Hardmask compositions, hardmask layers, and patterning methods

Abstract

To provide a hard mask composition that can be effectively applied to a hard mask layer.SOLUTION: A hardmask composition includes a polymer including a structural unit represented by Chemical Formula 1 and a solvent. The Chemical Formula 1 is as defined in the specifications.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Recently, the semiconductor industry has been evolving from patterns of hundreds of nanometers to ultra-fine technology having patterns of several to tens of nanometers, and effective lithographic techniques are essential to realize such ultra-fine technology.

[0003] A typical lithographic technique includes forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist pattern 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 has become difficult to form a fine pattern having a good profile using only the typical lithographic techniques described above. Therefore, a supplementary layer called a hard mask layer can be formed between a material layer to be etched and a photoresist layer to form a fine pattern. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2021-0026569 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is 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 hard mask composition.

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

[0009] A hard mask composition according to an 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 group having a structure represented by the following chemical formula 2: B is at least one substituted or unsubstituted moiety selected from Group 1 below, X 1 and X 2 are each independently at least one substituted or unsubstituted moiety selected from Group 2 below: * indicates the connection point:

[0012] [ka]

[0013] In the above chemical formula 2, R 1 is a hydroxyl group, an amino group (-NH 2 ), thiol group (-SH), or -OR a (where R ais a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; n is an integer between 2 and 6:

[0014] [ka]

[0015] R in the above chemical formula 2 1 is a hydroxyl group, an amino group (-NH 2 ), thiol group (-SH), or -OR a (where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms), and n is an integer of 2 to 4.

[0016] R in the above chemical formula 2 1 is a hydroxy group, or -OR a (where R a may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 16 carbon atoms), and n may be 2 or 3.

[0017] A in the above chemical formula 1 can be a group having at least one of the structures represented by the following chemical formulas 2-1 to 2-3.

[0018] [ka]

[0019] In the above chemical formulas 2-1 to 2-3, n is 2 or 3.

[0020] B in the above Chemical Formula 1 is preferably at least one of the unsubstituted moieties selected from Group 1 above.

[0021] B in the above Chemical Formula 1 is at least one substituted moiety selected from the above Group 1, and is preferably at least one of a hydroxyl group, a halogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a moiety substituted with a substituent that is a combination thereof.

[0022] X in the above chemical formula 1 1 and X 2 is preferably at least one of substituted or unsubstituted moieties selected from Group 2-1 below.

[0023] [ka]

[0024] X in the above chemical formula 1 1 and X 2 is preferably at least one of substituted or unsubstituted moieties selected from Group 2-2 below.

[0025] [ka]

[0026] The structural unit represented by the above chemical formula 1 is preferably at least one of the structural units represented by the following chemical formulas 1-1 to 1-6.

[0027] [ka]

[0028] [ka]

[0029] In the above Chemical Formula 1-1 to Chemical Formula 1-6, X 11 ~X 16 and X 21 ~X 26 are each independently at least one substituted or unsubstituted moiety selected from Group 2-2 below:

[0030] [ka]

[0031] The structural unit represented by the above chemical formula 1 is preferably at least one of the structural units represented by the following chemical formulas 1-7 to 1-10.

[0032] [ka]

[0033] The weight average molecular weight of the polymer is preferably 1,000 g / mol to 200,000 g / mol.

[0034] The polymer is preferably contained in an amount of 0.1% by mass to 30% by mass based on the total mass of the hard mask composition.

[0035] 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.

[0036] According to another embodiment of the present invention, there is provided a hard mask layer comprising a cured product of the above-mentioned hard mask composition.

[0037] According to yet another embodiment of the present invention, there is provided a method of forming a pattern, comprising 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 portions of the material layer, and etching the exposed portions of the material layer.

[0038] 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

[0039] According to the present invention, a hardmask composition can be provided that can be effectively applied to a hardmask layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] 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 can 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.

[0041] Unless otherwise defined in this specification, "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 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 phosphate 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 aryl group having 2 to 3 ... It means that the alkyl group is substituted with a substituent selected from an alkynyl group having from 20 carbon atoms, an aryl group having from 6 to 30 carbon atoms, an arylalkyl group having from 7 to 30 carbon atoms, an arylaryl group having from 9 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, a heteroalkyl group having from 1 to 20 carbon atoms, a heteroarylalkyl group having from 3 to 20 carbon atoms, a cycloalkyl group having from 3 to 30 carbon atoms, a cycloalkenyl group having from 3 to 15 carbon atoms, a cycloalkynyl group having from 6 to 15 carbon atoms, a heterocycloalkyl group having from 3 to 30 carbon atoms, and combinations thereof.

[0042] In addition, two adjacent substituents among 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 bonded to form a ring.

[0043] In this specification, the term "polymer" includes both an oligomer and a polymer.

[0044] Unless otherwise specified in this specification, the "weight average molecular weight" is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using 1200 series Gel Permeation Chromatography (GPC) manufactured by Agilent Technologies (using a Shodex LF-804 column and Shodex polystyrene as the standard sample).

[0045] In the semiconductor industry, there is a constant demand to reduce the size of chips. To meet this demand, the line width of the resist patterned in the lithography technology must be several tens of nanometers in size. Therefore, the height that can be withstood by 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, an auxiliary layer called a hardmask layer is used between the material layer to be etched and the photoresist layer. This hardmask layer serves as an intermediate film that transfers the fine pattern of the photoresist to the material layer through selective etching. Therefore, the hardmask layer is required to have etching resistance so that it can withstand the etching process required for pattern transfer.

[0046] Existing hard mask layers have been formed by chemical or physical vapor deposition, but this requires a large scale of equipment and high process costs, resulting in poor 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 and planarization characteristics of a hard mask layer manufactured using this method may be superior. However, a hard mask layer formed using the spin coating method has a problem that the required etching resistance is somewhat reduced. Therefore, a hard mask composition that can be applied to the spin coating method and a hard mask layer formed using this method are required to have the same etching resistance as a hard mask layer formed using a chemical or physical vapor deposition method.

[0047] Therefore, in order to improve the etching resistance of the hard mask layer, research has been conducted to maximize the carbon content of the hard mask composition. However, as the carbon content of the polymer contained in the hard mask composition increases, the solubility of the polymer in the solvent tends to decrease. Therefore, it is required to maximize the carbon content of the polymer contained in the hard mask composition to improve the etching resistance of the hard mask layer formed therefrom, and at the same time, to have the polymer have high solubility in the solvent.

[0048] The hard mask composition according to the embodiment of the present invention can increase the carbon content by including a polymer containing an aromatic macromonomolecular structure. Therefore, the etching resistance of the hard mask layer obtained from the composition is improved, and a thick hard mask layer can be formed. In addition, the polymer can increase the carbon content in the polymer by including a tertiary carbon, and at the same time, the functional group can increase the solubility in a solvent.

[0049] 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.

[0050] [ka]

[0051] In the above chemical formula 1, A is a group having a structure represented by the following chemical formula 2: B is at least one substituted or unsubstituted moiety selected from Group 1 below, X 1 and X 2 are each independently at least one substituted or unsubstituted moiety selected from Group 2 below: * indicates the connection point:

[0052] [ka]

[0053] In the above chemical formula 2, R 1 is a hydroxyl group, an amino group (-NH 2 ), thiol group (-SH), or -OR a (where R ais a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; n is an integer between 2 and 6:

[0054] [ka]

[0055] In the above chemical formula 2, n is one of integers from 2 to 6, for example, n is one of integers from 2 to 4, for example, n is 2 or 3.

[0056] As an example, the structure represented by Chemical Formula 2 above may be at least one of the structures represented by Chemical Formulas 2-1 to 2-3 below.

[0057] As represented by the above chemical formula 1, the polymer according to one embodiment of the present invention has an aromatic hydrocarbon such as coronene or benzoperylene and an aromatic hydrocarbon structure of the above chemical formula 2 or group 2, thereby increasing the carbon content in the polymer. Therefore, a thin film formed from a hard mask composition containing the above polymer has excellent etching resistance and can ensure excellent pattern formability. The structural units represented by the above chemical formula 1 and the below-described chemical formulas 1-1 to 1-10 are repeating units contained in the polymer of the present invention. In the polymer of the present invention, the number of structural units (repeating units) represented by the above chemical formula 1 and the below-described chemical formulas 1-1 to 1-10, i.e., the degree of polymerization, is preferably 1 to 1,000, more preferably 2 to 100, and most preferably 3 to 20.

[0058] In addition, as represented by Chemical Formula 2, the main chain structure of the polymer according to one embodiment of the present invention has at least two substituents, thereby improving the solubility of the polymer in a solvent and improving the film density of the hard mask layer formed from a composition containing the polymer. By adjusting the number of hydrophilic functional groups such as hydroxyl groups and alkoxy groups in the structure represented by Chemical Formula 2, the solubility of the polymer in a solvent and the film density of the hard mask layer can be adjusted.

[0059] R in the above chemical formula 2 1 is a hydroxyl group, an amino group (-NH 2 ), thiol group (-SH), or -OR a (where R a is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. For example, R 1 is a hydroxy group, or -OR a (where R a is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 16 carbon atoms. For example, R 1 is a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyloxy group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 16 carbon atoms. For example, R 1 represents a hydroxy group, a substituted or unsubstituted alkoxy group having 2 to 5 carbon atoms, or a substituted or unsubstituted alkynyloxy group having 2 to 5 carbon atoms.

[0060] In the above chemical formula 2, n is one of integers from 2 to 6, for example, n is one of integers from 2 to 4, for example, n is 2 or 3.

[0061] As an example, the structure represented by Chemical Formula 2 above may be at least one of the structures represented by Chemical Formulas 2-1 to 2-3 below.

[0062] [ka]

[0063] In the above chemical formulas 2-1 to 2-3, n is 2 or 3.

[0064] The moiety of B in the above Chemical Formula 1 may be unsubstituted or substituted. When the moiety of B is substituted, the substituent may be a hydroxy group, a halogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a combination thereof, such as a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a combination thereof, such as a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, or a combination thereof, but is not limited thereto.

[0065] X in the above chemical formula 1 1 and X 2 may each independently be at least one type of substituted or unsubstituted moiety selected from Group 2-1 below, for example, at least one type of substituted or unsubstituted moiety selected from Group 2-2 below, but is not limited thereto.

[0066] [ka]

[0067] X in the above chemical formula 1 1 and X 2More preferably, each independently represents at least one of substituted or unsubstituted moieties selected from Group 2-2 below.

[0068] [ka]

[0069] The structural unit represented by the above chemical formula 1 is more preferably at least one of the structural units represented by the following chemical formulas 1-1 to 1-6.

[0070] [ka]

[0071] [ka]

[0072] In the above Chemical Formula 1-1 to Chemical Formula 1-6, X 11 ~X 16 and X 21 ~X 26 are each independently at least one substituted or unsubstituted moiety selected from Group 2-2 above.

[0073] The structural unit represented by the above Chemical Formula 1 can be at least one of the structural units represented by the following Chemical Formulas 1-7 to 1-10, or a combination thereof.

[0074] [ka]

[0075] 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, 1,200 g / mol to 50,000 g / mol, for example, 1,200 g / mol to 10,000 g / mol, but is not limited thereto. By having a weight average molecular weight in such a range, the carbon content and solubility in a solvent of the hard mask composition containing the polymer can be adjusted and optimized.

[0076] The polymer of the present invention can be synthesized by appropriately referring to a conventionally known synthesis method. More specifically, a person skilled in the art can easily synthesize the polymer by referring to the synthesis methods described in the Examples.

[0077] 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. The content may be, for example, 0.2% by mass to 30% by mass, for example, 0.5% by mass to 30% by mass, for example, 1% by mass to 30% by mass, for example, 1.5% by mass to 25% by mass, for example, 2% by mass to 20% by mass, and is not limited thereto. By containing the polymer in such a content range, the thickness, surface roughness, and flatness of the hard mask can be easily adjusted.

[0078] The hard mask composition according to one embodiment of the present invention may include a solvent. Examples of the solvent include, but are 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 in the polymer.

[0079] The hard mask composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

[0080] 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.

[0081] Examples of the crosslinking agent include melamine-based agents, substituted urea-based agents, and polymers thereof. Preferably, a crosslinking agent having at least two crosslink-forming substituents can be used, such as a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea.

[0082] 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, a naphthalene ring) in the molecule can be used.

[0083] Examples of the thermal acid generator 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.

[0084] According to another embodiment of the present invention, there is provided a hardmask layer comprising the cured hardmask composition described above.

[0085] A method for forming a pattern using the above-described hard mask composition will now be described.

[0086] A patterning method according to one 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 portions of the material layer, and etching the exposed portions of the material layer.

[0087] The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. The material layer is the material to be ultimately 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.

[0088] The hard mask composition may be prepared in the form of a solution as described above and applied by spin coating. In this case, the thickness of the hard mask composition is not particularly limited, but may be, for example, 50 to 200,000 Å.

[0089] The step of heat treating the hard mask composition may be performed, for example, at 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 a plurality of heat treatment steps, for example, a first heat treatment step and a second heat treatment step.

[0090] In one embodiment, the step of heat treating the hard mask composition may include a heat treatment step performed at, for example, 100° C. to 1000° C. for 10 seconds to 1 hour. For example, the heat treatment step may be performed in an air atmosphere or a nitrogen atmosphere, and may also be performed in an atmosphere having an oxygen concentration of 1% by weight or less.

[0091] In an embodiment, the step of heat treating the hard mask composition includes a first heat treatment step performed at, 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 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.

[0092] Also, it may include a second heat treatment step successively performed at, 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 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. As an example, the first heat treatment step and the second heat treatment step may be performed in an air atmosphere or a nitrogen atmosphere, and may also be performed in an atmosphere with an oxygen concentration of 1% by mass or less.

[0093] 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.

[0094] In one embodiment, forming the hard mask layer may include a UV-Visible light curing step and / or a NIR curing step.

[0095] In one embodiment, 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 curing step, and a near-infrared curing step, or may include two or more of these steps consecutively.

[0096] In one embodiment, the method can further include forming a silicon-containing thin film layer on the hard mask layer. The silicon-containing thin film layer can be formed of a material such as, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiO, and / or SiN.

[0097] In one embodiment, 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 the hard mask layer.

[0098] In one embodiment, the step of exposing the photoresist layer can be performed using, for example, ArF, KrF, EUV, etc. After the exposure, a heat treatment process can be performed at 100° C. to 700° C.

[0099] In one embodiment, etching the exposed portions of the material layer may be performed by dry etching using an etching gas, e.g., N 2 / O 2 , CHF 3 , C.F. 4 , Cl 2 , BCl 3 , and mixtures of these gases can be used.

[0100] The etched material layer can be formed into a variety of patterns, including metal patterns, semiconductor patterns, insulating patterns, and the like, and can be used as a variety of patterns within a semiconductor integrated circuit device, for example. EXAMPLES

[0101] The above-mentioned embodiments of the present invention will be described in more detail with reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0102] [Polymer synthesis] (Comparative Synthesis Example 1) In a 500 ml two-neck flask equipped with a mechanical stirrer and a condenser, 30.0 g (0.1 mol) of coronene and 34 g (0.2 mol) of 2-naphthoyl chloride were dissolved in 300 g of 1,2-dichloroethane. After 15 minutes, aluminum chloride (AlCl 315g (0.11 mol) of tetrahydrofuran was gradually added and reacted at room temperature for 5 hours. After the reaction was completed, aluminum chloride was removed using water, and then the mixture was concentrated using an evaporator. 160g of tetrahydrofuran was added to the compound obtained by concentration to obtain a solution. 16g (0.42 mol) of sodium borohydride aqueous solution was gradually added to the obtained solution at room temperature and stirred for 12 hours. After the reaction was completed, the pH was adjusted to 5 using a 7% by mass aqueous hydrogen chloride solution, extracted with ethyl acetate, and the organic solvent was distilled off under reduced pressure to obtain compound A represented by the following chemical formula A.

[0103] [ka]

[0104] (Comparative Synthesis Example 2) Compound B represented by the following chemical formula B was obtained in the same manner as in Comparative Synthesis Example 1 above, except that benzoperylene was used instead of coronene.

[0105] [ka]

[0106] (Comparative Synthesis Example 3) 50g (0.23 mol) of 1-hydroxypyrene and 38.0g (0.23 mol) of 1,4-bis(methoxymethyl)benzene were sequentially placed in a 500ml flask and dissolved in 100g of propylene glycol monomethyl ether acetate (PGMEA), followed by adding 4.35g (0.02 mol) of paratoluenesulfonic acid and stirring for about 20 hours at 100°C. Samples were taken from the product obtained by the polymerization reaction at one-hour intervals, and the reaction was terminated when the weight-average molecular weight of the sample reached 2,500g / mol to 2,600g / mol, to obtain a comparative polymer C consisting of a structural unit represented by the following compound C (Mw: 2,500g / mol, PD: 1.54).

[0107] [ka]

[0108] (Comparative Synthesis Example 4) In a 500 ml flask, 50 g (0.23 mol) of 1-hydroxypyrene and 24.3 g (0.23 mol) of benzaldehyde were sequentially added and dissolved in 130 g of propylene glycol monomethyl ether acetate (PGMEA), and then 13.1 g (0.07 mol) of paratoluenesulfonic acid was added and stirred at 110° C. for about 24 hours. Samples were taken from the product obtained by the polymerization reaction at one-hour intervals, and the reaction was terminated when the weight-average molecular weight of the sample reached 3,000 g / mol to 3,500 g / mol, to obtain a comparative polymer D consisting of a structural unit represented by the following chemical formula D (Mw: 3,400 g / mol, PD: 1.61).

[0109] [ka]

[0110] (Comparative Synthesis Example 5) In a 500 ml two-neck flask equipped with a mechanical stirrer and a cooling tube, 50 g (0.08 mol) of compound A, 11.2 g (0.08 mol) of 1-naphthol, 0.47 g (0.002 mol) of paratoluenesulfonic acid, and 148 g of 1,4-dioxane were placed and stirred at 70°C for 24 hours. After the polymerization reaction, the temperature was lowered to 30°C, 300 g of tetrahydrofuran was added to prevent the compound from solidifying, and the pH of the compound was adjusted to 5 to 6 using a 7% by mass aqueous sodium bicarbonate solution. 1,000 ml of ethyl acetate was added here and stirred continuously, and only the organic layer was extracted using a separatory funnel. 500 ml of water was placed in the separatory funnel, and the process of removing the acid and sodium salt was repeated three or more times to extract the organic layer. The extracted organic solution was concentrated using an evaporator, and 700 g of tetrahydrofuran was added to the compound obtained by concentration to obtain the compound in the form of a solution. The obtained solution was gradually added dropwise to a beaker containing 3,000 ml of hexane in a stirred state to form a precipitate, thereby obtaining a comparative polymer E consisting of a structural unit represented by the following chemical formula E.

[0111] The weight average molecular weight (Mw) and polydispersity (PD) of Comparative Polymer E were measured by gel permeation chromatography, and the weight average molecular weight (Mw) was 1,450 g / mol and the polydispersity (PD) was 1.21.

[0112] [ka]

[0113] (Comparative Synthesis Example 6) Comparative polymer F consisting of a structural unit represented by the following chemical formula F was obtained in the same manner as in Comparative Synthesis Example 4, except that 1,5-dihydroxynaphthalene was used instead of 1-hydroxypyrene and benzo[ghi]perylenecarboxaldehyde was used instead of benzaldehyde. The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized comparative polymer F were measured using gel permeation chromatography, and the weight average molecular weight (Mw) was 1,600 g / mol and the polydispersity (PD) was 1.23.

[0114] [ka]

[0115] (Synthesis Example 1) In a 500 ml two-neck flask equipped with a mechanical stirrer and a cooling tube, 50 g (0.08 mol) of compound A, 13.1 g (0.08 mol) of 1,5-dihydroxynaphthalene, 0.47 g (0.002 mol) of paratoluenesulfonic acid, and 148 g of 1,4-dioxane were placed and stirred at 70 ° C for 24 hours to carry out a polymerization reaction. After the reaction was completed, the temperature was lowered to 30 ° C, 300 g of tetrahydrofuran was added to prevent the compound from solidifying, and the pH of the compound was adjusted to 5 to 6 with a 7 mass % aqueous sodium bicarbonate solution. 1,000 ml of ethyl acetate was added here and stirred continuously, and only the organic layer was extracted using a separatory funnel. 500 ml of water was placed in the separatory funnel, and the process of removing the acid and sodium salt was repeated three or more times to extract the organic layer. The extracted organic solution was concentrated using an evaporator, and 700 g of tetrahydrofuran was added to the compound obtained by concentration to obtain the compound in the form of a solution. The obtained solution was gradually dropped into a beaker containing 3,000 ml of hexane in a stirred state to form a precipitate, thereby obtaining a polymer G consisting of a structural unit represented by the following chemical formula 1-8.

[0116] The weight average molecular weight (Mw) and polydispersity (PD) of polymer G were measured by gel permeation chromatography, and the weight average molecular weight (Mw) was 2,550 g / mol and the polydispersity (PD) was 1.64.

[0117] [ka]

[0118] (Synthesis Example 2) Polymer H consisting of a structural unit represented by the following chemical formula 1-7 was obtained in the same manner as in Synthesis Example 1, except that compound B was used instead of compound A. The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer H were measured using gel permeation chromatography (GPC), and the weight average molecular weight (Mw) was 2,900 g / mol and the polydispersity (PD) was 1.65.

[0119] [ka]

[0120] (Synthesis Example 3) Polymer I consisting of a structural unit represented by the following chemical formula 1-9 was obtained in the same manner as in Synthesis Example 1, except that 1,5-dimethoxynaphthalene was used instead of 1,5-dihydroxynaphthalene. The weight average molecular weight (Mw) and polydispersity (PD) of the synthesized polymer I were measured by gel permeation chromatography, and the weight average molecular weight (Mw) was 2,100 g / mol and the polydispersity (PD) was 1.45.

[0121] [ka]

[0122] (Synthesis Example 4) Polymer J having a structural unit represented by the following Chemical Formula 1-10 was obtained in the same manner as in Synthesis Example 1, except that 1-5-diacetyleneoxynaphthalene was used instead of 1,5-dihydroxynaphthalene. The weight average molecular weight (Mw) and polydispersity (PD) of polymer J synthesized were measured using gel permeation chromatography, and the weight average molecular weight (Mw) was 1,950 g / mol and the polydispersity (PD) was 1.37.

[0123] [ka]

[0124] [Preparation of hard mask composition] Example 1 A hard mask composition was prepared by dissolving 1.2 g of the polymer G obtained in Synthesis Example 1 in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) (volume ratio: 7:3) and filtering the solution through a 0.1 μm Teflon filter.

[0125] Example 2 A hard mask composition was prepared in the same manner as in Example 1, except that Polymer H was used instead of Polymer G.

[0126] Example 3 A hard mask composition was prepared in the same manner as in Example 1, except that Polymer I was used instead of Polymer G.

[0127] Example 4 A hard mask composition was prepared in the same manner as in Example 1, except that Polymer J was used instead of Polymer G.

[0128] Comparative Example 1 1.5 g of the compound A obtained in Comparative Synthesis Example 1 is dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate and cyclohexanone (volume ratio of 7:3), and filtered through a 0.1 μm Teflon filter to prepare a hard mask composition.

[0129] Comparative Example 2 A hard mask composition was prepared in the same manner as in Comparative Example 1, except that compound B was used instead of compound A.

[0130] Comparative Example 3 A hard mask composition was prepared in the same manner as in Comparative Example 1, except that Comparative Polymer C was used instead of Compound A.

[0131] Comparative Example 4 A hard mask composition was prepared in the same manner as in Comparative Example 1, except that Comparative Polymer D was used instead of Compound A.

[0132] Comparative Example 5 A hard mask composition was prepared in the same manner as in Comparative Example 1, except that Comparative Polymer E was used instead of Compound A.

[0133] Comparative Example 6 A hard mask composition was prepared in the same manner as in Comparative Example 1, except that Comparative Polymer F was used instead of Compound A.

[0134] (Evaluation 1: Etching resistance evaluation) The hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 6 were spin-coated on a silicon wafer, and then heat-treated on a hot plate at 400° C. for 2 minutes to form a thin film having a thickness of 4,000 Å. The thickness of the thin film was measured using a thin film thickness measuring device manufactured by K-MAC. 4 / CHF 3 After dry etching for 100 seconds using the mixed gas, the thickness of the thin film was measured again. The bulk etch rate (BER) (unit: Å / sec) was calculated from the thickness of the thin film before and after dry etching and the etching time according to the following formula 1.

[0135]

number

[0136] The measurement results of the etching rate are shown in Table 1 below.

[0137] [Table 1]

[0138] As is clear from Table 1 above, the thin films formed from the hard mask compositions of Examples 1 to 4 have superior resistance to etching gas (etching resistance) compared to the thin films formed from the hard mask compositions of Comparative Examples 1 to 6.

[0139] (Evaluation 2: Solubility evaluation) The compounds or polymers of the above Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 6 were dissolved in 20 g of propylene glycol monomethyl ether acetate to confirm the solubility. The amount of the compound or polymer dissolved in 20 g of the solvent was measured and calculated as a percentage.

[0140]

number

[0141] The solubility measurement results are shown in Table 2 below.

[0142] [Table 2]

[0143] As is clear from Table 2 above, it can be confirmed that the polymers of Synthesis Examples 1 to 4 are superior in solubility in a solvent to the compounds or polymers of Comparative Synthesis Examples 1 to 6.

[0144] (Evaluation 3: Storage stability evaluation) The hard mask compositions obtained from Examples 1 to 4 and Comparative Examples 1 to 6 were stored in a 40°C oven for one month while blocking far-ultraviolet rays, and then the changes in the compositions were observed using gel permeation chromatography (GPC). If there was a change in the molecular weight distribution curve and molecular weight measured by GPC (10% or more compared to the initial value), it was judged as 'X', and if there was no change, it was judged as 'O'. The results are shown in Table 3 below.

[0145] [Table 3]

[0146] As is clear from Table 3 above, it was confirmed that there was no change in the molecular weight distribution curves in Examples 1 to 4, whereas there was a change in the molecular weight distribution curves in Comparative Examples 1 to 6, except for Comparative Example 6. It was confirmed that the hard mask compositions according to the examples have superior storage stability compared to the hard mask compositions according to the comparative examples.

[0147] (Evaluation 4: Film density evaluation) The hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 6 were applied onto a silicon wafer by spin coating, and then heat-treated on a hot plate at 400° C. for 2 minutes to form a thin film having a thickness of 4,000 Å. The film density of the obtained thin film was measured using an X-ray diffraction analyzer manufactured by Panalytical. The measurement results of the film density are shown in Table 4 below.

[0148] [Table 4]

[0149] As is clear from Table 4 above, the film densities of the thin films produced from the hard mask compositions of Examples 1 to 4 are superior to the film densities of the thin films produced from the hard mask compositions of Comparative Examples 1 to 6.

[0150] 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 belong to 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 group having a structure represented by the following chemical formula 2: B is at least one of substituted or unsubstituted moieties selected from Group 1 below: X １ and X ２ are each independently at least one substituted or unsubstituted moiety selected from Group 2 below: * is the connection point: 【Chemistry 2】 In the above Chemical Formula 2, R １ represents a hydroxyl group, an amino group (-NH ２ ), a thiol group (-SH), or -OR ａ (Here, R ａ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; n is an integer from 2 to 6. 【Chemistry 3】

2. R in Formula 2 １ represents a hydroxyl group, an amino group (-NH ２ ), a thiol group (-SH), or -OR ａ (Here, R ａ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; 2. The hard mask composition of claim 1, wherein n is one of the integers from 2 to 4.

3. R in Formula 2 １ is a hydroxy group, or -OR ａ (Here, R ａ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 16 carbon atoms; 2. The hard mask composition of claim 1, wherein n is 2 or 3.

4. The hard mask composition according to claim 1, wherein A in the formula 1 is a group having at least one structure selected from the structures represented by the following formulas 2-1 to 2-3: 【Chemistry 4】 In the above chemical formulas 2-1 to 2-3, n is 2 or 3.

5. 2. The hard mask composition of claim 1, wherein B in Formula 1 is at least one unsubstituted moiety selected from Group 1.

6. 2. The hard mask composition of claim 1, wherein B in Formula 1 is at least one substituted moiety selected from Group 1, the at least one being a hydroxyl group, a halogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a moiety substituted with a substituent that is a combination thereof.

7. X in Formula 1 １ and X ２ The hard mask composition of claim 1 , wherein each of the groups is independently at least one of substituted or unsubstituted moieties selected from Group 2-1 below: 【Chemistry 5】

8. X in Formula 1 １ and X ２ The hard mask composition of claim 1 , wherein each of the groups is independently at least one of substituted or unsubstituted moieties selected from Group 2-2 below: 【Chemistry 6】

9. The hard mask composition according to claim 1, wherein the structural unit represented by Chemical Formula 1 is at least one of structural units represented by the following Chemical Formulas 1-1 to 1-6: 【Chemistry 7】 【Chemistry 8】 In the above Chemical Formula 1-1 to Chemical Formula 1-6, X １１ ~X １６ and X ２１ ~X ２６ are each independently at least one substituted or unsubstituted moiety selected from Group 2-2 below. 【Chemistry 9】

10. 2. The hard mask composition of claim 1, wherein the structural unit represented by Formula 1 is at least one of structural units represented by Formulas 1-7 to 1-10 below. 【Chemistry 10】

11. 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.

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

13. 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.

14. A hardmask layer comprising a cured product of the hardmask composition according to any one of claims 1 to 13.

15. providing a layer of material over a substrate; applying a hard mask composition according to any one of claims 1 to 13 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; and etching exposed portions of the layer of material; A pattern forming method comprising:

16. The method of claim 15, wherein the step of forming the hard mask layer comprises a step of performing a heat treatment at a temperature of 100° C. to 1,000° C.

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