Hardmask composition, hardmask layer and patterning method

Abstract

To provide a hardmask composition capable of forming a hardmask layer that may have excellent film strength and improved film density, thereby ensuring excellent pattern formation.SOLUTION: The invention relates to: a hardmask composition comprising a solvent and a self-polymer of a compound represented by chemical formula 1 in the figure; a hardmask layer produced from the hardmask composition; and a method of forming patterns from the hardmask composition. The definition of 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 including a cured product of the hard mask composition, and a patterning 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 layer 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 with a good profile using the typical lithographic techniques described above. Therefore, a supplementary layer called a hard mask layer can be formed between the material layer to be etched and the photoresist layer to form a fine pattern. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2016-0145480 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 capable of forming a hard mask layer having excellent film strength and improved film density, thereby ensuring excellent pattern formability.

[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] The hard mask composition according to the present invention includes a self-polymer of a compound represented by the following Chemical Formula 1, and a solvent.

[0010] [ka]

[0011] In the above chemical formula 1, the ring represented by A is a 5- or 6-membered ring formed through a saturated or unsaturated bond, and the skeleton of the ring is composed entirely of carbon atoms or carbon atoms and one or more oxygen atoms or nitrogen atoms; L 1 and L 2 are each independently —(C═O)H, R 1 and R 2 are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms; m1 and m2 are each independently 0 or 1, and m1+m2=1; n1 is an integer from 0 to 3, and n2 is 0 or 1; k is 0 or 1, If k=0, then m1=1.

[0012] R in the above chemical formula 1 1 and R 2 are each independently a deuterium atom, a halogen atom, a hydroxy group, 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, or a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and n1+n2 is preferably an integer of 1 to 4.

[0013] R in the above chemical formula 1 1 and R 2 are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and n1 is preferably an integer of 1 to 3.

[0014] The compound represented by the above chemical formula 1 is preferably at least one of the compounds represented by the following chemical formulas 2 to 5.

[0015] [ka]

[0016] In the above chemical formulas 2 to 5, R a and R bare each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms; X 3 -CR c R d -, -O-, or -NR e - and X 4 and X 5 are each independently -CR f -, or -N-, In this case, the above R c ~R f are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, na is an integer between 0 and 3, nb is 0 or 1.

[0017] R in the above chemical formulas 2 to 5 a and R b are each independently a deuterium atom, a halogen atom, a hydroxy group, 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, or a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and na+nb is preferably an integer of 1 to 4.

[0018] R in the above chemical formulas 2 to 5 a and R bare each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and na is preferably an integer of 1 to 3.

[0019] X in the above chemical formula 3 3 is -O-, or -NR e -, and X in the above chemical formula 4 4 and X in the above formula 5 5 are each independently -CR f - and Above R e and R f are preferably each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0020] The weight average molecular weight of the self-polymer is preferably 1,000 g / mol to 200,000 g / mol.

[0021] The self-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.

[0022] The solvent is preferably 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.

[0023] According to another embodiment, there is provided a hard mask layer comprising a cured product of the hard mask composition described above.

[0024] According to yet another embodiment, there is provided a patterning method including the steps of: providing a material layer on a substrate; applying the above-described hard mask composition on the material layer; heat-treating the hard mask composition to form a hard mask layer; forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hard mask layer using the photoresist pattern to expose portions of the material layer; and etching the exposed portions of the material layer.

[0025] The step of forming the hard mask layer preferably includes a step of performing a heat treatment at 100°C to 1,000°C. [Effects of the Invention]

[0026] According to the present invention, there is provided a hard mask composition capable of forming a hard mask layer having excellent film strength and improved film density, thereby ensuring excellent pattern formability. DETAILED DESCRIPTION OF THE INVENTION

[0027] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to exemplary embodiments thereof, so that those skilled in the art will be able to easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein.

[0028] Unless otherwise defined in this specification, "substituted" means that a hydrogen atom in a compound has been replaced with a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azide group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl 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, a vinyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a carbon atom, It means that the group is substituted with a substituent selected from an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an arylaryl group having 9 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a heteroarylalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 15 carbon atoms, a cycloalkynyl group having 6 to 15 carbon atoms, a heterocycloalkyl group having 3 to 30 carbon atoms, and combinations thereof.

[0029] Furthermore, two adjacent substituents among the above-mentioned substituted halogen atoms (F, Br, Cl, or I), hydroxy groups, nitro groups, cyano groups, amino groups, azide groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamoyl groups, thiol groups, ester groups, carboxy groups and salts thereof, sulfonic acid groups and salts thereof, phosphoric acid groups and salts thereof, alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, heteroalkyl groups having 1 to 20 carbon atoms, heteroarylalkyl groups having 3 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, or heterocyclic groups having 2 to 30 carbon atoms may be bonded to form a ring.

[0030] Unless otherwise defined herein, the term "aryl group" refers to a group having one or more aromatic hydrocarbon moieties, and broadly includes aromatic hydrocarbon moieties linked by a single bond and non-aromatic fused rings to which aromatic hydrocarbon moieties are directly or indirectly fused. Aryl groups include monocyclic, polycyclic, and fused polycyclic (i.e., polycyclic groups containing rings that share adjacent pairs of carbon atoms) functional groups.

[0031] More specifically, the substituted or unsubstituted aryl group having 6 to 30 carbon atoms 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 phenanthrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, or a combination thereof.

[0032] Unless otherwise defined herein, the term "hetero" refers to a group containing 1 to 3 heteroatoms selected from N, O, S, Se, and P.

[0033] Unless otherwise defined in this specification, the term "alkyl group" refers to a monovalent straight or branched chain hydrocarbon group consisting of carbon atoms linked by single bonds.

[0034] Unless otherwise defined herein, the term "alkenyl group" refers to a monovalent straight or branched chain hydrocarbon group containing at least one double bond between carbon atoms.

[0035] Unless otherwise defined herein, the term "alkynyl group" refers to a monovalent straight or branched chain hydrocarbon group containing at least one triple bond between carbon atoms.

[0036] Unless otherwise defined in this specification, the term "cycloalkyl group" refers to a monovalent cyclic hydrocarbon group formed by linking carbon atoms with single bonds.

[0037] Unless otherwise defined in this specification, the term "heteroalkyl group" refers to a monovalent linear or branched hydrocarbon group consisting of a single bond between carbon atoms in which at least one carbon atom is substituted with at least one heteroatom selected from N, O, S, Se, and P.

[0038] Unless otherwise defined in this specification, the term "heterocycloalkyl group" refers to a monovalent cyclic hydrocarbon group in which at least one carbon atom within the group is substituted with at least one heteroatom selected from N, O, S, Se, and P.

[0039] In this specification, the term "polymer" can include both oligomers and polymers.

[0040] Unless otherwise specified in this specification, the "weight average molecular weight" is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using Agilent Technologies' 1200 series gel permeation chromatography (GPC) (using a Shodex LF-804 column and Shodex polystyrene as the standard sample).

[0041] The semiconductor industry is constantly demanding smaller chip sizes. To meet this demand, the linewidth of resists patterned using lithography must be on the order of several tens of nanometers. Therefore, the height that can be tolerated by the linewidth of the resist pattern is limited, resulting in cases where the resist cannot adequately withstand the etching step. To address this issue, an auxiliary layer known as a hard mask layer is used between the material layer to be etched and the photoresist layer. This hard mask layer serves as an intermediate layer that transfers the fine pattern of the photoresist to the material layer through selective etching. Therefore, the hard mask layer must have high film density and improved film strength to withstand the etching process required for pattern transfer.

[0042] The hard mask composition according to the present invention includes a self-polymer (homopolymer). The self-polymer has excellent cross-linking properties and densely connects structural units. Therefore, when a composition including the self-polymer is heat-treated, a dense film structure can be formed due to the dense connection between the polymer or structural units. Therefore, the hard mask layer formed from the hard mask composition according to the present invention can have high film density and improved film strength.

[0043] Specifically, the hard mask composition according to the present invention includes a self-polymer of a compound represented by the following Chemical Formula 1, and a solvent.

[0044] [ka]

[0045] In the above chemical formula 1, The ring represented by A is a 5- or 6-membered ring formed through a saturated or unsaturated bond, and the skeleton of the ring is composed entirely of carbon atoms or carbon atoms and one or more oxygen atoms or nitrogen atoms; L 1 and L 2 are each independently —(C═O)H, R1 and R 2 are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms; m1 and m2 are each independently 0 or 1, and m1+m2=1; n1 is an integer from 0 to 3, and n2 is 0 or 1; k is 0 or 1, If k=0, then m1=1.

[0046] The compound represented by Chemical Formula 1 contains aromatic rings and / or heterocycles with a high carbon content, which can harden the film of a hard mask layer containing a self-polymer of the compound. In addition, the compound contains aromatic rings and / or heterocycles with a relatively small size, which can be more densely connected to each other, thereby increasing the film density and film strength of the hard mask layer containing the self-polymer.

[0047] A self-polymer according to one embodiment of the present invention is formed by the self-polymerization of a compound represented by Chemical Formula 1. Bonds are formed between the compounds via aldehyde groups contained in the compounds, and this bond formation may occur randomly. Specifically, within one molecule, a carbon atom on an aromatic ring of another molecule may be bonded to a carbon atom of an aldehyde, and thus the bond may occur randomly. In other words, a self-polymer according to one embodiment may have a structure in which compounds represented by Chemical Formula 1 are randomly linked in a branched manner. The initial reaction in which bonds between compounds occur randomly can be simply represented by Reaction Scheme 1 below. However, Reaction Scheme 1 below is merely an example of a bonding reaction between compounds, and is not intended to be limiting.

[0048] [ka]

[0049] When the compound self-polymerizes as shown in Reaction Scheme 1, the connections between the structural units can be denser than in a copolymer formed by linking two or more different structural units together. Therefore, a hard mask layer formed from a composition including the self-polymer of the compound represented by Chemical Formula 1 can have improved film strength.

[0050] The ring represented by A in the above Chemical Formula 1 is a 5- or 6-membered ring formed via a saturated or unsaturated bond, i.e., a single bond or a double bond, and the skeleton of the ring may be composed entirely of carbon atoms or may be composed of carbon atoms and one or more oxygen or nitrogen atoms. The number of atoms constituting the ring A may be, for example, 5 or 6. When the ring A has 5 atoms, one of the atoms may be oxygen (O) or nitrogen (N), and the ring represented by A may be, but is not limited to, a furan ring or a pyrrole ring.

[0051] R in the above chemical formula 1 1 and R 2 are each independently a deuterium atom, a halogen atom, a hydroxy group, 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, or a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms. For example, they are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as, but not limited to, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.

[0052] In the above Chemical Formula 1, n1+n2 is an integer of 0 to 4, for example, an integer of 1 to 4, for example, an integer of 1 to 3, but is not limited thereto. In this case, n1 is an integer of 0 to 3, for example, an integer of 1 to 3, but is not limited thereto.

[0053] In the above chemical formula 1, m1 and m2 are each independently 0 or 1, and when m1 and m2 are not simultaneously 0, m1+m2=1.

[0054] The compound represented by the above chemical formula 1 is preferably at least one of the compounds represented by the following chemical formulas 2 to 5.

[0055] [ka]

[0056] In the above chemical formulas 2 to 5, Above R a and R b are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms.

[0057] For example, the above R a and R bare each independently a deuterium atom, a halogen atom, a hydroxy group, 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, or a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms; for example, are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, but are not limited to these.

[0058] As an example, R a and R b are each independently a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, for example, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, or a substituted alkyl group having 1 to 5 carbon atoms, but are not limited to these.

[0059] Above X 3 -CR c R d -, -O-, or -NR e - and the above X 4 and X 5 are each independently -CR f = or -N = and the above R c ~R f are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. c ~R f are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 16 carbon atoms; for example, are each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, but are not limited to these.

[0060] For example, X in the above chemical formula 33 -CR c R d -, -O-, or -NR e -(where R e is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.) Examples thereof include -CH2-, -CH(CH3)-, -O-, or -NH-, such as, but not limited to, -O- or -NH-.

[0061] For example, X in the above chemical formula 4 4 and X in the above formula 5 5 are each independently -CR f = where R f is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as R f is a hydrogen atom or a deuterium atom, but is not limited to these.

[0062] In Chemical Formula 2 to Chemical Formula 5, na is an integer of 0 to 3, for example, but not limited to, an integer of 1 to 3. In addition, nb in Chemical Formula 3 to Chemical Formula 5 is 0 or 1.

[0063] The self-polymer may have a weight-average molecular weight of 1,000 g / mol to 200,000 g / mol. For example, the weight-average molecular weight may be, but is not limited to, 1,000 g / mol to 150,000 g / mol, such as 1,000 g / mol to 100,000 g / mol, such as 1,200 g / mol to 50,000 g / mol, or 1,200 g / mol to 10,000 g / mol. By having a weight-average molecular weight within this range, the carbon content and solubility in a solvent of a hard mask composition containing the self-polymer can be adjusted and optimized.

[0064] The self-polymer may be included in an amount of 0.1% to 30% by weight based on the total weight of the hard mask composition. For example, it may be included in an amount of 0.2% to 30% by weight, such as 0.5% to 30% by weight, such as 1% to 30% by weight, such as 1.5% to 25% by weight, or such as 2% to 20% by weight, but is not limited thereto. By including the polymer in this range, the thickness, surface roughness, and degree of planarization of the hard mask can be easily adjusted.

[0065] The hard mask composition according to one embodiment of the present invention may include a solvent. In one embodiment, 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 in the polymer.

[0066] The hard mask composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

[0067] 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.

[0068] 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 methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea.

[0069] Furthermore, 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 crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be used.

[0070] Examples of the thermal acid generator 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.

[0071] According to another embodiment, there is provided a hard mask layer comprising a cured product of the hard mask composition described above.

[0072] A method for forming a pattern using the above-described hard mask composition will now be described.

[0073] A patterning method according to one embodiment includes the steps of providing a material layer on a substrate, applying a hard mask composition on the material layer, the hard mask composition including the polymer and a solvent described above, 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.

[0074] 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 a chemical vapor deposition method.

[0075] The hard mask composition may be prepared in the form of a solution and applied by a spin-on coating method, as described above. The thickness of the hard mask composition is not particularly limited, but may be, for example, 50 to 200,000 Å.

[0076] 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 multiple heat-treatment steps, for example, a first heat-treatment step and a second heat-treatment step.

[0077] In one embodiment, the step of heat-treating the hard mask composition may include a single 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 or nitrogen atmosphere, or in an atmosphere having an oxygen concentration of 1% by weight or less.

[0078] In one 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 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.

[0079] Furthermore, a second heat treatment step may be 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 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.

[0080] At least one of the heat-treating steps of 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 an etching process.

[0081] 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.

[0082] 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 UV / Vis curing step, and the near IR curing step, or may include two or more of these steps sequentially.

[0083] 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.

[0084] 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.

[0085] In one embodiment, the step of exposing the photoresist layer can be performed using, for example, ArF, KrF, or EUV, etc. After the exposure, a heat treatment process can be performed at 100°C to 700°C.

[0086] In one embodiment, the step of etching the exposed portions of the material layer can be performed by dry etching using an etching gas, such as N2 / O2, CHF3, CF4, Cl2, BCl3, and mixtures thereof.

[0087] The etched material layer can be formed in a variety of patterns, such as metal patterns, semiconductor patterns, and insulating patterns, and can be applied as various patterns within a semiconductor integrated circuit device, for example. [Example]

[0088] 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.

[0089] [Synthesis of self-polymers] (Synthesis Example 1) A solution was prepared by dissolving 122 g of 4-hydroxybenzaldehyde and 19 g of p-toluenesulfonic acid monohydrate in 200 g of propylene glycol monomethyl ether acetate in a 1 L three-neck flask. The solution was then stirred in a thermostatic chamber at 90-100°C for 40 hours. After the polymerization reaction was completed, the intermediate product was gradually cooled to room temperature. The intermediate product was added to 400 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was then removed, and the precipitate was dissolved in 200 g of propylene glycol monomethyl ether acetate (PGMEA). The remaining methanol and distilled water were then removed under reduced pressure to obtain self-polymer A (Mw: 1,500 g / mol).

[0090] (Synthesis Example 2) A solution was prepared by dissolving 174 g of 4-trifluoromethylbenzaldehyde and 19 g of p-toluenesulfonic acid monohydrate in 200 g of propylene glycol monomethyl ether acetate in a 1 L three-neck flask. The solution was then stirred in a thermostatic chamber at 90-100°C for 10 hours. After the polymerization reaction was completed, the intermediate product was gradually cooled to room temperature. The intermediate product was added to 400 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was then removed, and the precipitate was dissolved in 200 g of propylene glycol monomethyl ether acetate (PGMEA). The remaining methanol and distilled water were then removed under reduced pressure to obtain self-polymer B (Mw: 2,000 g / mol).

[0091] (Synthesis Example 3) A solution was prepared by dissolving 138 g of 3,4-dihydroxybenzaldehyde and 19 g of p-toluenesulfonic acid monohydrate in 200 g of propylene glycol monomethyl ether acetate in a 1 L three-neck flask. The solution was then stirred in a thermostatic chamber at 90-100°C for 20 hours. After the polymerization reaction was completed, the intermediate product was gradually cooled to room temperature. The intermediate product was added to 400 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was then removed, and the precipitate was dissolved in 200 g of propylene glycol monomethyl ether acetate (PGMEA). The remaining methanol and distilled water were then removed under reduced pressure to obtain self-polymer C (Mw: 1,500 g / mol).

[0092] (Comparative synthesis example) A solution was prepared by dissolving 160 g of 1-naphthol, 30 g (0.2 mol) of paraformaldehyde, and 19 g of p-toluenesulfonic acid monohydrate in 200 g of propylene glycol monomethyl ether acetate in a 1 L three-neck flask. The solution was then stirred in a thermostatic chamber at 90-100°C for 5 hours. After the polymerization reaction was completed, the intermediate product was gradually cooled to room temperature. The intermediate product was added to 400 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was then removed, and the precipitate was dissolved in 200 g of propylene glycol monomethyl ether acetate (PGMEA). The remaining methanol and distilled water were then removed under reduced pressure to obtain a comparative polymer (Mw: 2,000 g / mol).

[0093] [Examples and Comparative Examples: Preparation of Hard Mask Composition] Example 1 5 g of the self-polymer A obtained in Synthesis Example 1 was stirred with 50 g of a mixture of cyclohexanone / propylene glycol monomethyl ether acetate (1:1 volume ratio) for 60 minutes and filtered through a 0.45 μm Teflon filter to prepare a hard mask composition.

[0094] Example 2 A hard mask composition was prepared in the same manner as in Example 1, except that the self-polymer B was used instead of the self-polymer A.

[0095] Example 3 A hard mask composition was prepared in the same manner as in Example 1, except that the self-polymer C was used instead of the self-polymer A.

[0096] (Comparative Example) A hard mask composition was prepared in the same manner as in Example 1, except that the comparative polymer was used instead of the self-polymer A.

[0097] [Evaluation 1: Evaluation of film density] Each of the hard mask compositions according to Examples 1 to 3 and the Comparative Example was spin-coated onto a silicon wafer and then heat-treated on a hot plate at 400°C for 2 minutes to form a hard mask layer with a thickness of 1,000 Å. The film density of the formed hard mask layer was measured using an X-ray diffraction analyzer (PANalytical). The results are shown in Table 1 below.

[0098] [Table 1]

[0099] Referring to Table 1, it can be seen that the hard mask layers formed using the hard mask compositions according to Examples 1 to 3 have superior film density compared to the hard mask layers formed using the hard mask compositions according to the Comparative Example.

[0100] [Evaluation 2: Evaluation of membrane strength] The hard mask compositions according to Examples 1 to 3 and the Comparative Example were spin-coated onto silicon wafers to a thickness of 5,000 Å and then heat-treated on a hot plate at 400°C for 2 minutes to form thin films. The hardness (H) and modulus of elasticity (E) of the thin films were then measured using a nanoindenter (cube corner tip, Pmax = 300 μN).

[0101] The measurement results are shown in Table 2 below.

[0102] [Table 2]

[0103] Referring to Table 2, the hard masks formed from the hard mask compositions according to Examples 1 to 3 exhibit significantly higher hardness and elastic modulus than the hard masks formed from the hard mask compositions according to the Comparative Examples. In other words, it can be seen that the hard masks formed from the hard mask compositions according to the Examples exhibit superior film strength and provide hard masks with excellent mechanical properties compared to the hard masks formed from the hard mask compositions according to the Comparative Examples.

[0104] 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 present invention defined in the claims also fall within the scope of the present invention.

Claims

1. A hard mask composition comprising a self-polymer of a compound represented by the following Chemical Formula 1, and a solvent: 【Chemical 1】 (In the above chemical formula 1, the ring represented by A is a 5- or 6-membered ring formed through a saturated or unsaturated bond, and the skeleton of the ring is composed entirely of carbon atoms or carbon atoms and one or more oxygen atoms or nitrogen atoms; L １ and L ２ are each independently —(C═O)H, R １ and R ２ are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms; m1 and m2 each independently represent 0 or 1, and m1+m2=1; n1 is an integer from 0 to 3, and n2 is 0 or 1; k is 0 or 1; When k=0, m1=1; When a hydroxy group is selected for R 1 and R 2 , the carbon atom to which the hydroxy group is introduced is not adjacent to the carbon atom to which —(C═O)H is introduced in L 1 and L 2 .

2. R in the above formula 1 １ and R ２ are each independently a deuterium atom, a halogen atom, a hydroxy group, 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, or a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and n1+n2 is an integer of 1 to 4.

3. R in the above formula 1 １ and R ２ are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and n1 is an integer of 1 to 3.

4. 2. The hard mask composition according to claim 1, wherein the compound represented by Chemical Formula 1 is at least one of compounds represented by Chemical Formulas 2 to 5: 【Chemistry 2】 (In the above chemical formulas 2 to 5, R ａ and R ｂ are each independently a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms; When a hydroxy group is selected for R a and R b , the carbon atom to which the hydroxy group is introduced and the carbon atom to which —(C═O)H is introduced are not adjacent to each other; X ３ is -CR ｃ R ｄ -, -O-, or -NR ｅ - and X ４ and X ５ are each independently -CR ｆ - or -N-; At this time, the R ｃ ~R ｆ are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, na is an integer from 0 to 3; nb is 0 or 1.

5. R in the above chemical formulas 2 to 5 ａ and R ｂ are each independently a deuterium atom, a halogen atom, a hydroxyl group, 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, or a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and na+nb is an integer of 1 to 4.

6. R in the above chemical formulas 2 to 5 ａ and R ｂ are each independently a deuterium atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and na is an integer of 1 to 3.

7. X in the above formula 3 ３ is —O— or —NR ｅ -, and X in the above chemical formula 4 ４ and X in the above formula 5 ５ are each independently -CR ｆ - and The above R ｅ and R ｆ and each independently represent a hydrogen atom, a deuterium atom, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

8. The hard mask composition described in claim 1, wherein the compound represented by the above chemical formula 1 is a compound represented by the following chemical formula 2. 【Chemistry 3】 (In the above chemical formula 2, R a is a deuterium atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, 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, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 1 to 30 carbon atoms; When a hydroxy group is selected for R a , the carbon atom to which the hydroxy group is introduced and the carbon atom to which —(C═O)H is introduced are not adjacent to each other; na is an integer from 0 to 3.

9. The hard mask composition according to claim 8, wherein when a hydroxy group is selected for R a in the above chemical formula 2, the compound represented by the above chemical formula 1 is at least one of the compounds represented by the following formulas: 【Chemistry 4】

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

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

12. 2. The hard mask composition of claim 1, wherein the solvent is 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.

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

14. providing a layer of material over a substrate; applying a hard mask composition according to any one of claims 1 to 12 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 portions of the material layer; and etching the exposed portions of the layer of material; A pattern forming method comprising:

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

Images