit represented by the following formula 1, and a solvent:

[0010] [ka]

[0011] In the above chemical formula 1, A is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms; X 1 and X 2 each independently represents a single bond, -C(=O)-, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, or a combination thereof; Y is a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, * indicates a connection point.

[0012] In the above chemical formula 1, A is preferably at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1 below.

[0013] [ka]

[0014] A in the above Chemical Formula 1 can be at least one selected from the group consisting of aromatic hydrocarbon groups listed in Group 1 above substituted with a deuterium atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a combination thereof.

[0015] X in the above chemical formula 1 1 and X 2 It is preferable that each of them independently represents -C(=O)-, a substituted alkylene group having 1 to 20 carbon atoms, or a combination thereof.

[0016] Y in the above chemical formula 1 is preferably a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms.

[0017] A in the above Chemical Formula 1 can be at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 below.

[0018] [ka]

[0019] The structural unit represented by the above Chemical Formula 1 may be at least one of a structural unit represented by the following Chemical Formula 1-1 and a structural unit represented by the following Chemical Formula 1-2.

[0020] [ka]

[0021] In the above Chemical Formula 1-1 and Chemical Formula 1-2, A is independently at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 below, and X 1 and X 2are each independently a single bond, -C(=O)-, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, or a combination thereof, and * is preferably a linking point.

[0022] [ka]

[0023] The structural unit represented by Chemical Formula 1 above may be at least one selected from the group consisting of structural units represented by Chemical Formulas 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4 below.

[0024] [ka]

[0025] [ka]

[0026] In the above chemical formulas 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4, A 1 ~A 6 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0027] A in the above chemical formulas 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4 1 ~A 6 may each independently be at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 below.

[0028] [ka]

[0029] The polymer may further include a structural unit represented by the following formula 2:

[0030] [ka]

[0031] In the above chemical formula 2, B is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms; L is a single bond or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; * indicates a connection point.

[0032] B in the above Chemical Formula 2 can be at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 2 below.

[0033] [ka]

[0034] L in the above formula 2 can be a substituted or unsubstituted methylene group.

[0035] The weight average molecular weight of the polymer may be from 1,000 g / mol to 200,000 g / mol.

[0036] The polymer may be included in an amount of 0.1% by mass to 30% by mass based on the total mass of the hard mask composition.

[0037] The solvent is preferably at least one selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, 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, acetylacetone, and ethyl 3-ethoxypropionate.

[0038] According to another embodiment of the present invention, there is provided a hardmask layer comprising a cured product of the hardmask composition described above.

[0039] According to yet another embodiment of the present invention, there is provided a patterning method including the steps of: providing a material layer on a substrate; applying the above-described hard mask composition on the material layer; heat-treating the hard mask composition to form a hard mask layer; forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer; and etching the exposed portion of the material layer.

[0040] The step of forming the hard mask layer preferably includes a step of performing a heat treatment at 100°C to 1,000°C. Effect of the Invention

[0041] According to the present invention, a hard mask composition capable of forming a hard mask layer having excellent crosslinking properties and ensuring excellent mechanical properties and pattern formability can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to exemplary embodiments thereof, so that those skilled in the art will be able to easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

[0043] Unless otherwise defined in this specification, "substituted" means that a hydrogen atom in a compound is replaced with a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxy group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a vinyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkyl ... It means that the group is substituted with a substituent selected from an alkynyl group having 6 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an arylaryl group having 9 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heteroarylalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 15 carbon atoms, a cycloalkynyl group having 6 to 15 carbon atoms, a heterocycloalkyl group having 3 to 30 carbon atoms, and combinations thereof.

[0044] In addition, two adjacent substituents in a substituted halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxy group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heteroarylalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 15 carbon atoms, a cycloalkynyl group having 6 to 15 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms may be condensed to form a ring. For example, a substituted aryl group having 6 to 30 carbon atoms can be condensed with another adjacent substituted aryl group having 6 to 30 carbon atoms to form a substituted or unsubstituted fluorene ring.

[0045] Unless otherwise defined in this specification, the term "aromatic hydrocarbon group" refers to a group having one or more aromatic hydrocarbon moieties, and includes not only non-condensed aromatic hydrocarbon rings and condensed aromatic hydrocarbon rings, but also forms in which hydrocarbon aromatic moieties are linked by single bonds, forms in which hydrocarbon aromatic moieties are directly or indirectly condensed into non-aromatic fused rings, or combinations thereof.

[0046] More specifically, the substituted or unsubstituted aromatic hydrocarbon group is a substituted or unsubstituted phenyl group (phenylene group), a substituted or unsubstituted naphthyl group (naphthylene group), a substituted or unsubstituted anthracenyl group (anthracenylene group), a substituted or unsubstituted phenanthryl group (phenanthrylene group), a substituted or unsubstituted naphthacenyl group (naphthacenylene group), a substituted or unsubstituted pyrenyl group (pyrenylene group), a substituted or unsubstituted biphenyl group (biphenylene group), a substituted or unsubstituted phenyl group ( ... Alternatively, it may be, but is not limited to, an unsubstituted terphenyl group (terphenylene group), a substituted or unsubstituted quaterphenyl group (quaterphenylene group), a substituted or unsubstituted chrysenyl group (chrysenylene group), a substituted or unsubstituted triphenylenyl group (triphenylenylene group), a substituted or unsubstituted perylenyl group (perylenylene group), a substituted or unsubstituted indenyl group (indenylene group), a combination thereof, or a condensed form of a combination thereof.

[0047] Unless otherwise defined in this specification, "hetero" means containing 1 to 3 or more heteroatoms selected from N (nitrogen atom), O (oxygen atom), S (sulfur atom), Se (selenium atom), and P (phosphorus atom).

[0048] Unless otherwise defined in this specification, a "heteroalkyl group" refers to a group that contains a heteroatom selected from the group consisting of N, O, S, P, and Si (silicon atom) in place of one or more carbon atoms forming the alkyl group.

[0049] Unless otherwise defined herein, a "heteroaryl group" refers to an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked by a sigma bond, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused together. If the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0050] In this specification, a polymer may include both an oligomer and a polymer. Furthermore, in this specification, a "structural unit" refers to a repeating unit contained in an oligomer or polymer.

[0051] Unless otherwise specified in this specification, the "weight average molecular weight" is a value measured by dissolving a powder sample in tetrahydrofuran (THF) and then using a 1200 series gel permeation chromatography (GPC) manufactured by Agilent Technologies, Inc. (the column used was LF-804 manufactured by Resonac Corporation, and the standard sample was polystyrene manufactured by Resonac Corporation).

[0052] In the semiconductor industry, there is still a demand to reduce the size of chips, and to meet this demand, the line width of the resist patterned by lithography technology must be several tens of nanometers in size. Therefore, the height that can withstand the line width of the resist pattern is limited, and the resist may not have sufficient resistance in the etching step. To compensate for this, there is a technology that uses an auxiliary layer called a hard mask layer between the material layer to be etched and the photoresist layer. Since this hard mask layer serves as an intermediate film that transfers the fine pattern of the photoresist to the material layer through selective etching, the hard mask layer is required to have etching resistance and crosslinking properties so that it can withstand the etching process required for pattern transfer.

[0053] Conventional hard mask layers are formed by chemical or physical vapor deposition, which requires large-scale equipment and has a problem of high process cost and low economic efficiency. Therefore, a technology for forming a hard mask layer by a spin coating method has been developed recently. The spin coating method is easier to process than conventional methods, and the gap fill property and planarization property of the hard mask layer manufactured by the spin coating method are more excellent, but the etching resistance required for the hard mask layer tends to be somewhat lower.

[0054] Therefore, a hard mask composition that can be applied to a spin coating method and a hard mask layer formed therefrom are required to have the same etching resistance as a hard mask layer formed by a chemical or physical vapor deposition method. Therefore, in order to improve the etching resistance of a hard mask layer, research into increasing the carbon content of the hard mask composition has been actively conducted.

[0055] The present inventors have conducted intensive development to produce a hard mask composition that can be applied to a spin coating method and can form a hard mask layer that does not deteriorate in etching resistance. As a result, they have found a composition for forming a hard mask that can increase the carbon content in a polymer to improve the etching resistance of the hard mask layer, and can improve the crosslinking properties by including a heteroatom-containing functional group and an unsaturated hydrocarbon group in the polymer, thereby improving the mechanical properties of the hard mask layer produced therefrom, and have completed the present invention.

[0056] Specifically, a hard mask composition according to an embodiment of the present invention includes a polymer having a structural unit represented by the following Chemical Formula 1, and a solvent.

[0057] [ka]

[0058] In the above chemical formula 1, A is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms; X 1 and X 2 each independently represents a single bond, -C(=O)-, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, or a combination thereof; Y is a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, * indicates a connection point.

[0059] As described above, the polymer contained in the hard mask composition according to the embodiment of the present invention contains an aromatic hydrocarbon group, which increases the carbon content in the polymer containing the structural unit, and the hard mask layer formed from the hard mask composition containing the polymer may have high etching resistance.

[0060] In addition, the structural unit represented by the above chemical formula 1 contains an unsaturated hydrocarbon group, which increases the number of crosslinks (crosslink density) due to a cycloaddition reaction when the hard mask composition is cured, thereby ensuring etching resistance and heat resistance. In addition, since the composition does not form rings before curing, the polymer has excellent solubility in a solvent and has excellent planarization and gap-fill properties when applied by a spin coating method.

[0061] In addition, by including the unsaturated hydrocarbon group in the main chain of the polymer, the loss of the unsaturated hydrocarbon group can be reduced during the heat treatment and curing conditions of the hard mask composition, and the number of crosslinks (crosslink density) in the polymer can be increased to enhance the crosslinking characteristics of the hard mask composition, compared to when the unsaturated hydrocarbon group is included in the side chain or end of the polymer, and therefore the hard mask layer formed therefrom can have excellent film strength.

[0062] In one embodiment of the present invention, A in the above Chemical Formula 1 may be at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1 below.

[0063] [ka]

[0064] As an example, when A is a substituted aromatic hydrocarbon group listed in Group 1 above, it may be substituted with a deuterium atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a combination thereof.

[0065] As another example, A in the above Chemical Formula 1 may be at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 below, such as a substituted or unsubstituted biphenylenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted benzoperylenylene group.

[0066] [ka]

[0067] In one embodiment of the present invention, X in the above formula 1 1 and X 2 may each independently be -C(=O)-, a substituted alkylene group having 1 to 20 carbon atoms, or a combination thereof. For example, the substituted alkylene group having 1 to 20 carbon atoms is a group in which some of the hydrogen atoms of a group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, or an octylene group have been substituted with a substituent, and may be, for example, a substituted methylene group, a substituted ethylene group, or a substituted propylene group.

[0068] The substituent of the substituted alkylene group having 1 to 20 carbon atoms may be selected from a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a cyano group, an azide group, a carbonyl group, a thiol group, an ester group, a vinyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, and combinations thereof. For example, the substituent may be a hydroxy group, an alkoxy group, a carbonyl group, or an aryl group having 6 to 30 carbon atoms.

[0069] As shown above, X 1 and X 2 contains -C(=O)- or a hydroxy group and / or an aryl group having 6 to 30 carbon atoms as a substituent, the number of crosslinks (crosslink density) in the polymer can be increased during curing of the hard mask composition, thereby improving the crosslinking characteristics of the hard mask composition, and the strength of the hard mask layer formed therefrom can be improved, thereby improving the pattern formability.

[0070] In one embodiment of the present invention, Y in the above Chemical Formula 1 is a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms. The substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms is, for example, an alkenylene group having 2 to 10 carbon atoms, for example, an alkenylene group having 2 to 7 carbon atoms, for example, an alkenylene group having 2 to 5 carbon atoms, and is an unsaturated aliphatic hydrocarbon group containing at least one carbon-carbon double bond. The substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms is, for example, an alkynylene group having 2 to 10 carbon atoms, for example, an alkynylene group having 2 to 7 carbon atoms, for example, an alkynylene group having 2 to 5 carbon atoms, and is an unsaturated aliphatic hydrocarbon group containing at least one carbon-carbon triple bond.

[0071] In one embodiment of the present invention, the structural unit represented by the above Chemical Formula 1 may be at least one of a structural unit represented by the following Chemical Formula 1-1 and a structural unit represented by the following Chemical Formula 1-2.

[0072] [ka]

[0073] In the above Chemical Formula 1-1 and Chemical Formula 1-2, A is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1 above, and X 1 and X 2 are each independently a single bond, -C(=O)-, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, or a combination thereof, and * is a linking point. In one embodiment of the present invention, A in the above Chemical Formula 1-1 and Chemical Formula 1-2 may be at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in the above Group 1-1.

[0074] Specifically, the structural unit represented by Chemical Formula 1 above can be at least one selected from the group consisting of structural units represented by Chemical Formulas 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4 below.

[0075] [ka]

[0076] [ka]

[0077] In the above chemical formulas 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4, A 1 ~A 6 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and may be, for example, at least one selected from the group consisting of the substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1 above. In one embodiment of the present invention, in Chemical Formulas 1-1-1 to 1-1-4 and Chemical Formulas 1-2-1 to 1-2-4 above, A 1 ~A 6may each independently be at least one selected from the group consisting of the substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 above.

[0078] In one embodiment of the present invention, A in the above chemical formulas 1-1-1 to 1-1-4 and the above chemical formulas 1-2-1 to 1-2-4 2 , A 3 , A 5 , and A 6 may each independently be a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a benzoperylenyl group, or the like, for example, but not limited to, a naphthyl group, a biphenyl group, a pyrenyl group, a benzoperylenyl group, or the like.

[0079] In one embodiment of the present invention, A in the above chemical formulas 1-1-1 to 1-1-4 and the above chemical formulas 1-2-1 to 1-2-4 1 and A 4 may each independently be a phenylene group, a naphthylene group, a biphenylene group, an anthracenylene group, a phenanthrenylene group, a pyrenylene group, a benzoperylenylene group, or the like, for example, a naphthylene group, a biphenylene group, a pyrenylene group, a benzoperylenylene group, or the like, but is not limited to these.

[0080] In another embodiment of the present invention, the polymer may further include a structural unit represented by the following Formula 2:

[0081] [ka]

[0082] In the above chemical formula 2, B is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms; L is a single bond or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; * indicates a connection point.

[0083] B in the above Chemical Formula 2 can be at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 2 below.

[0084] [ka]

[0085] L in the above formula 2 can be a substituted or unsubstituted methylene group, for example, an unsubstituted methylene group.

[0086] The above polymers can be synthesized by appropriately referring to conventionally known synthesis methods. More specifically, those skilled in the art can easily synthesize the polymers by referring to the synthesis methods described in the Examples.

[0087] When the above polymer has multiple types of structural units, the bonding form may be a block form (block copolymer), a random form (random copolymer), or an alternating form (alternating copolymer).

[0088] The polymer may have a weight average molecular weight of 1,000 g / mol to 200,000 g / mol. The polymer may have a weight average molecular weight of, for example, 1,000 g / mol to 150,000 g / mol, for example, 1,000 g / mol to 100,000 g / mol, for example, 1,000 g / mol to 10,000 g / mol, for example, 1,200 g / mol to 5,000 g / mol, but is not limited thereto. By having a weight average molecular weight in the above range, the carbon content and solubility in a solvent of the hard mask composition containing the polymer can be adjusted and optimized.

[0089] The polymer may be contained in a content of 0.1% by mass to 30% by mass based on the total mass of the hard mask composition. For example, the content may be, but is not limited to, 0.2% by mass to 30% by mass, such as 0.5% by mass to 30% by mass, such as 1% by mass to 30% by mass, such as 1% by mass to 25% by mass, such as 1% by mass to 20% by mass. By containing the polymer in the above content range, the thickness, surface roughness, flattening properties, etc. of the hard mask can be easily adjusted.

[0090] The hard mask composition according to one embodiment of the present invention includes a solvent. The solvent may include, but is not limited to, at least one selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, 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, N-methyl-2-pyrrolidone, 1-methyl-2-pyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate. The solvent is not particularly limited as long as it has sufficient solubility and / or dispersibility in the polymer.

[0091] The hard mask composition may further include additives such as surfactants, crosslinkers, thermal acid generators, plasticizers, and the like.

[0092] Examples of the surfactant that can be used include, but are not limited to, fluoroalkyl compounds, alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, and quaternary ammonium salts.

[0093] Examples of the crosslinking agent include melamine-based agents, substituted urea-based agents, and polymers thereof. A crosslinking agent having at least two crosslink-forming substituents is preferable, and for example, compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and butoxymethylated thiourea can be used.

[0094] In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As the crosslinking agent having high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be used.

[0095] Examples of thermal acid generators that can be used include, but are not limited to, acidic compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid, and / or 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters.

[0096] According to another embodiment of the present invention, there is provided a hardmask layer comprising a cured product of the hardmask composition described above.

[0097] A method for forming a pattern using the above-described hard mask composition will now be described.

[0098] A method for forming a pattern according to an embodiment of the present invention includes the steps of: providing a material layer on a substrate, applying a hard mask composition comprising the above-mentioned polymer and a solvent on the material layer, heat-treating the hard mask composition to form a hard mask layer, forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer, and etching the exposed portion of the material layer. The substrate can be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

[0099] The material layer is the material that is ultimately to be patterned and may be, for example, a metal layer such as aluminum, copper, etc., a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, etc. The material layer may be formed, for example, by chemical vapor deposition.

[0100] The hard mask composition may be prepared in the form of a solution and applied by spin coating, as described above. In this case, the thickness of the hard mask composition is not particularly limited, but may be, for example, 50 to 200,000 Å.

[0101] The step of heat treating the hard mask composition may be performed for 10 seconds to 1 hour at a temperature of, for example, 100° C. to 1,000° C. In one embodiment, the step of heat treating the hard mask composition may include a plurality of heat treatment steps, for example, a first heat treatment step and a second heat treatment step.

[0102] In one embodiment of the present invention, the step of heat treating the hard mask composition may include one heat treatment step performed for 10 seconds to 1 hour at 100° C. to 1000° C. For example, the heat treatment step may be performed in an air atmosphere, a nitrogen atmosphere, or an atmosphere having an oxygen concentration of 1% by mass or less.

[0103] In one embodiment of the present invention, the step of heat treating the hard mask composition includes a first heat treatment step performed at a temperature of, for example, 100° C. to 1,000° C., for example, 100° C. to 800° C., for example, 100° C. to 500° C., for example, 100° C. to 400° C. for 10 seconds to 1 hour, and may successively include a second heat treatment step performed at a temperature of, for example, 100° C. to 1,000° C., for example, 300° C. to 1,000° C., for example, 500° C. to 1,000° C., for example, 500° C. to 800° C. for 10 seconds to 1 hour. As an example, the first heat treatment step and the second heat treatment step may be performed in an air atmosphere, a nitrogen atmosphere, or an atmosphere having an oxygen concentration of 1% by mass or less.

[0104] By performing at least one of the steps of heat treating the hard mask composition at a high temperature of 200° C. or higher, the hard mask composition can exhibit high etching resistance that can withstand etching gases and chemical solutions to which the hard mask composition is exposed in subsequent steps, including an etching step.

[0105] In one embodiment of the present invention, the step of forming a hardmask layer may include a UV / Vis cure step and / or a near IR cure step.

[0106] In one embodiment of the present invention, the step of forming the hard mask layer may include at least one of a first heat treatment step, a second heat treatment step, an ultraviolet / visible light (UV / Vis) curing step, and a near infrared (near IR) curing step, or may include two or more steps consecutively.

[0107] In an embodiment of the present invention, the method may further include forming a silicon-containing thin film layer on the hard mask layer, the silicon-containing thin film layer being formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and / or SiN.

[0108] In one embodiment of the present invention, before the step of forming the photoresist layer, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer or on the hard mask layer.

[0109] In one embodiment of the present invention, the step of exposing the photoresist layer can be performed using, for example, an ArF excimer laser, a KrF excimer laser, or extreme ultraviolet (EUV), etc. After the exposure, a heat treatment process can be further performed in which the substrate is heat-treated at a temperature of 100°C to 700°C.

[0110] In one embodiment of the present invention, the step of etching the exposed portions of the material layer can be performed by dry etching using an etching gas, which can be, for example, N2 / O2, CHF3, CF4, Cl2, BCl3, and mixtures thereof.

[0111] The etched material layer can be formed in a variety of patterns, which can be diverse, such as metal patterns, semiconductor patterns, insulating patterns, etc., and can be applied as a variety of patterns within a semiconductor integrated circuit device, for example. EXAMPLES

[0112] The above-mentioned embodiments of the present invention will be described in more detail with reference to the following examples. However, the following examples are merely for illustrative purposes and are not intended to limit the scope of the present invention.

[0113] [Synthesis Examples 1 to 3: Polymer Synthesis] (Synthesis Example 1) 2-Hydroxypyrene (15.8g, 0.05mol), 1,1'-biphenyl-4-ol (8.5g, 0.05mol), and dimethyl fumarate (14.4g, 0.1mol) were added to a 250ml flask. Next, p-toluenesulfonic acid monohydrate (0.57g, 0.03mmol) was dissolved in 100g of propylene glycol monomethyl ether acetate (PGMEA), and the solution was added to the flask and stirred at 100°C. Samples were taken from the polymerization reaction product every hour, and the reaction was terminated when the weight-average molecular weight of the sample was 2,000-2,500g / mol. After the polymerization reaction was terminated, the reaction product was cooled to room temperature and added to 300g of distilled water and 300g of methanol, vigorously stirred, and allowed to stand. The supernatant was removed, and the precipitate was dissolved in 100 g of propylene glycol monomethyl ether acetate (PGMEA), vigorously stirred with 300 g of methanol and 300 g of distilled water, and then allowed to stand (first step). The supernatant obtained at this time was removed again, and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (second step). The first and second steps were combined into one purification step, and this purification step was carried out three times in total. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and the methanol and distilled water remaining in the solution were distilled off under reduced pressure to obtain a polymer consisting of structural units represented by the following chemical formulas 1-1-1 to 1-1-4. In the following chemical formulas 1-1-1 to 1-1-4, A 1 ~A 3 each independently represents a moiety derived from 2-hydroxypyrene or 1,1'-biphenyl-4-ol.

[0114] [ka]

[0115] (Synthesis Example 2) A polymer composed of structural units represented by the following chemical formulas 1-2-1 to 1-2-5 was obtained in the same manner as in Synthesis Example 1, except that 2,2'-biphenol (18.6 g, 0.1 mol), dimethyl acetylenedicarboxylate (14.2 g, 0.05 mol), and paraformaldehyde (1.5 g, 0.05 mol) were used as reaction raw materials. 4 ~A 7 are all moieties derived from 2,2'-biphenol.

[0116] [ka]

[0117] (Synthesis Example 3) Using 2-hydroxypyrene (15.8 g, 0.05 mol), 2,2'-biphenol (18.6 g, 0.1 mol), fumaric acid (11.6 g, 0.1 mol), and paraformaldehyde (1.5 g, 0.05 mol) as reactants, a polymer consisting of structural units represented by the following chemical formulas 1-3-1 to 1-3-5 was obtained in the same manner as in Synthesis Example 1. 8 ~A 11 each independently represents a moiety derived from 2-hydroxypyrene or 2,2'-biphenol.

[0118] [ka]

[0119] (Synthesis Example 4) 1-naphthol (14.4g, 0.1mol) and dimethyl fumarate (14.4g, 0.1mol) were added to a 250ml flask. Next, p-toluenesulfonic acid monohydrate (0.57g, 0.03mmol) was dissolved in 100g of propylene glycol monomethyl ether acetate (PGMEA), and the solution was added to the flask and stirred at 100°C. Samples were taken from the polymerization reaction product every hour, and the reaction was terminated when the weight average molecular weight of the sample was 2,000 to 2,500g / mol. After the polymerization reaction was terminated, the reaction product was cooled to room temperature and added to 300g of distilled water and 300g of methanol, vigorously stirred, and then allowed to stand. The supernatant was removed, and the precipitate was dissolved in 100 g of propylene glycol monomethyl ether acetate (PGMEA), and then vigorously stirred with 300 g of methanol and 300 g of distilled water, and then allowed to stand (first step). The supernatant was removed again, and the precipitate was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA) (second step). The first and second steps were combined into one purification step, and this purification step was carried out three times in total. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and the methanol and distilled water remaining in the solution were distilled off under reduced pressure to obtain a polymer consisting of structural units represented by the following chemical formulas 1-4-1 to 1-4-4. In the following chemical formulas 1-4-1 to 1-4-4, A 12 ~A 14 each independently represents a moiety derived from 1-naphthol.

[0120] [ka]

[0121] (Comparative Synthesis Example 1) Pyrene (20.2g, 0.1mol) and 4-hydroxybenzaldehyde (12.2g, 0.1mol) were added to a 250ml flask. Next, p-toluenesulfonic acid monohydrate (0.57g, 0.03mmol) was dissolved in 100g of propylene glycol monomethyl ether acetate (PGMEA), and the solution was added to the flask and stirred at 100°C. Samples were taken from the polymerization reaction product every hour, and the reaction was terminated when the weight-average molecular weight of the sample was 2,000-2,500g / mol. After the polymerization reaction was terminated, the reaction product was cooled to room temperature and added to 300g of distilled water and 300g of methanol, vigorously stirred, and allowed to stand. The supernatant was removed, and the precipitate was dissolved in 100g of propylene glycol monomethyl ether acetate (PGMEA), and then vigorously stirred with 300g of methanol and 300g of distilled water and allowed to stand (first step). The supernatant was removed again, and the precipitate was dissolved in 80g of propylene glycol monomethyl ether acetate (PGMEA) (second step). The first and second steps were combined into one purification step, and this purification step was carried out three times in total. The purified polymer was dissolved in 80g of propylene glycol monomethyl ether acetate (PGMEA), and the methanol and distilled water remaining in the solution were distilled off under reduced pressure to obtain a polymer containing a structural unit represented by the following chemical formula P.

[0122] [ka]

[0123] (Comparative Synthesis Example 2) A polymer containing a structural unit represented by the following chemical formula Q was obtained in the same manner as in Comparative Synthesis Example 1, except that 2-hydroxypyrene (21.8 g, 0.1 mol) was used instead of pyrene and naphthaldehyde (15.6 g, 0.1 mol) was used instead of 4-hydroxybenzaldehyde.

[0124] [ka]

[0125] (Comparative Synthesis Example 3) In a 500 ml two-neck flask equipped with a mechanical stirrer and a cooling tube, methoxypyrene (40 g, 0.172 mol) and terephthaloyl chloride (17.48 g, 0.086 mol) were added to 300 g of dichloroethane and mixed well. After 15 minutes, trichloroaluminum (25.26 g, 0.189 mol) was slowly added, and the reaction solution was reacted at room temperature (25 ° C) for 5 hours. After the reaction was completed, trichloroaluminum was removed using water, and then concentrated with an evaporator. Next, the compound obtained above (40.96 g, 0.068 mol) was added to the flask, and 1-dodecanethiol (41.78 g, 0.21 mol), potassium hydroxide (15.46 g, 0.27 mol), and N,N-dimethylformamide (230 g) were added, and the mixture was stirred at 120 ° C for 8 hours. The resulting mixture was cooled, neutralized to pH 7 with 5% by mass aqueous hydrogen chloride solution, extracted with ethyl acetate, and dried. 160 g of tetrahydrofuran was added to the resulting compound to obtain a solution state. An aqueous solution of sodium borohydride (32 g, 0.84 mol) was slowly added to this solution and stirred at room temperature (25°C) for 12 hours. When the reaction was completed, the mixture was acidified to pH 5 with 7% by mass aqueous hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was distilled off under reduced pressure. The polymer (10 g, 0.017 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh3)2Cl2, 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 60 mL of tetrahydrofuran. 3.5g of ethynyltrimethylsilane was added thereto, and the mixture was stirred at 80°C for 3 hours. After the reaction was completed, the mixture was filtered using silica gel and purified. 12.5g (1 equivalent) of the purified solid was dissolved in 250ml of methanol / THF (volume ratio = 1 / 2) solvent, to which 20g of potassium carbonate (7 equivalents) was added, and the mixture was stirred at room temperature (25°C) for 6 hours. After the reaction was completed, the mixture was extracted with ethyl acetate and distilled off under reduced pressure to obtain a compound represented by the following chemical formula R.

[0126] [ka]

[0127] [Examples and Comparative Examples: Production of Hard Mask Composition] Example 1 A hard mask composition was prepared by dissolving 3 g of the polymer obtained in Synthesis Example 1 in 10 g of propylene glycol monomethyl ether acetate (PGMEA) and filtering the solution through a 0.1 μm Teflon filter.

[0128] Example 2 A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.

[0129] Example 3 A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.

[0130] Example 4 A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 4 was used instead of the polymer obtained in Synthesis Example 1.

[0131] Comparative Example 1 A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 1 was used instead of the polymer obtained in Synthesis Example 1.

[0132] Comparative Example 2 A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Comparative Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.

[0133] Comparative Example 3 A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.

[0134] [Evaluation 1: Evaluation of membrane strength] The hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 3 were spin-coated on a silicon wafer to a thickness of 5,000 Å, and then heat-treated on a hot plate at 400° C. for 2 minutes to form a thin film (hard mask layer). Next, the hardness (H) and elastic modulus (E) of the thin film were measured using a nanoindenter (cube corner tip, Pmax=300 μN). The measurement results are shown in Table 1 below.

[0135] [Table 1]

[0136] Referring to Table 1, the hardmask layers formed from the hardmask compositions according to Examples 1 to 4 exhibit much higher hardness and modulus than the hardmask layers formed from the hardmask compositions according to Comparative Examples 1 to 3. In other words, it was found that the hardmasks formed from the hardmask compositions according to the Examples exhibited superior film strength and provided hardmasks with excellent mechanical properties compared to the hardmask compositions formed from the hardmask compositions according to Comparative Examples.

[0137] [Evaluation 2: Evaluation of pattern formability] A 3,000 Å thick silicon oxide (SiO X A silicon nitride (SiN) layer was formed on the silicon oxide layer by chemical vapor deposition (CVD). Next, the hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 3 were applied on the silicon oxide layer by spin coating, and then heat-treated at 350°C for 120 seconds to form a hard mask layer. Next, a silicon nitride (SiN XA KrF photoresist was then spin-coated and heat-treated at 110°C for 60 seconds, after which it was exposed to light using an ASML exposure tool (XT:1400, NA 0.93) and developed with tetramethylammonium hydroxide (2.38 mass% TMAH aqueous solution). The patterned photoresist was then used as a mask to form a silicon nitride (SiN) layer using CHF3 / CF4 mixed gas plasma. X The silicon nitride (SiN) layer was then dry etched. X Using the SiO2 / O2 mixed gas plasma as a mask, the hard mask layers formed from the hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 3 were dry etched. A scanning electron microscope (SEM) was used to observe the cross sections of the hard mask patterns. While the hard mask layers formed from the compositions according to the Comparative Examples showed pattern collapse, the hard mask layers formed from the compositions according to the Examples were observed to have good vertical shapes, demonstrating excellent pattern formability.

[0138] As described above, it has been found that a hard mask prepared from a hard mask composition according to an embodiment of the present invention exhibits excellent hardness and modulus, has excellent mechanical properties such as film strength, and exhibits excellent coatability in a solution state, and thus, the prepared hard mask layer exhibits superior smoothness and pattern formability.

[0139] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the invention defined in the claims below also fall within the scope of the present invention.

Claims

1. A hard mask composition comprising a polymer having a structural unit represented by the following chemical formula 1, and a solvent: 【Chemistry 1】 In the above Chemical Formula 1, A is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms; X １ and X ２ each independently represents a single bond, —C(═O)—, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, or a combination thereof; Y is a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms; * indicates a connection point.

2. 2. The hard mask composition of claim 1, wherein A in Formula 1 is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1 below. 【Chemistry 2】

3. 3. The hard mask composition of claim 2, wherein A in Chemical Formula 1 is at least one selected from the group consisting of aromatic hydrocarbon groups listed in Group 1 substituted with a deuterium atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a combination thereof.

4. X in Formula 1 １ and X ２ The hard mask composition of claim 1 , wherein each of the groups is independently —C(═O)—, a substituted alkylene group having 1 to 20 carbon atoms, or a combination thereof.

5. 2. The hard mask composition of claim 1, wherein Y in Formula 1 is a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, or a substituted or unsubstituted alkynylene group having 2 to 10 carbon atoms.

6. 2. The hard mask composition of claim 1, wherein A in Formula 1 is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 below. 【Chemistry 3】

7. The hard mask composition according to claim 1, wherein the structural unit represented by Chemical Formula 1 is at least one of a structural unit represented by Chemical Formula 1-1 and a structural unit represented by Chemical Formula 1-2: 【Chemistry 4】 In the above Chemical Formula 1-1 and Chemical Formula 1-2, A is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 below, X １ and X ２ each independently represents a single bond, —C(═O)—, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, or a combination thereof; * indicates a connection point. 【Chemistry 5】

8. The hard mask composition according to claim 1, wherein the structural unit represented by Chemical Formula 1 is at least one selected from the group consisting of structural units represented by Chemical Formulas 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4: 【Chemistry 6】 【Chemistry 7】 In the above Chemical Formulae 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4, A １ ~A ６ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.

9. A in the above Chemical Formulae 1-1-1 to 1-1-4 and 1-2-1 to 1-2-4 １ ~A ６ is independently at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 1-1 below. 【Chemistry 8】

10. 2. The hard mask composition of claim 1, wherein the polymer further comprises a structural unit represented by the following formula 2: 【Chemistry 9】 In the above Chemical Formula 2, B is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms; L is a single bond or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; * indicates a connection point.

11. 11. The hard mask composition of claim 10, wherein B in Formula 2 is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbon groups listed in Group 2 below. 【Chemistry 10】

12. 11. The hard mask composition of claim 10, wherein L in Formula 2 is a substituted or unsubstituted methylene group.

13. 2. The hard mask composition of claim 1, wherein the weight average molecular weight of the polymer is from 1,000 g / mol to 200,000 g / mol.

14. The hard mask composition of claim 1 , wherein the polymer is included in an amount of 0.1% by weight to 30% by weight based on the total weight of the hard mask composition.

15. 2. The hard mask composition of claim 1, wherein the solvent is at least one selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, 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, acetylacetone, and ethyl 3-ethoxypropionate.

16. A hardmask layer comprising a cured product of the hardmask composition according to any one of claims 1 to 15.

17. Providing a layer of material on a substrate; applying a hard mask composition according to any one of claims 1 to 15 onto the material layer; heat-treating the hard mask composition to form a hard mask layer; forming a photoresist layer over the hard mask layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hard mask layer using the photoresist pattern to expose portions of the material layer; etching the exposed portions of the layer of material; A pattern forming method comprising:

18. The method of claim 17, wherein the step of forming the hard mask layer comprises a step of performing a heat treatment at 100° C. to 1,000° C.

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