Hard mask composition, hard mask layer, and method of forming pattern

Abstract

A hard mask layer including a cured product of a hard mask composition, and a method of forming a pattern using the hard mask layer including the cured product of the hard mask composition are provided. The hard mask composition includes a polymer including a structural unit represented by Chemical Formula 1; and a solvent. [Chemical Formula 1] # imgabs0 #

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2024 - 0012616, filed with the Korean Intellectual Property Office on January 26, 2024, the entire content of which is incorporated herein by reference. Technical field

[0003] Embodiments relate to a hard mask composition, a hard mask layer including a cured product of the hard mask composition, and a method of forming a pattern using the hard mask composition. Background art

[0004] Recently, the semiconductor industry has developed ultra - fine technologies with patterns sized from a few nanometers to dozens of nanometers. Such ultra - fine technologies may use effective lithography techniques.

[0005] Some lithography techniques may include providing a material layer on a semiconductor substrate; coating a photoresist layer thereon; exposing and developing it to provide a photoresist pattern; and using the photoresist pattern as a mask to etch the material layer. Summary of the invention

[0006] Embodiments relate to a hard mask composition including a polymer represented by Chemical Formula 1; and a solvent,

[0007] [Chemical Formula 1]

[0008]

[0009] Wherein, in Chemical Formula 1, Ar 1 to Ar 6 are each independently a substituted or unsubstituted C6 - C20 aromatic hydrocarbon ring, X 1 to X 6 are each independently a substituted or unsubstituted C6 - C20 aromatic hydrocarbon group, L 1 and L 2 are each independently a divalent organic group, and n is an integer from 1 to 100.

[0010] Ar 1 to Ar 6 may each independently be a substituted or unsubstituted aromatic hydrocarbon ring of Group 1,

[0011] [Group 1]

[0012]

[0013] X 1 to X 6 may each independently include a substituted or unsubstituted moiety of Group 2, [Group 2]

[0014]

[0015] L 1 and L 2 may each independently be represented by one of Chemical Formulas 2 to 5,

[0016] [Chemical Formula 2]

[0017]

[0018] [Chemical Formula 3]

[0019]

[0020] [Chemical Formula 4]

[0021]

[0022] [Chemical Formula 5]

[0023]

[0024] In Chemical Formulas 2 to 5, M 1 to M 4 may each independently include a substituted or unsubstituted moiety of Group 3, p1 to p3 and q1 to q3 may each independently be an integer from 0 to 4, p4 may be an integer from 1 to 5, and * is a point of attachment,

[0025] [Group 3]

[0026]

[0027] In Group 3, L a to L c may each independently be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, or a combination thereof, Z a and Z b may each independently be -O-, -S-, -SO2-, -C(=O)- or -NR a -, where R a may be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, s1 and s2 may each independently be 0 or 1, and t may be an integer from 0 to 4.

[0028] L 1 and L 2 may each independently be represented by one of Chemical Formulas 7 to 13, where * is a point of attachment,

[0029] [Chemical Formula 7]

[0030]

[0031] [Chemical Formula 8]

[0032]

[0033] [Chemical Formula 9]

[0034]

[0035] [Chemical Formula 10]

[0036]

[0037] [Chemical Formula 11]

[0038]

[0039] [Chemical Formula 12]

[0040]

[0041] [Chemical Formula 13]

[0042]

[0043] The polymer can be represented by one of Chemical Formulas 1-1 to 1-3,

[0044] [Chemical Formula 1-1]

[0045]

[0046] [Chemical Formula 1-2]

[0047]

[0048] [Chemical Formula 1-3]

[0049]

[0050] In Chemical Formulas 1-1 to 1-3, R 1 to R 6 can each independently be deuterium, a hydroxyl group, a substituted or unsubstituted C1 to C5 alkoxy group, a substituted or unsubstituted C1 to C5 alkyl group, or a combination thereof, y1 to y6 can each independently be an integer from 1 to 4, and n can be an integer from 1 to 100.

[0051] The polymer can have a weight-average molecular weight of about 1,000 g / mol to about 10,000 g / mol.

[0052] The polymer may be included in an amount of about 0.1 wt% to about 30 wt% based on the total weight of the hard mask composition.

[0053] The solvent may be propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetylacetone, or ethyl 3-ethoxypropionate.

[0054] This embodiment may be implemented by providing a hard mask layer including a cured product of the hard mask composition.

[0055] This embodiment may be implemented by providing a patterning method that includes: providing a material layer on a substrate; applying the hard mask composition to the material layer; heat-treating the hard mask composition to form a hard mask layer; forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer; and etching the exposed portion of the material layer.

[0056] The heat treatment may be performed at about 100 °C to about 1,000 °C. Description of the Drawings

[0057] By referring to the accompanying drawings and describing the exemplary embodiments in detail, those skilled in the art will understand their features:

[0058] Figure 1 is a reference figure schematically showing a cross-section of the hard mask layer for explaining a method of evaluating planarization characteristics. Detailed Description

[0059] Exemplary embodiments will now be described more fully with reference to the accompanying drawings; however, they may be embodied in different forms and should not be construed as limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the exemplary implementations to those skilled in the art.

[0060] In the drawings, for clarity of illustration, the dimensions of layers and regions may be exaggerated. It should also be understood that when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or there may also be intervening layers. In addition, it should be understood that when a layer is referred to as being "under" another layer, it can be directly under it, and there may also be one or more intervening layers. Further, it should be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or there may also be one or more intervening layers. The same reference numerals refer to the same elements throughout the specification. As used herein, the term "or" is not necessarily an exclusive term; for example, "A or B" will include A, B, or A and B. As used herein, hydrogen substitution (-H) may include deuterium substitution (-D) or tritium substitution (-T). For example, any hydrogen in any of the compounds described herein can be protium, deuterium, or tritium (e.g., based on natural or artificial substitution).

[0061] As used herein, when no other definition is provided, "substituted" may refer to a hydrogen atom of a compound being replaced by a substituent selected from halogen atoms (F, Br, Cl, or I), hydroxyl group, alkoxy group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid group or its salt, vinyl group, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C6-C30 aryl group, C7-C30 aralkyl group, C9-C30 allylaryl group, C1-C30 alkoxy group, C1-C20 heteroalkyl group, C3-C20 heteroaralkyl group, C3-C30 cycloalkyl group, C3-C15 cycloalkenyl group, C6-C15 cycloalkynyl group, C3-C30 heterocycloalkyl group, or a combination thereof.

[0062] In addition, two adjacent substituents, including substituted halogen atoms (F, Br, Cl, or I), hydroxyl group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid group or its salt, C1-C30 alkyl group, C2-C30 alkenyl group, C2-C30 alkynyl group, C6-C30 aryl group, C7-C30 aralkyl group, C1-C30 alkoxy group, C1-C20 heteroalkyl group, C3-C20 heteroaralkyl group, C3-C30 cycloalkyl group, C3-C15 cycloalkenyl group, C6-C15 cycloalkynyl group, C2-C30 heterocyclic group, may fuse to form a ring.

[0063] As used herein, unless otherwise defined, "aromatic hydrocarbon ring" refers to a group comprising at least one hydrocarbon aromatic moiety, and includes forms in which the hydrocarbon aromatic moiety is connected by a single bond, non-aromatic fused ring forms in which the hydrocarbon aromatic moiety is directly or indirectly fused, or combinations thereof, as well as non-fused aromatic hydrocarbon rings or fused aromatic hydrocarbon rings.

[0064] For example, a substituted or unsubstituted aromatic hydrocarbon ring can be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, combinations thereof, or a fused ring of combinations of the foregoing groups.

[0065] As used herein, unless otherwise defined, "combination" refers to mixing or copolymerizing.

[0066] As used herein, unless otherwise defined, a polymer may include oligomers and polymers.

[0067] Unless otherwise specified in this specification, the "weight-average molecular weight" is measured by dissolving a powder sample in tetrahydrofuran (THF), and then using a 1200 series Gel Permeation Chromatography (GPC) of Agilent Technologies (the column is LF-804 of Shodex Company, and the standard sample is polystyrene of Shodex Company).

[0068] In the semiconductor industry, the size of chips may be reduced. Therefore, the line width of a photoresist pattern in lithography technology may be on the order of dozens of nanometers. The height that can withstand the line width of the photoresist pattern may be limited, and the photoresist may not have sufficient etch resistance during the etching step. To compensate for this, an auxiliary layer called a hard mask layer can be used between the material layer to be etched and the photoresist layer. Such a hard mask layer can serve as an intermediate layer to transfer the fine pattern of the photoresist to the material layer by selective etching. Therefore, the hard mask layer may have etch resistance and heat resistance to withstand the etching process required for pattern transfer.

[0069] In addition, in order to achieve a fine pattern of a photoresist, forming a multiple pattern may be essential, and a gap filling property of a composition may be required to fill the gap in the fine pattern without voids. Additionally, if there are steps on a substrate to be processed, or if there are patterned regions and non-patterned regions on the same wafer, a planarization property may be required to form a flat surface of a hard mask layer.

[0070] Some other hard mask layers may be formed by chemical or physical deposition methods, and there may be a problem of low economic efficiency due to large equipment and high process costs. Therefore, a method of forming a hard mask layer by a spin coating technique has been recently considered. The spin coating technique may be easier to process than other methods. In addition, it may help to ensure that the hard mask layer formed thereby has excellent gap filling properties and planarization properties.

[0071] In a hard mask layer formed using the spin coating technique, the required etching resistance may be reduced. Therefore, a hard mask composition according to an embodiment may be applied using the spin coating technique and may ensure etching resistance comparable to that of a hard mask layer formed by a chemical or physical deposition method.

[0072] To help improve the etching resistance of the hard mask layer, maximizing the carbon content of the hard mask composition may be considered. As the carbon content of the polymer contained in the hard mask composition is maximized, the solubility in a solvent may be reduced. According to an embodiment, maximizing the carbon content of the polymer contained in the hard mask composition can not only improve the etching resistance of the hard mask layer formed by the hard mask composition, but also help to ensure high solubility of the polymer in the solvent.

[0073] A hard mask composition according to some embodiments may include a polymer having a high carbon content but a low molecular weight, and thus may have excellent fine pattern gap filling properties. In addition, by including a linking group having high fluidity in the polymer, the polymer may have excellent solubility in a solvent, and the planarization property of the hard mask layer formed by the composition may be improved.

[0074] A hard mask composition according to some embodiments may include a polymer represented by Chemical Formula 1, and a solvent.

[0075] [Chemical Formula 1]

[0076]

[0077] In Chemical Formula 1, Ar 1 to Ar 6 may each independently be or include, for example, a substituted or unsubstituted C6 to C20 aromatic hydrocarbon ring,

[0078] X 1 to X 6may each independently be or include, for example, a substituted or unsubstituted C6 to C20 aromatic hydrocarbon group.

[0079] L 1 and L 2 may each independently be or include, for example, a divalent organic group.

[0080] n may be an integer from 1 to 100, and the average value of n may be a value from 1 to 10 (for example, the average value of n for all polymer molecules in the composition may be from 1 to 10).

[0081] The polymer may include a portion containing an aromatic hydrocarbon ring, for example, X 1 、X 2 、Ar 1 and Ar 2 as well as X 5 、X 6 、Ar 5 and Ar 6 , at both ends, thereby improving the gap filling characteristics of the composition and the heat resistance of the hard mask layer formed from the composition. In addition, these portions may have a three-dimensional structure and may include flow connecting groups represented by L1 and L2, such that the polymer has excellent solubility and coating properties in a solvent. Therefore, the planarization characteristics of the hard mask layer formed from the composition can be improved.

[0082] In one embodiment, Ar 1 to Ar 6 may each independently be or include a substituted or unsubstituted aromatic hydrocarbon ring of Group 1, for example, a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, or a substituted or unsubstituted pyrene.

[0083] [Group 1]

[0084]

[0085] In one embodiment, X 1 to X 6 may each independently include, for example, a substituted or unsubstituted portion of Group 2, for example, a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted anthracene, a substituted or unsubstituted pyrene, or a combination thereof, or a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted pyrene, or a combination thereof.

[0086] [Group 2]

[0087]

[0088] In one embodiment, X 1 to X6 The moieties can each independently be substituted by deuterium, a halogen atom, an amino group, a hydroxyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

[0089] In one embodiment, L 1 and L 2 can each independently be represented by one of Chemical Formulas 2 to 5.

[0090] [Chemical Formula 2]

[0091]

[0092] [Chemical Formula 3]

[0093]

[0094] [Chemical Formula 4]

[0095]

[0096] [Chemical Formula 5]

[0097]

[0098] In Chemical Formulas 2 to 5, M 1 to M 4 can each independently be one of the substituted or unsubstituted moieties of Group 3, for example, substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, or a combination thereof, or substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, or a combination thereof.

[0099] [Group 3]

[0100]

[0101] In Group 3, L a to L c can each independently be, for example, a single bond, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C2-C10 alkenylene group, or a combination thereof, for example, a single bond or a substituted or unsubstituted C1-C5 alkylene group, or a combination thereof.

[0102] In one embodiment, Z a and Z b can each independently be, for example, -O-, -S-, -SO2-, -C(=O)-, or -NR a - (wherein, Ra may be, for example, hydrogen, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted C6-C20 aryl group), for example, -O-, or -S-.

[0103] In one embodiment, s1 and s2 may each independently be 0 or 1, and t may be an integer from 0 to 4.

[0104] In one embodiment, in Chemical Formulas 2 to 4, p1 to p3 and q1 to q3 may each independently be an integer from 0 to 4, for example, an integer from 0 to 3, 0, or 1.

[0105] In one embodiment, in Chemical Formula 5, p4 may be an integer from 1 to 5, for example, an integer from 1 to 3, 1, or 2. In one embodiment, in Chemical Formulas 2 to 5, * is a connection point.

[0106] In one embodiment, L 1 and L 2 may each independently be represented by one of Chemical Formulas 7 to 13.

[0107] [Chemical Formula 7]

[0108]

[0109] [Chemical Formula 8]

[0110]

[0111] [Chemical Formula 9]

[0112]

[0113] [Chemical Formula 10]

[0114]

[0115] [Chemical Formula 11]

[0116]

[0117] [Chemical Formula 12]

[0118]

[0119] [Chemical Formula 13]

[0120]

[0121] In Chemical Formulas 7 to 13, * is a connection point.

[0122] In one embodiment, n in Chemical Formula 1 can be an integer from 1 to 100, and the average value of n can be a value from 1 to 10. In one embodiment, n can be an integer from 1 to 50, for example, an integer from 1 to 40 or an integer from 1 to 30, and the average value of n can be a value from 1 to 10, for example, a value from 1 to 7 or a value from 1 to 5. The average value of n refers to the number calculated by dividing the weight-average molecular weight of the polymer by the molecular weight of the repeating structural unit within the polymer.

[0123] In one embodiment, the polymer can be represented by one of Chemical Formulas 1-1 to 1-3.

[0124] [Chemical Formula 1-1]

[0125]

[0126] [Chemical Formula 1-2]

[0127]

[0128] [Chemical Formula 1-3]

[0129]

[0130] In Chemical Formulas 1-1 to 1-3, R1 to R6 can each independently be or include, for example, deuterium, a hydroxyl group, a substituted or unsubstituted C1 to C5 alkoxy group, a substituted or unsubstituted C1 to C5 alkyl group, or a combination thereof, or deuterium, a hydroxyl group, a substituted or unsubstituted C1 to C5 alkoxy group, or a combination thereof.

[0131] In Chemical Formulas 1-1 to 1-3, y1 to y6 can each independently be an integer from 1 to 4, for example, an integer from 1 to 3, 1, or 2.

[0132] In Chemical Formulas 1-1 to 1-3, the average value of n can be from 1 to 10, for example, a value from 1 to 7 or a value from 1 to 5.

[0133] The polymer may have a weight-average molecular weight of, for example, from about 1,000 g / mol to about 100,000 g / mol. In one embodiment, the polymer may have a weight-average molecular weight of, for example, from about 1,000 g / mol to about 9,500 g / mol, from about 1,000 g / mol to about 9,000 g / mol, from about 1,200 g / mol to about 9,000 g / mol, from about 1,200 g / mol to about 8,000 g / mol, from about 1,500 g / mol to about 8,000 g / mol, from about 1,500 g / mol to about 7,000 g / mol, from about 1,500 g / mol to about 6,000 g / mol, from about 1,500 g / mol to about 5,000 g / mol, or from about 1,500 g / mol to about 3,000 g / mol. Maintaining the weight-average molecular weight within the above ranges can help ensure that the carbon content and solubility in the solvent of the hard mask composition containing the polymer can be adjusted, so that a hard mask layer with optimal gap filling and planarization characteristics can be prepared.

[0134] The polymer may be included in an amount of, for example, from about 0.1 wt% to about 30 wt% based on the total weight of the hard mask composition. In one embodiment, the polymer may be included in an amount of from about 0.2 wt% to about 30 wt%, such as from about 0.5 wt% to about 30 wt%, from about 1 wt% to about 30 wt%, from about 1.5 wt% to about 25 wt%, or from about 2 wt% to about 20 wt%. Maintaining the amount of the polymer within the above ranges can help ensure that the thickness, surface roughness, and degree of planarization of the hard mask can be easily adjusted.

[0135] The hard mask composition according to one embodiment may include a solvent. In one embodiment, the solvent may be, for example, propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetylacetone, ethyl 3-ethoxypropionate, or the like. In one embodiment, a suitable solvent may be used as long as it has sufficient solubility or dispersibility for the polymer.

[0136] In one embodiment, the hard mask composition may further include additives, such as surfactants, crosslinking agents, thermal acid generators, and plasticizers.

[0137] The surfactant may include, for example, fluoroalkyl compounds, alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, or the like.

[0138] The crosslinking agent may include, for example, melamine, substituted urea, or a polymer crosslinking agent. In one embodiment, it may be a crosslinking agent having at least two crosslinking substituents, such as methoxymethylated glycoruryl, butoxymethylated glycoruryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea.

[0139] In one embodiment, as the crosslinking agent, a crosslinking agent having high heat resistance may be used. The crosslinking agent having high heat resistance may include a compound containing a crosslinking substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule.

[0140] In one embodiment, the thermal acid generator may include an acid compound, such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, or 2,4,4,6-tetrabromocyclohexadienone, benzoyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, or other organic sulfonic acid alkyl esters.

[0141] According to some embodiments, a hard mask layer including a cured product of the above hard mask composition may be provided.

[0142] A method of forming a pattern using the above hard mask composition is described below.

[0143] The method of forming a pattern according to some embodiments may include, for example, providing a material layer on a substrate, applying the hard mask composition including the above polymer and solvent onto the material layer, heat-treating the hard mask composition to form a hard mask layer, forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern to expose a part of the material layer, and etching the exposed part of the material layer.

[0144] The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. The material layer may be a material to be ultimately patterned, such as a metal layer such as an aluminum layer and a copper layer, a semiconductor layer such as a silicon layer, or an insulating layer such as a silicon dioxide layer and a silicon nitride layer. The material layer may be formed by a method such as a chemical vapor deposition (CVD) process.

[0145] The hard mask composition is the same as described above and can be applied by spin coating in the form of a solution. Here, the applied thickness of the hard mask composition can be, for example, about to about

[0146] The heat treatment of the hard mask composition can be carried out at about 100 °C to about 1,000 °C for about 10 seconds to about 1 hour. In one embodiment, the heat treatment of the hard mask composition may include a plurality of heat treatment processes, for example, a first heat treatment process and a second heat treatment process.

[0147] In one embodiment, the heat treatment of the hard mask composition may include, for example, one heat treatment process carried out at about 100 °C to about 1,000 °C for about 10 seconds to about 1 hour. In one embodiment, the heat treatment can be carried out in an air or nitrogen atmosphere, or in an atmosphere with an oxygen concentration of about 1 wt% or less.

[0148] In one embodiment, the heat treatment of the hard mask composition may include, for example, a first heat treatment process carried out at about 100 °C to about 1,000 °C, about 100 °C to about 800 °C, about 100 °C to about 500 °C, or about 150 °C to about 400 °C for about 30 seconds to about 1 hour or about 30 seconds to about 30 minutes, about 30 seconds to about 10 minutes, or 30 seconds to about 5 minutes.

[0149] In one embodiment, the heat treatment may include a second heat treatment process carried out continuously, for example, at about 100 °C to about 1,000 °C, about 300 °C to about 1,000 °C, about 500 °C to about 1,000 °C, or about 500 °C to about 600 °C for about 30 seconds to about 1 hour, for example, about 30 seconds to about 30 minutes, about 30 seconds to about 10 minutes, or about 30 seconds to 5 minutes. In one embodiment, the first heat treatment process and the second heat treatment process can be carried out in an air or nitrogen atmosphere, or can be carried out in an atmosphere with an oxygen concentration of about 1 wt% or less.

[0150] By carrying out at least one heat treatment step of the hard mask composition at a high temperature of 200 °C or higher, high etch resistance capable of withstanding the etch gases and chemical liquids exposed in subsequent processes (including the etching process) can be exhibited.

[0151] In one embodiment, forming the hard mask layer may include a UV / Vis curing process and / or a near-IR curing process.

[0152] In one embodiment, forming the hard mask layer may include at least one of a first heat treatment process, a second heat treatment process, a UV / Vis curing process, and a near-IR curing process, or may include two or more processes carried out continuously.

[0153] In one embodiment, the method may further include forming a silicon-containing thin layer on the hard mask layer. The silicon-containing thin layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, SiN, or the like.

[0154] In one embodiment, the method may further include forming a bottom antireflective coating (BARC) on the silicon-containing thin layer or the hard mask layer before forming the photoresist layer.

[0155] In one embodiment, the exposure of the photoresist layer may be performed using, for example, ArF, KrF, or EUV. After exposure, a heat treatment may be performed at about 100 °C to about 700 °C.

[0156] In one embodiment, the etching process of the exposed portion of the material layer may be performed by a dry etching process using an etching gas. In one embodiment, the etching gas may be, for example, N2 / O2, CHF3, CF4, Cl2, BCl3, or a mixed gas thereof.

[0157] The etched material layer may be formed into a plurality of patterns, and these plurality of patterns may include metal patterns, semiconductor patterns, insulating patterns, or the like, such as various patterns of semiconductor integrated circuit devices.

[0158] The following examples and comparative examples are provided to highlight the features of one or more embodiments, but it should be understood that these examples and comparative examples should not be construed as limiting the scope of the embodiments, and the comparative examples should not be construed as exceeding the scope of the embodiments. In addition, it should be understood that the embodiments are not limited to the specific details described in the examples and comparative examples.

[0159] Synthesis of Polymer

[0160] Synthesis Example 1

[0161] 1.8 moles of 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 1 mole of 4,4'-oxybis((methoxymethyl)benzene), 123 grams of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 grams of diethyl sulfate were added to a flask, and then the mixture was stirred at 100 °C to carry out a polymerization reaction.

[0162] After the polymerization reaction is completed, the intermediate product therein is slowly cooled to room temperature, 40 g of distilled water and 400 g of methanol are added, and then the mixture is stirred vigorously and allowed to stand. After removing the supernatant, the precipitate therein is dissolved in 80 g of cyclohexanone, and then 320 g of methanol is used to stir vigorously and allowed to stand (primary). Here, after removing the obtained supernatant again, the precipitate therein is dissolved in 80 g of cyclohexanone (secondary). The primary process and the secondary process are regarded as one purification process and repeated three times. The purified polymer is dissolved in 80 g of cyclohexanone, and the residual methanol and distilled water in the solution are removed under reduced pressure to obtain a polymer represented by Chemical Formula 1-4 (Mw: 3,000 g / mol).

[0163] [Chemical Formula 1-4]

[0164]

[0165] Synthesis Example 2

[0166] A polymer represented by Chemical Formula 1-5 (Mw: 3,400 g / mol) was obtained in the same manner as in Synthesis Example 1, except that 1.6 mol of 9,9-bis(3,4-dihydroxyphenyl)fluorene was used instead of 1.8 mol of 9,9-bis(6-hydroxy-2-naphthyl)fluorene, and 1 mol of 4,4'-oxybis((methoxymethyl)benzene) was used.

[0167] [Chemical Formula 1-5]

[0168]

[0169] Synthesis Example 3

[0170] A polymerization reaction was carried out by adding 1.8 mol of 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 1 mol of 1,4-bis(methoxymethyl)benzene, 123 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of diethyl sulfate to a flask, and then stirring the mixture at 100 °C.

[0171] After the polymerization reaction is completed, the intermediate product therein is slowly cooled to room temperature, 40 g of distilled water and 400 g of methanol are added, and then the mixture is stirred vigorously and allowed to stand. After removing the supernatant, the precipitate therein is dissolved in 80 g of cyclohexanone, and then 320 g of methanol is used to stir vigorously and allowed to stand (primary). Here, the obtained supernatant is removed again, and the obtained precipitate is dissolved in 80 g of cyclohexanone (secondary). The primary process and the secondary process are regarded as one purification process and repeated three times. The purified polymer is dissolved in 80 g of cyclohexanone, and the residual methanol and distilled water in the solution are removed under reduced pressure to obtain a polymer represented by Chemical Formula 1-6 (Mw: 3,000 g / mol).

[0172] [Chemical Formula 1-6]

[0173]

[0174] Comparative Synthesis Example 1

[0175] A polymerization reaction was carried out by adding 1 mole of 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 1 mole of 4,4'-oxybis((methoxymethyl)benzene), 123 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of diethyl sulfate to a flask, and then stirring the mixture at 100 °C.

[0176] After the polymerization reaction was completed, the intermediate product therein was slowly cooled to room temperature, 40 g of distilled water and 400 g of methanol were added, and then it was stirred vigorously and allowed to stand. After removing the supernatant, the precipitate therein was dissolved in 80 g of cyclohexanone, and then it was stirred vigorously with 320 g of methanol and allowed to stand (primary). Here, the obtained supernatant was removed again, and the precipitate was dissolved in 80 g of cyclohexanone (secondary). The primary process and the secondary process were regarded as one purification process and repeated three times. The purified polymer was dissolved in 80 g of cyclohexanone, and the residual methanol and distilled water in the solution were removed under reduced pressure to obtain a polymer represented by Chemical Formula 1-7 (Mw: 3,000 g / mol).

[0177] [Chemical Formula 1-7]

[0178]

[0179] Comparative Synthesis Example 2

[0180] A polymerization reaction was carried out by adding 1 mole of 9,9-bis(3,4-dihydroxyphenyl)fluorene, 1 mole of 1,4-bis(methoxymethyl)benzene, 123 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of diethyl sulfate to a flask, and then stirring the mixture at 100 °C.

[0181] After the polymerization reaction was completed, the intermediate product therein was slowly cooled to room temperature, 40 g of distilled water and 400 g of methanol were added, and then it was stirred vigorously and allowed to stand. After removing the supernatant, the precipitate therein was dissolved in 80 g of cyclohexanone, and then it was stirred vigorously with 320 g of methanol and allowed to stand (primary). Here, the obtained supernatant was removed again, and the obtained precipitate was dissolved in 80 g of cyclohexanone (secondary). The primary process and the secondary process were regarded as one purification process and repeated three times. The purified polymer was dissolved in 80 g of cyclohexanone, and the residual methanol and distilled water in the solution were removed under reduced pressure to obtain a polymer represented by Chemical Formula 1-8 (Mw: 3,400 g / mol).

[0182] [Chemical Formula 1-8]

[0183]

[0184] Preparation of Hard Mask Composition

[0185] Examples 1 to 3 and Comparative Examples 1 to 2

[0186] To prepare the hard mask composition, 3 grams of each of the polymers in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2 were dissolved in 17 grams of cyclohexanone, and filtered through 0.1 μm polytetrafluoroethylene (TEFLON).

[0187] Evaluation 1: Evaluation of Gap-Filling Property and Planarization Property

[0188] Figure 1 is a reference diagram for explaining the method of evaluating the planarization property by the level difference of the hard mask layer. By adjusting the mass ratio of the solute to the solvent to 3:97, each hard mask composition of Examples 1 to 3 and Comparative Examples 1 to 2 was coated on each silicon pattern wafer, and then baked to form a thick hard mask layer. The gap-filling property of the hard mask layer was evaluated by examining the pattern cross-section using a scanning electron microscope (SEM) to determine whether voids were generated. The planarization property was evaluated by measuring and calculating the average film thickness (h1) of any three points on the non-patterned substrate part and another average film thickness (h2) of any three points on the patterned substrate part using a film thickness meter produced by K-MAC Co., Ltd., to calculate the level difference (|h1 - h2|). The smaller the level difference (|h1 - h2|), the more excellent the planarization property. The results are shown in Table 1.

[0189] [Table 1]

[0190]

[0191] Referring to Table 1, compared with the hard mask layers formed from the hard mask compositions of the comparative examples, the hard mask layers formed from the hard mask compositions of Examples 1 to 3 exhibited excellent planarization properties and gap-filling properties.

[0192] Evaluation 2: Solubility

[0193] Weigh each of the polymers of Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2 and add them to 20 g of ethyl lactate (hereinafter referred to as EL), propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and propylene glycol monomethyl ether (hereinafter referred to as PGME) to evaluate solubility. Solubility was evaluated by measuring the amount of each polymer dissolved in 20 g of the same solvent and converting it to a percentage as follows.

[0194] Solubility (%) = {mass of polymer (g) / mass of solvent (20 g)}

[0195] [Table 2]

[0196] EL (%) PGMEA (%) PGME (%) Example 1 50.7 38.7 55.7 Example 2 37.1 33.5 47.1 Example 3 40.2 34.1 35.8 Comparative Example 1 13.2 1.5 10.4 Comparative Example 2 23.4 0 26.4

[0197] Referring to Table 2, the polymers of the synthesis examples showed more excellent solubility in the EL, PGMEA, and PGME solvents than the polymers of the comparative synthesis examples.

[0198] By summarizing and reviewing, as the pattern to be formed is miniaturized, it may be difficult to provide a fine pattern with excellent profile using only certain lithography techniques. Therefore, an auxiliary layer called a hard mask layer can be formed between the material layer and the photoresist layer to provide a fine pattern.

[0199] One or more embodiments can provide a hard mask composition that can be effectively applied to a hard mask layer.

[0200] The hard mask composition formed according to some embodiments can help ensure excellent solubility in a solvent and can be effectively applied to a hard mask layer.

[0201] According to some embodiments, the hard mask layer formed from the hard mask composition can help ensure excellent gap filling characteristics and planarization characteristics.

[0202] Exemplary embodiments have been disclosed herein. Although specific terms are used, they are used and interpreted in a general and descriptive sense only and not for purposes of limitation. In some cases, as will be apparent to those of ordinary skill in the art at the time of filing of this application, features, characteristics, and / or elements related to a particular embodiment can be used alone or in combination with features, characteristics, and / or elements related to other embodiments, unless otherwise clearly stated. Accordingly, those skilled in the art will understand that various changes in form and detail can be made without departing from the spirit and scope of the invention as set forth in the following claims.

Claims

1. A hard mask composition, comprising: A polymer represented by Chemical Formula 1; And A solvent, [Chemical Formula 1] Wherein, in Chemical Formula 1, Ar 1 to Ar 6 each independently is a substituted or unsubstituted C6 to C20 aromatic hydrocarbon ring, X 1 to X 6 each independently is a substituted or unsubstituted C6-C20 aromatic hydrocarbon group, L 1 and L 2 each independently represents a divalent organic group, and n is an integer from 1 to 100.

2. The hard mask composition according to claim 1, wherein Ar 1 to Ar 6 are each independently a substituted or unsubstituted aromatic hydrocarbon ring of Group 1: [Group 1] 3. The hard mask composition according to claim 1, wherein X 1 to X 6 each independently comprises a substituted or unsubstituted moiety of Group 2: [Group 2] 4. The hard mask composition according to claim 1, wherein: L 1 and L 2 each independently represented by one of Chemical Formula 2 to Chemical Formula 5: [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] In Chemical Formulas 2 to 5, M 1 to M 4 each independently includes a substituted or unsubstituted moiety of Group 3, p1 to p3 and q1 to q3 are each independently an integer from 0 to 4, p4 is an integer from 1 to 5, and * is a connection point, [Group 3] In Group 3, L a to L c each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, or a combination thereof Z a and Z b each independently is -O-, -S-, -SO2-, -C(=O)- or -NR a -, where R a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group s1 and s2 are each independently 0 or 1, and t is an integer from 0 to 4.

5. The hard mask composition according to claim 1, wherein: L 1 and L 2 each independently represented by one of Chemical Formulas 7 to 13, where * is the point of attachment: [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] 6. The hard mask composition according to claim 1, wherein: The polymer is represented by one of Chemical Formulas 1-1 to 1-3: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In Chemical Formulas 1-1 to 1-3, R 1 to R 6 each independently is deuterium, a hydroxyl group, a substituted or unsubstituted C1-C5 alkoxy group, a substituted or unsubstituted C1-C5 alkyl group, or a combination thereof y1 to y6 are each independently an integer from 1 to 4, and n is an integer from 1 to 100.

7. The hard mask composition according to claim 1, wherein the polymer has a weight average molecular weight of 1,000 g / mol to 10,000 g / mol.

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

9. The hard mask composition according to claim 1, wherein the solvent is propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetylacetone or ethyl 3-ethoxypropionate.

10. A hard mask layer, comprising a cured product of the hard mask composition according to claim 1.

11. A method of forming a pattern, the method comprising: Providing a material layer on a substrate; Applying the hard mask composition according to claim 1 to the material layer; Thermally treating the hard mask composition to form a hard mask layer; Forming a photoresist layer on the hard mask layer; Exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer; And Etching the exposed portion of the material layer.

12. The method according to claim 11, wherein the thermal treatment is performed at 100 °C to 1,000 °C.

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