Hardmask composition, hardmask layer and patterning method

Abstract

To provide a hardmask composition, a hardmask layer including a cured product of the hardmask composition, and a method of forming patterns using the hardmask composition, where the hardmask composition can form the hardmask layer capable of securing excellent etch resistance and has excellent crosslinking characteristics.SOLUTION: The hardmask composition comprises a compound represented by the chemical formula 1 in the figure, and a solvent.(The definition of the chemical formula 1 is as described in the specification.)SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, the semiconductor industry has evolved from patterns of several hundred nanometers to ultrafine technology with patterns of several to several tens of nanometers. To realize such ultrafine technology, effective lithographic techniques are essential.

[0003] A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the material 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 the pattern to be formed decreases, it has become difficult to form a fine pattern with a good profile using only the typical lithographic techniques described above. Therefore, in order to assist in the formation of a fine pattern, a technology has been developed in which a layer called a hard mask layer is provided between the material layer to be etched and the photoresist layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2021-0113909 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a hard mask composition that can form a hard mask layer that can ensure excellent etching resistance and has excellent crosslinking properties.

[0007] Another object of the present invention is to provide a hard mask layer comprising a cured product of the 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] A hard mask composition according to one embodiment of the present invention includes a compound represented by the following Chemical Formula 1 and a solvent:

[0010] [ka]

[0011] In the above chemical formula 1, R 1 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, R 2 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 carbon atoms, or a combination thereof; n is R 1 is an integer greater than or equal to 1, with the maximum number of substitutions allowed.

[0012] R in the above chemical formula 1 2 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 10 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 6 to 30 carbon atoms, or a combination thereof.

[0013] R in the above chemical formula 1 1 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, and R 2are each independently a substituted or unsubstituted aromatic hydrocarbon group having 10 to 30 carbon atoms, and n may be 2.

[0014] R in the above chemical formula 1 1 may be a substituted or unsubstituted group consisting of at least one of the structures selected from Group 1 below:

[0015] [ka]

[0016] R in the above chemical formula 1 2 may each independently be a substituted or unsubstituted group consisting of at least one of structures selected from Group 2 and Group 3 below:

[0017] [ka]

[0018] [ka]

[0019] Among the above group 3, Z 1 and Z 2 are each independently -O-, -S-, or -NR'- (wherein R' is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms).

[0020] R in the above chemical formula 1 1 may be a substituted or unsubstituted group consisting of at least one structure selected from Group 1-1 below, and R 2 may be a substituted or unsubstituted group consisting of at least one of the structures selected from Group 2-1 below.

[0021] [ka]

[0022] In the above formula 1, n may be 2, and in this case, two R 2 may be the same group.

[0023] The compound represented by the above Chemical Formula 1 may be a compound represented by any one of the following Chemical Formulas 1-1 to 1-3:

[0024] [ka]

[0025] In the above chemical formulas 1-1 to 1-3, R a and R b are each independently a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an amino group, or a thiol group, and each p is independently R a is an integer of 0 or more, with the upper limit being the number of substitutions that can be made for R, b is an integer greater than or equal to 0, with the upper limit being the number that can be replaced by

[0026] The molecular weight of the compound may be from 300 g / mol to 5,000 g / mol.

[0027] The compound may be contained in an amount of 0.1% by mass to 30% by mass based on the total mass of the hard mask composition.

[0028] The solvent may include, but is not limited to, 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, or ethyl 3-ethoxypropionate.

[0029] According to another aspect of the present invention, there is provided a hard mask layer comprising a cured product of the hard mask composition described above.

[0030] According to yet another aspect of the present invention, there is provided a pattern formation method including the steps of: forming 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.

[0031] The step of forming the hard mask layer may include a step of performing a heat treatment at 100°C to 1,000°C. [Effects of the Invention]

[0032] The hard mask composition according to the present invention has excellent crosslinking properties, and a hard mask layer formed from the composition can ensure excellent etching resistance. DETAILED DESCRIPTION OF THE INVENTION

[0033] Although the present invention may be embodied in many different forms, it is to be understood that the invention is not limited to the embodiments set forth herein, and that the present invention may be practiced in various different forms.

[0034] In this specification, unless otherwise defined, the term "substituted" means that a hydrogen atom in a compound is substituted 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 azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a formyl group, a carbamoyl group, a thiol group, an ester group (alkoxycarbonyl group, acyloxy group), a carboxyl group and salts thereof, a sulfonic acid group and salts thereof, a phosphoric acid group and salts thereof, 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, an aromatic hydrocarbon group having 6 to 30 carbon atoms, It means being substituted with a substituent selected from the group consisting of (aryl groups), arylalkyl groups having 7 to 30 carbon atoms, arylaryl groups having 9 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, alkylamino groups having 1 to 20 carbon atoms, dialkylamino groups having 2 to 20 carbon atoms, aromatic heterocyclic groups (heteroaryl groups) having 3 to 20 carbon atoms, heteroarylalkyl groups having 4 to 20 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms, cycloalkenyl groups having 3 to 15 carbon atoms, cycloalkynyl groups having 6 to 15 carbon atoms, aliphatic heterocyclic groups (heterocycloalkyl groups) having 3 to 30 carbon atoms, and combinations thereof.

[0035] In addition, the substituents may include a halogen atom (F, Br, Cl, or I), a hydroxy 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 formyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid 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 aryl group having 7 to 30 carbon atoms, an aryl group having 8 to 30 carbon atoms, an aryl group having 9 to 30 carbon atoms, an aryl group having 10 to 30 carbon atoms, an aryl group having 11 to 30 carbon atoms, an aryl group having 12 to 30 carbon atoms, an aryl group having 13 to 30 carbon atoms, an aryl group having 14 to 30 carbon atoms, an aryl group having 15 to 30 carbon atoms, an aryl group having 16 to 30 carbon atoms, an aryl group having 17 to 30 carbon atoms, an aryl group having 18 to 30 carbon atoms, an aryl group having 19 to 20 carbon atoms, an aryl group having 20 to 30 carbon atoms, an aryl group having 21 to 30 carbon atoms, an aryl group having 21 to 30 carbon atoms, an aryl group having 22 to 30 carbon atoms, an aryl group having 23 to 30 carbon atoms, an aryl group having 24 to 30 carbon atoms, an aryl group having 25 to 30 carbon atoms, an aryl group having 26 to 30 carbon atoms, an aryl group having 27 to 30 carbon atoms Two adjacent substituents in an arylalkyl group having 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a heteroarylalkyl group having 4 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 bonded to or fused to form a ring.

[0036] Unless otherwise defined in this specification, the term "aromatic hydrocarbon ring" refers to a ring (excluding aromatic heterocycles) having one or more aromatic hydrocarbon moieties, and includes not only non-fused aromatic hydrocarbon rings and fused aromatic hydrocarbon rings, but also forms in which aromatic hydrocarbon moieties are linked by a single bond, and fused ring forms containing a non-aromatic moiety to which an aromatic hydrocarbon moiety is directly or indirectly fused, as well as combinations thereof.

[0037] More specifically, the substituted or unsubstituted aromatic hydrocarbon ring may be, but is not limited to, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a combination thereof, or a group in which a combination thereof is bound or fused.

[0038] In this specification, unless otherwise defined, "hetero" means containing at least one heteroatom selected from N, O, S, Se and P.

[0039] Unless otherwise defined, the term "aromatic heterocycle" as used herein refers to an aromatic ring containing at least one heteroatom selected from N, O, S, Se, and P. Two or more aromatic heterocycles may be directly linked via a sigma bond, or two or more aromatic heterocycles may be fused together. When the aromatic heterocycle is a fused ring, the entire structure of the fused ring or one of the rings constituting the fused ring may contain 1 to 3 heteroatoms.

[0040] As used herein, the term "polymer" may include an oligomer and a polymer.

[0041] In this specification, unless otherwise specified, the term "molecular weight" refers to the sum of the atomic weights of the atoms contained in a molecule.

[0042] In the semiconductor industry, the demand for smaller chip sizes continues to grow. To meet this demand, the linewidth of photoresists patterned using lithography techniques must be on the order of tens of nanometers. Therefore, the height that can be accommodated by the linewidth of the photoresist pattern is limited, resulting in the photoresist not being sufficiently resistant to the etching step. To address this issue, an auxiliary layer known as a hardmask layer is used between the material layer to be etched and the photoresist layer. This hardmask layer serves as an intermediate layer that transfers the fine pattern of the photoresist to the material layer through selective etching. Therefore, the hardmask layer must have excellent etching resistance to withstand the etching process required for pattern transfer, and the hardmask composition must have good crosslinking properties, i.e., good curing efficiency.

[0043] Conventional methods for forming hard mask layers have employed chemical or physical vapor deposition processes, but these require large-scale equipment, have high process costs, and are associated with poor economic efficiency. Therefore, in recent years, a technology for forming hard mask layers via spin coating has been developed. Spin coating is easier than conventional methods and can result in better gap-fill and planarization properties for hard mask layers manufactured using this method. However, the etch resistance of the hard mask layer tends to be somewhat reduced. Therefore, it is preferable to use a hard mask composition that can be applied to spin coating, and that the hard mask layer formed using this method has the same etch resistance as a hard mask layer formed using a chemical or physical vapor deposition method.

[0044] Therefore, in order to improve the etching resistance of the hard mask layer, research has been actively conducted to increase the carbon content of the hard mask composition. However, as the carbon content of the compound contained in the hard mask composition increases, the solubility in the solvent tends to decrease. Therefore, it is necessary to increase the carbon content of the compound contained in the hard mask composition to improve the etching resistance of the hard mask layer formed therefrom while maintaining good solubility in the solvent of the compound.

[0045] A hard mask composition according to one embodiment of the present invention may include a compound containing multiple aromatic hydrocarbon rings or aromatic heterocyclic rings in one molecule, thereby increasing the carbon content. Therefore, the hard mask layer obtained from the composition may have improved etching resistance. Furthermore, the compound may have specific functional groups on the aromatic hydrocarbon rings or aromatic heterocyclic rings, thereby improving the solubility of the compound in solvents despite containing multiple aromatic hydrocarbon rings or aromatic heterocyclic rings.

[0046] Specifically, a hard mask composition according to one embodiment of the present invention includes a compound represented by the following Chemical Formula 1 and a solvent:

[0047] [ka]

[0048] In the above chemical formula 1, R 1 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, R 2 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 carbon atoms, or a combination thereof; n is R 1 is an integer greater than or equal to 1, with the maximum number of substitutions allowed.

[0049] The hard mask composition according to one embodiment of the present invention is a compound represented by Formula 1, wherein the central aromatic hydrocarbon ring (R 1 By directly introducing an ethynylene group (-C≡C-) into the carbon atom of the aryl group, the carbon content can be further increased, and the crosslinking properties of a composition containing the aryl group can be improved. Therefore, a hard mask layer obtained from the composition can ensure excellent etching resistance. Furthermore, by including a hydroxy group in the compound, the solubility in a solvent of a compound containing multiple aromatic hydrocarbon rings or aromatic heterocycles can be improved.

[0050] R in the above chemical formula 1 1 is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms, for example, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms, for example, a substituted or unsubstituted group consisting of at least one of the structures selected from Group 1 below.

[0051] [ka]

[0052] As an example, R in Chemical Formula 1 1 is a substituted or unsubstituted group consisting of at least one structure selected from Group 1-1 below.

[0053] [ka]

[0054] As an example, R in Chemical Formula 1 1 may be a substituted or unsubstituted group consisting of at least one selected from the group consisting of benzene, naphthalene, and pyrene, and may be, for example, benzene or naphthalene, but is not limited to these.

[0055] R in the above chemical formula 1 2may be a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 6 to 30 carbon atoms, or a combination thereof. For example, R 2 may be a substituted or unsubstituted aromatic hydrocarbon group having 10 to 30 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 6 to 30 carbon atoms, or a combination thereof. For example, R 2 may be a substituted or unsubstituted group consisting of at least one of the structures selected from Group 2 and Group 3 below.

[0056] [ka]

[0057] [ka]

[0058] Among the above group 3, Z 1 and Z 2 are each independently -O-, -S-, or -NR'- (wherein R' is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms).

[0059] For example, R in the above chemical formula 1 2 is a substituted aromatic hydrocarbon group having 10 to 30 carbon atoms, for example, R 2 is a substituted or unsubstituted aromatic hydrocarbon group containing four or more rings, and examples thereof include R 2 is a substituted or unsubstituted group consisting of at least one structure selected from the following Group 2-1:

[0060] [ka]

[0061] As an example, R 2is a substituted or unsubstituted group consisting of at least one selected from the group consisting of pyrene, perylene, benzoperylene, and coronene, but is not limited to these. 2 When the compound represented by Chemical Formula 1 has the above structure, the etching resistance of the hard mask layer produced from the composition containing the compound represented by Chemical Formula 1 can be improved.

[0062] n in the above chemical formula 1 is R 1 In this specification, the "substitutable number" refers to the number of groups or structures that can be bonded to other groups. For example, R 1 For example, if R is a benzene ring, the number of carbon atoms in the benzene ring is 6, so the "number of possible substitutions" for the benzene ring is 6. 1 When R is a benzene ring, the range of n is 1 to 6. 1 In the case of a phenanthrene ring, the number of carbon atoms in the phenanthrene ring is 14, but the number of carbon atoms that can be substituted is 10, so the "number of possible substitutions" for the phenanthrene ring is 10. Therefore, R 1 When the ring is a phenanthrene ring, the range of n is 1 or more and 10 or less.

[0063] In the above Chemical Formula 1, n is, for example, an integer of 1 to 6, for example, an integer of 1 to 4, for example, an integer of 1 to 3, for example, 1 or 2, for example, but is not limited to, 2. When n is an integer of 2 or more, two or more R 2 may be the same group as each other, or may be different groups, or some may be the same group and the rest may be different groups.

[0064] As an example, the compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-3 below.

[0065] [ka]

[0066] In the above chemical formulas 1-1 to 1-3, R a and R b are each independently a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an amino group, a thiol group, or a combination thereof, and each p is independently R a is an integer of 0 or more, with the upper limit being the number of substitutions that can be made for R, b In other words, in Chemical Formula 1-1 and Chemical Formula 1-3, p and q are each independently an integer of 0 to 9, and in Chemical Formula 1-2, p and q are each independently an integer of 0 to 11.

[0067] Above R a and R b are each independently a hydroxy group, a methoxy group, an ethoxy group, or a thiol group, for example, a hydroxy group or a methoxy group. The above p and q are, for example, integers of 0 to 5, for example, integers of 0 to 2, but are not limited thereto.

[0068] The compound may have a molecular weight of 300 g / mol to 5,000 g / mol. For example, the compound may have a molecular weight of 300 g / mol to 4,500 g / mol, such as 300 g / mol to 4,000 g / mol, such as 350 g / mol to 4,500 g / mol, such as 350 g / mol to 4,000 g / mol, such as 400 g / mol to 5,000 g / mol, such as 400 g / mol to 4,500 g / mol, such as 400 g / mol to 4,000 g / mol, such as 400 g / mol to 3,500 g / mol, but is not limited thereto. By having a molecular weight within the above range, the carbon content and solubility in a solvent of a hard mask composition containing the compound can be adjusted and optimized.

[0069] The compound may be contained in an amount of 0.1% by mass to 30% by mass based on the total mass of the hard mask composition. For example, the amount 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, or such as 1% by mass to 20% by mass. By containing the compound in the above range, the thickness, surface roughness, and degree of planarization of the hard mask layer formed from the hard mask composition can be easily adjusted.

[0070] The compound represented by the above Chemical Formula 1 can be synthesized by appropriately referring to conventionally known methods. More specifically, a person skilled in the art can easily synthesize the compound by referring to the synthesis methods described in the Examples.

[0071] The hard mask composition according to one embodiment of the present invention may include a solvent, and 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, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate. The solvent is not particularly limited as long as it has sufficient solubility and / or dispersibility for the compound.

[0072] The hard mask composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

[0073] 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.

[0074] Examples of the crosslinking agent include melamine-based agents, substituted urea-based agents, and polymers containing these as monomers. A crosslinking agent having at least two crosslink-forming substituents is preferred, and 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.

[0075] Furthermore, a crosslinking agent having high heat resistance can be used as the crosslinking agent, such as a compound having an aromatic hydrocarbon ring structure (e.g., a benzene ring or a naphthalene ring) and a crosslink-forming substituent in the molecule.

[0076] Examples of the thermal acid generator that can be used include, but are not limited to, compounds that are acidic themselves, 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 compounds that generate an acid upon thermal decomposition, such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and organic sulfonic acid alkyl esters.

[0077] According to another aspect of the present invention, there is provided a hard mask layer comprising a cured product of the hard mask composition described above.

[0078] A method for forming a pattern using the above-described hard mask composition will now be described.

[0079] A pattern formation method according to one embodiment of the present invention includes the steps of forming a material layer on a substrate, applying a hard mask composition containing the above-described compound and a solvent onto 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.

[0080] The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. The material layer is a material to be finally patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide or silicon nitride. The material layer may be formed, for example, by chemical vapor deposition.

[0081] The hard mask composition may be prepared in the form of a solution and applied by spin coating, as described above. The thickness of the applied hard mask composition is not particularly limited, but may be, for example, 50 to 200,000 Å.

[0082] The step of heat-treating the hard mask composition may be performed, for example, at a temperature of 100° C. to 1,000° C. for 10 seconds to 1 hour. For example, the step of heat-treating the hard mask composition may include multiple heat-treatment steps, for example, a first heat-treatment step and a second heat-treatment step.

[0083] In one embodiment, the step of heat-treating the hard mask composition may include a single heat-treatment step performed at a temperature of 100°C to 1000°C for 10 seconds to 1 hour. For example, the heat-treatment step may be performed in an air or nitrogen atmosphere, or in an atmosphere with an oxygen concentration of 1% by mass or less.

[0084] In one embodiment, 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, 150°C to 400°C, for example, 30 seconds to 1 hour, for example, 30 seconds to 30 minutes, for example, 30 seconds to 10 minutes, for example, 30 seconds to 5 minutes.

[0085] The method may also include a second heat treatment step, which is performed consecutively 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 600°C, for example, 30 seconds to 1 hour, for example, 30 seconds to 30 minutes, for example, 30 seconds to 10 minutes, for example, 30 seconds to 5 minutes. For example, the first and second heat treatment steps may be performed in an air or nitrogen atmosphere, or in an atmosphere with an oxygen concentration of 1% by mass or less.

[0086] At least one of the steps of heat treating the hard mask composition is performed at a high temperature of 200°C or higher, thereby exhibiting high etching resistance that can withstand etching gases and chemical solutions to which the hard mask composition is exposed in subsequent processes, including etching processes.

[0087] In one embodiment, forming the hard mask layer may include an ultraviolet / visible (UV / Vis) curing step and / or a near infrared (near IR) curing step.

[0088] In one embodiment, the step of forming the hard mask layer may include at least one of the first heat treatment step, the second heat treatment step, the ultraviolet / visible light (UV / Vis) curing step, and the near-infrared (NIR) curing step, or may include two or more of these steps sequentially.

[0089] In one embodiment, 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.

[0090] In one embodiment, before forming the photoresist layer, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer or the hard mask layer.

[0091] In one embodiment, the photoresist layer may be exposed to light using, for example, ArF, KrF, or EUV, and may be subjected to a heat treatment process at 100°C to 700°C after the exposure.

[0092] In one embodiment, the step of etching the exposed portions of the material layer may be performed by dry etching using an etching gas, such as N2 / O2, CHF3, CF4, Cl2, BCl3, and mixtures thereof.

[0093] The etched material layer can be formed in multiple patterns, which can be diverse, such as metal patterns, semiconductor patterns, insulating patterns, etc., and can be applied as various patterns within a semiconductor integrated circuit device, for example. [Example]

[0094] The above-described embodiments of the present invention will be described in more detail with reference to the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention.

[0095] Compound synthesis Synthesis Example 1 Under a nitrogen atmosphere, 3 mmol (0.33 mL) of 1,4-diethynylbenzene, 1.5 mmol (0.75 mL) of diethylzinc, and 4 mL of toluene were placed in a flask and stirred at 120°C for 5 hours. After cooling the reaction solution to 0°C, a solution of 1 mmol (230 mg) of pyrene-1-carboxaldehyde in 10 mL of toluene was slowly added over 20 minutes and stirred at room temperature for 12 hours. After confirming the completion of the reaction by thin-layer chromatography (TLC), 10 mL of saturated aqueous ammonium chloride (sat. NHCl) was added to the reaction solution and extracted with ethyl acetate. The resulting organic layer was dried over sodium sulfate (NaSO), filtered, and the solvent was removed. The resulting residue was purified by column chromatography to obtain the compound represented by formula 2 (molecular weight = 586.69 g / mol).

[0096] [ka]

[0097] Synthesis Example 2 A compound represented by the following chemical formula 3 was obtained in the same manner as in Synthesis Example 1, except that perylene-1-carboxaldehyde was used instead of pyrene-1-carboxaldehyde. (Molecular weight = 688.83 g / mol)

[0098] [ka]

[0099] Synthesis Example 3 A compound represented by the following chemical formula 4 was obtained in the same manner as in Synthesis Example 1, except that 2,7-diethynylnaphthalene was used instead of 1,4-diethynylbenzene. (Molecular weight = 636.75 g / mol)

[0100] [ka]

[0101] Synthesis Example 4 A compound represented by Chemical Formula 5 was obtained in the same manner as in Synthesis Example 1, except that 2,7-diethynylnaphthalene was used instead of 1,4-diethynylbenzene and 6-hydroxypyrene-1-carbaldehyde was used instead of pyrene-1-carboxaldehyde. (Molecular weight = 668.75 g / mol)

[0102] [ka]

[0103] Comparative synthesis example 1 Under a nitrogen atmosphere, 3 mmol (0.33 mL) of divinylbenzene, 1.5 mmol (0.75 mL) of diethylzinc, and 4 mL of toluene were added to a flask and stirred at 120°C for 5 hours. After cooling the reaction solution to 0°C, a solution of 1 mmol (230 mg) of pyrene-1-carboxaldehyde in 10 mL of toluene was slowly added over 20 minutes and stirred at room temperature for 12 hours. After confirming the completion of the reaction by thin-layer chromatography (TLC), the intermediate product was added with 10 mL of saturated aqueous ammonium chloride (sat. NH4Cl) and extracted with ethyl acetate. The organic layer was then dried over sodium sulfate (Na2SO4), filtered, and the solvent was removed. The resulting residue was purified by column chromatography to obtain the compound represented by the following formula 6: (Molecular weight = 590.72 g / mol).

[0104] [ka]

[0105] Comparative synthesis example 2 A compound represented by the following chemical formula 7 was obtained in the same manner as in Comparative Synthesis Example 1, except that 6-hydroxypyrene-1-carbaldehyde was used instead of pyrene-1-carboxaldehyde and divinylnaphthalene was used instead of divinylbenzene. (Molecular weight = 672.78 g / mol)

[0106] [ka]

[0107] Preparation of hard mask composition Example 1 3.5 g of the compound represented by Chemical Formula 2 obtained in Synthesis Example 1 was dissolved in 10 g of a solvent prepared by mixing propylene glycol methyl ether acetate (PGMEA) and cyclohexanone (ANONE) in a ratio of 7:3, and then filtered through a syringe filter to prepare a hard mask composition.

[0108] Example 2 A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 3 was used instead of Chemical Formula 2.

[0109] Example 3 A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 4 was used instead of Chemical Formula 2.

[0110] Example 4 A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 5 was used instead of Chemical Formula 2.

[0111] Comparative Example 1 A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 6 was used instead of Chemical Formula 2.

[0112] Comparative Example 2 A hard mask composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 7 was used instead of Chemical Formula 2.

[0113] Evaluation 1: Evaluation of etching resistance The hard mask compositions of Examples 1-4 and Comparative Examples 1 and 2 were diluted in PGMEA or PGMEA / ANONE solution to a solids concentration (each compound) of 15% by mass and applied to a silicon wafer. The wafer was then heat-treated on a hot plate at 400°C for 2 minutes to form a 4,000 Å-thick thin film, which was then measured using a K-MAC thin film thickness measuring device. The thin film was then dry-etched using a CFx mixed gas or an N2 / O2 mixed gas, and the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated from the thin film thickness before and after etching and the etching time using Equation 1 below, and the results are shown in Table 1 below.

[0114]

number

[0115] [Table 1]

[0116] Referring to Table 1 above, it can be seen that the hard masks formed from the hard mask compositions of Examples 1 to 4 have equivalent etching rates when etched with N2 / O2 mixed gas and CFx gas compared to the hard masks formed from the hard mask compositions of Comparative Examples 1 and 2. This demonstrates that the hard masks formed from the compositions of Examples 1 to 4 have equivalent etching resistance to the hard masks formed from the compositions of Comparative Examples 1 and 2.

[0117] Evaluation 2: Evaluation of crosslinking properties For evaluation of the crosslinking properties of the compositions according to Examples 1 to 4 and Comparative Examples 1 and 2, an SC1 solution was prepared by mixing ammonia, hydrogen peroxide, and water in a ratio of 1:1:5.

[0118] The hard mask compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were diluted in PGMEA or PGMEA / ANONE solution to a solids concentration (each compound) of 10% by mass, and then coated onto a silicon wafer. The resulting solution was then coated onto a silicon substrate and heat-treated at 400°C for 1 minute to form a hard mask layer with a thickness of 200 nm. The silicon substrate on which the hard mask layer was formed was immersed in SC1 solution heated to 60°C for 5 minutes, after which the thickness of the hard mask layer was measured and checked for any reduction in thickness to evaluate crosslinking properties. The evaluation results are shown in Table 2 below.

[0119] [Table 2]

[0120] Referring to Table 2 above, the hard mask layers formed from the compositions according to Examples 1 to 4 did not experience a decrease in thickness after immersion in SC1 solution, but a partial decrease was observed in the hard mask layers formed from the compositions according to Comparative Examples 1 and 2. This confirms that the hard mask compositions according to Examples 1 to 4 have improved crosslinking properties compared to the hard mask compositions according to Comparative Examples 1 and 2.

[0121] 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 compound represented by the following Chemical Formula 1 and a solvent: 【Chemical 1】 In the above chemical formula 1, R １ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms (excluding the carbon atoms of the substituents), R ２ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms (excluding the carbon atoms of the substituents), a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 carbon atoms (excluding the carbon atoms of the substituents), or a combination thereof; n is R １ is an integer of 1 or greater, with the upper limit being the number of substitutions that can be made.

2. R in the above chemical formula 1 ２ and each independently represent a substituted or unsubstituted aromatic hydrocarbon group having 10 to 30 carbon atoms (excluding the carbon atoms of the substituents), a substituted or unsubstituted aromatic heterocyclic group having 6 to 30 carbon atoms (excluding the carbon atoms of the substituents), or a combination thereof.

3. R in the above chemical formula 1 １ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms (excluding the carbon atoms of the substituents), and R ２ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 10 to 30 carbon atoms (excluding the carbon atoms of the substituents), and n is 2.

4. R in the above chemical formula 1 １ is a substituted or unsubstituted group consisting of at least one of the structures selected from Group 1 below: 【Chemistry 2】

5. R in the above chemical formula 1 ２ are each independently a substituted or unsubstituted group consisting of at least one of structures selected from Group 2 and Group 3 below: 【Chemistry 3】 【Chemistry 4】 In the above group 3, Z １ and Z ２ are each independently —O—, —S—, or —NR′— (wherein R′ is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (but not including the carbon atoms of the substituent)).

6. R in the above chemical formula 1 １ is a substituted or unsubstituted group consisting of at least one structure selected from Group 1-1 below, R ２ is a substituted or unsubstituted group consisting of at least one of structures selected from the following Group 2-1: 【Chemistry 5】

7. In the above chemical formula 1, n is 2, and two R ２ The hard mask composition of claim 1 , wherein

8. The hard mask composition according to claim 1, wherein the compound represented by Chemical Formula 1 is any one of compounds selected from the following Chemical Formulas 1-1 to 1-3: 【Chemistry 6】 In the above chemical formulas 1-1 to 1-3, R ａ and R ｂ are each independently a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms (excluding the carbon atoms of the substituents), a halogen atom, an amino group, a thiol group, or a combination thereof; and p is each independently R ａ is an integer of 0 or more, with the upper limit being the number of groups that can be substituted with R, ｂ is an integer of 0 or more, with the upper limit being the number that can be replaced by

9. 2. The hard mask composition of claim 1, wherein the compound represented by Formula 1 has a molecular weight of 300 g / mol to 5,000 g / mol.

10. 2. The hard mask composition of claim 1, wherein the compound represented by Formula 1 is included in an amount of 0.1 to 30 wt %, based on 100 wt % of the total weight of the hard mask composition.

11. 2. The hard mask composition of claim 1, wherein the solvent comprises at least one selected from 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.

12. A hard mask layer comprising a cured product of the hard mask composition according to any one of claims 1 to 11.

13. forming a layer of material on a substrate; applying a hard mask composition according to any one of claims 1 to 11 onto 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 portions of the material layer.

14. 14. The pattern formation method of claim 13, wherein the forming of the hard mask layer comprises a heat treatment at 100 to 1,000 degrees Celsius.

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