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

Abstract

A hardmask composition, a hardmask layer manufactured from the hardmask composition, and a method of forming one or more patterns using the hardmask layer manufactured from the hardmask composition, the hardmask composition comprising: 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 priority to and the benefit of Korean Patent Application No. 10-2023-0091250 filed in the Korean Intellectual Property Office on July 13, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Various embodiments relate to a hard mask composition, a hard mask layer, and a method of forming a pattern. Background Art

[0004] Recently, the semiconductor industry has developed ultra-fine technology with patterns ranging from several nanometers to tens of nanometers in size. Such ultra-fine technology can utilize effective photolithography technology. Some photolithography technologies may include: providing a material layer on a semiconductor substrate; coating a photoresist layer on the material layer; exposing and developing the photoresist layer to provide a photoresist pattern; and etching the material layer using the photoresist pattern as a mask. Recently, with the miniaturization of the pattern to be formed, it may be difficult to provide a fine pattern with an excellent profile using only some photolithography technologies. Therefore, an auxiliary layer called a hard mask layer may be formed between the material layer and the photoresist layer to provide a fine pattern. Summary of the invention

[0005] The embodiment may be implemented by providing a hard mask composition including: a polymer including a structural unit represented by Chemical Formula 1; and a solvent,

[0006] [Chemical formula 1]

[0007]

[0008] Wherein, in Chemical Formula 1, A is a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, X 1 and X 2 Each is independently a single bond, -C(=O)-, a substituted or unsubstituted C1 to C30 alkylene group, or a combination thereof, Y is a substituted or unsubstituted C2 to C30 alkenylene group, or a substituted or unsubstituted C2 to C30 alkynylene group, and * is a connection point.

[0009] A may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group which is part of Group 1,

[0010] [Group 1]

[0011]

[0012] A may be a substituted C6 to C30 aromatic hydrocarbon group, and the substituent of the substituted C6 to C30 aromatic hydrocarbon group may be deuterium, a hydroxyl group, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 heteroalkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0013] X 1 and X 2 Each may independently be -C(=O)-, a substituted C1 to C20 alkylene group, or a combination thereof.

[0014] Y may be a substituted or unsubstituted C2 to C10 alkenylene group, or a substituted or unsubstituted C2 to C10 alkynylene group.

[0015] A may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group which is part of Group 1-1, [Group 1-1]

[0016]

[0017] Chemical formula 1 can be represented by Chemical formula 1-1 or Chemical formula 1-2, [Chemical formula 1-1]

[0018]

[0019] [Chemical formula 1-2]

[0020]

[0021] In Chemical Formula 1-1 and Chemical Formula 1-2, A may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that is part of Group 1-1, and X 1 and X 2 may each independently be a single bond, -C(=O)-, a substituted or unsubstituted C1 to C30 alkylene group, or a combination thereof, and * is a connection point,

[0022] [Group 1-1]

[0023]

[0024] Chemical Formula 1 may be represented by one of Chemical Formulas 1-1-1 to 1-1-4 and Chemical Formulas 1-2-1 to 1-2-4,

[0025] [Chemical formula 1-1-1]

[0026]

[0027] [Chemical formula 1-1-2]

[0028]

[0029] [Chemical formula 1-1-3]

[0030]

[0031] [Chemical formula 1-1-4]

[0032]

[0033] [Chemical formula 1-2-1]

[0034]

[0035] [Chemical formula 1-2-2]

[0036]

[0037] [Chemical formula 1-2-3]

[0038]

[0039] [Chemical formula 1-2-4]

[0040]

[0041] In Chemical Formulas 1-1-1 to 1-1-4 and Chemical Formulas 1-2-1 to 1-2-4, A 1 To A 6 Each independently may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group.

[0042] A 1 To A 6 a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group which may each independently be part of group 1-1,

[0043] [Group 1-1]

[0044]

[0045] The polymer may further include a structural unit represented by Chemical Formula 2,

[0046] [Chemical formula 2]

[0047]

[0048] In Chemical Formula 2, B may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, L may be a single bond, or a substituted or unsubstituted C1 to C30 alkylene group, and * is a connection point.

[0049] B in Chemical Formula 2 may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that is part of Group 2,

[0050] [Group 2]

[0051]

[0052] L in Chemical Formula 2 may be a substituted or unsubstituted methylene group.

[0053] The polymer may have a weight average molecular weight of about 1,000 g / mol to about 200,000 g / mol.

[0054] The polymer may be included in an amount of about 0.1 wt % to about 30 wt % based on the total weight of the hardmask composition.

[0055] The solvent may include 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, methylpyrrolidone, acetylacetone or ethyl 3-ethoxypropionate.

[0056] The embodiment may be implemented by providing a hard mask layer including a cured product of the hard mask composition according to the embodiment.

[0057] An embodiment can be implemented by providing a method for forming a pattern, the method comprising: providing a material layer on a substrate; applying a hard mask composition according to an embodiment 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.

[0058] Forming the hard mask layer may include performing a heat treatment at about 100° C. to about 1,000° C. DETAILED DESCRIPTION

[0059] Exemplary embodiments will now be described more fully below; however, the embodiments may be implemented 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] It should also be understood that when a layer or element is referred to as being "on" another layer or element, the layer or element may be directly on the other layer or element, or intervening layers may also be present. In addition, it should also be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or one or more intervening layers may also be present.

[0061] When no definition is provided otherwise, "substituted" as described herein may refer to that a hydrogen atom of a compound is replaced by a substituent selected from the group consisting of a halogen atom (F, Br, Cl, or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazo 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 phosphate group or a salt thereof, a vinyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C6 to C30 allyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, or a combination thereof. As used herein, hydrogen substitution (-H) may include deuterium substitution (-D) or tritium substitution (-T). For example, any hydrogen in any compound described herein may be protium, deuterium, or tritium (e.g., based on natural substitution or artificial substitution). As used herein, the term "or" is not necessarily exclusive, for example, "A or B" will include A, B, or A and B. Unless otherwise stated, as used herein, * is a point of attachment.

[0062] In addition, two adjacent substituents in a substituted halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazone 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 C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclyl group may be fused to form a ring. For example, a substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

[0063] When no definition is otherwise provided, the “aromatic hydrocarbon group” described herein means a group having one or more hydrocarbon aromatic moieties, and includes a form in which the hydrocarbon aromatic moieties are connected by a single bond, a non-aromatic condensed ring form in which the hydrocarbon aromatic moieties are directly or indirectly condensed, or a combination thereof, as well as a non-condensed aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring.

[0064] More specifically, the substituted or unsubstituted aromatic hydrocarbon group may be substituted or unsubstituted phenyl (phenylene), substituted or unsubstituted naphthyl (naphthylene), substituted or unsubstituted anthracenyl (anthracenylene), substituted or unsubstituted phenanthryl (phenanthrylene), substituted or unsubstituted fused tetraphenyl (fused tetraphenylene), substituted or unsubstituted pyrenyl (pyrenylene), substituted or unsubstituted biphenyl (biphenylene), substituted or unsubstituted terphenyl (terphenylene), substituted or unsubstituted quaterphenyl (quaterphenylene), substituted or unsubstituted chrysene (chrysylene), substituted or unsubstituted triphenylene (triphenylene), substituted or unsubstituted perylene (perylene), substituted or unsubstituted indenyl (indenylene), combinations thereof, or fused rings of the combinations thereof, but are not limited thereto.

[0065] When no definition is otherwise provided, the “hetero” described herein refers to a group including 1 to 3 heteroatoms selected from N, O, S, Se and P.

[0066] When a definition is not otherwise provided, the "heteroalkyl group" described herein refers to a group including a heteroelement selected from N, O, S, P and Si instead of one or more carbon atoms forming an alkyl group.

[0067] When no additional definition is provided, "heteroaryl" as used herein refers to an aryl group comprising at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryl groups may be directly connected by a sigma bond, or when the heteroaryl group comprises two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0068] The polymer used herein may include both oligomers and polymers.

[0069] 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) (column is Shodex Company LF-804, standard sample is Showa Company polystyrene).

[0070] A hard mask composition according to some embodiments may include, for example: a polymer including a structural unit represented by Chemical Formula 1; and a solvent.

[0071] [Chemical formula 1]

[0072]

[0073] In Chemical Formula 1, A may be or may include, for example, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group.

[0074] X 1 and X 2 Each independently may be or include, for example, a single bond, -C(=O)-, a substituted or unsubstituted C1 to C30 alkylene group, or a combination thereof.

[0075] Y may be or may include, for example, a substituted or unsubstituted C2 to C30 alkenylene group, or a substituted or unsubstituted C2 to C30 alkynylene group.

[0076] * is the connection point.

[0077] According to some embodiments, a polymer included in a hard mask composition may include an aromatic hydrocarbon group. Therefore, the carbon content in the polymer including the structural unit may be increased, and a hard mask layer formed from the hard mask composition including the polymer may have high etching resistance.

[0078] In addition, the structural unit represented by Chemical Formula 1 may include an unsaturated hydrocarbon, so that the number of crosslinks caused by a cycloaddition reaction during the curing of the hard mask composition may be increased, thereby ensuring etching resistance and heat resistance. The composition may not form a ring in a pre-cured state, and when applied using a spin coating method, the composition may have excellent solubility properties and excellent planarization properties and gap filling characteristics.

[0079] Furthermore, by including unsaturated hydrocarbons in the main chain of the polymer, the loss of unsaturated hydrocarbons can be reduced during the heat treatment process and under the curing conditions of the hard mask composition, thereby increasing the number of crosslinks in the polymer compared to the case where the unsaturated hydrocarbons are included in the side chain or terminal of the polymer, and thus improving the crosslinking characteristics of the hard mask composition and ensuring excellent film strength of the hard mask layer formed by the hard mask composition.

[0080] In one embodiment, A may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, for example, a part of Group 1. The substituted or unsubstituted aromatic hydrocarbon group as a part described herein refers to an unsubstituted (e.g., divalent) group as one of the exemplified parts, or the group may be further substituted as described above.

[0081] [Group 1]

[0082]

[0083] In one embodiment, A may be a substituted aromatic hydrocarbon group, such as a part of Group 1, and may be substituted with deuterium, a hydroxyl group, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 heteroalkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof.

[0084] In one embodiment, A may be, for example, a substituted or unsubstituted aromatic hydrocarbon group that is part of Group 1-1. In one embodiment, A may be, for example, a substituted or unsubstituted biphenylene, pyrene, naphthalene, benzoperylene, and the like.

[0085] [Group 1-1]

[0086]

[0087] In one embodiment, X 1 and X 2 Each independently may be, for example, -C(=O)-, a substituted C1 to C20 alkylene group, or a combination thereof. In one embodiment, the substituted C1 to C20 alkylene group may be, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, etc., wherein hydrogen is replaced by a substituent group (e.g., a substituted methylene group, an ethylene group, or a propylene group).

[0088] The substituents of the substituted C1 to C20 alkylene group may include, for example, a halogen atom (F, Br, Cl or I), a hydroxyl group, an alkoxy group, a cyano group, an azido group, a carbonyl group, a thiol group, an ester group, a vinyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 heteroalkyl group, a C6 to C30 aryl group, a C3 to C20 heteroaryl group, or a combination thereof, such as a hydroxyl group, an alkoxy group, a carbonyl group or a C6 to C30 aryl group.

[0089] In one embodiment, X 1 and X 2 -C(=O)- or hydroxyl and / or C6 to C30 aromatic groups may be included as substituents, and when the hard mask composition is cured, the cross-linking properties of the hard mask composition can be improved by increasing the number of cross-links in the polymer, and the strength of the hard mask layer formed by the hard mask composition can be improved, thereby improving the pattern forming ability.

[0090] In one embodiment, Y may be, for example, a substituted or unsubstituted C2 to C10 alkenylene group, or a substituted or unsubstituted C2 to C10 alkynylene group. The substituted or unsubstituted C2 to C10 alkenylene group may be, for example, a C2 to C10 alkenylene group, a C2 to C7 alkenylene group, or a C2 to C5 alkenylene group, or an unsaturated aliphatic hydrocarbon group including at least one or more carbon double bonds. The substituted or unsubstituted C2 to C10 alkynylene group may be, for example, a C2 to C10 alkynylene group, a C2 to C7 alkynylene group, or a C2 to C5 alkynylene group, or may be an unsaturated aliphatic hydrocarbon group including at least one or more carbon triple bonds.

[0091] In one embodiment, Chemical Formula 1 may be represented by, for example, Chemical Formula 1-1 or Chemical Formula 1-2.

[0092] [Chemical formula 1-1]

[0093]

[0094] [Chemical formula 1-2]

[0095]

[0096] In Chemical Formula 1-1 and Chemical Formula 1-2, A may be, for example, a substituted or unsubstituted aromatic hydrocarbon group that is a part of Group 1 or a part of Group 1-1. 1 and X 2 Each independently may be, for example, a single bond, -C(=O)-, a substituted or unsubstituted C1 to C30 alkylene group, or a combination thereof. * is a connection point.

[0097] In one embodiment, Chemical Formula 1 may be represented by, for example, one of Chemical Formulas 1-1-1 to 1-1-4 and Chemical Formulas 1-2-1 to 1-2-4.

[0098] [Chemical formula 1-1-1]

[0099]

[0100] [Chemical formula 1-1-2]

[0101]

[0102] [Chemical formula 1-1-3]

[0103]

[0104] [Chemical formula 1-1-4]

[0105]

[0106] [Chemical formula 1-2-1]

[0107]

[0108] [Chemical formula 1-2-2]

[0109]

[0110] [Chemical formula 1-2-3]

[0111]

[0112] [Chemical formula 1-2-4]

[0113]

[0114] In Chemical Formulas 1-1-1 to 1-1-4 and Chemical Formulas 1-2-1 to 1-2-4, A 1 To A 6 Each of A and B may be, for example, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, such as a substituted or unsubstituted aromatic hydrocarbon group that is part of Group 1 or a part of Group 1-1. 1 To A 6 Each of A and B may independently be or include, for example, phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl or benzoperylene. 1 To A 6 Each independently may be or include, for example, a naphthyl group, a biphenyl group, a pyrenyl group or a benzoperylene group.

[0115] In one embodiment, the polymer may further include a structural unit represented by Chemical Formula 2.

[0116] [Chemical formula 2]

[0117]

[0118] In Chemical Formula 2, B may be or may include, for example, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group.

[0119] L may be or may include, for example, a single bond, or a substituted or unsubstituted C1 to C30 alkylene group.

[0120] * is the connection point.

[0121] B in Chemical Formula 2 may be a substituted or unsubstituted aromatic hydrocarbon group that is part of Group 2, for example.

[0122] [Group 2]

[0123]

[0124] In one embodiment, L in Chemical Formula 2 may be, for example, a substituted or unsubstituted methylene group. In one embodiment, L in Chemical Formula 2 may be, for example, an unsubstituted methylene group.

[0125] The polymer may have a weight average molecular weight of about 1,000 g / mol to about 200,000 g / mol. In one embodiment, the polymer may have a weight average molecular weight of, for example, about 1,000 g / mol to about 150,000 g / mol, about 1,000 g / mol to about 100,000 g / mol, about 1,000 g / mol to about 10,000 g / mol, or about 1,200 g / mol to about 15,000 g / mol. By making the weight average molecular weight within the above range, the carbon content and solubility in the solvent of the hard mask composition including the above polymer can be adjusted and optimized.

[0126] The polymer may be included in an amount of, for example, 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, for example, about 0.2 wt % to about 30 wt %, about 0.5 wt % to about 30 wt %, about 1 wt % to about 30 wt %, about 1 wt % to about 25 wt %, or about 1 wt % to about 20 wt %. By including the polymer within the above range, the thickness, surface roughness, and planarization degree of the hard mask may be easily adjusted.

[0127] The hard mask composition may include a solvent. In one embodiment, the solvent may include, 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, methyl pyrrolidone, methyl pyrrolidone, acetylacetone, ethyl 3-ethoxypropionate, or a similar solvent. In one embodiment, the solvent may be a suitable solvent having sufficient solubility or dispersibility for the polymer.

[0128] In one embodiment, the hard mask composition may further include additives such as a surfactant, a cross-linking agent, a thermal acid generator, or a plasticizer.

[0129] The surfactant may include, for example, fluoroalkyl compounds, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, and the like.

[0130] The crosslinking agent may be, for example, melamine, substituted urea or a polymer crosslinking agent. In one embodiment, the crosslinking agent may be a crosslinking agent having at least two crosslinking substituents, such as methoxymethylated glycouryl, butoxymethylated glycoluryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea or butoxymethylated thiourea.

[0131] 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 having a crosslinking substituent having an aromatic ring (eg, a benzene ring or a naphthalene ring) in a molecule.

[0132] In one embodiment, the thermal acid generator may be, for example, an acid compound (e.g., p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid) or 2,4,4,6-tetrabromocyclohexadienonone, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate or other organic alkyl sulfonates.

[0133] According to some embodiments, a hard mask layer including a cured product of the aforementioned hard mask composition may be provided.

[0134] Hereinafter, a method of forming a pattern using the aforementioned hard mask composition is described.

[0135] According to some embodiments, the method of forming a pattern may include: providing a material layer on a substrate; applying a hard mask composition including the aforementioned polymer and a solvent 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. The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

[0136] The material layer may be a material to be finally patterned, such as a metal layer (such as an aluminum layer or a copper layer), a semiconductor layer (such as a silicon layer) or an insulating layer (such as a silicon oxide layer or a silicon nitride layer). The material layer may be formed by a method such as a chemical vapor deposition (CVD) process.

[0137] The hard mask composition may be the same as described above and may be applied by spin coating from a solution. In one embodiment, the hard mask composition may be applied to a thickness of, for example, about To date

[0138] The hard mask composition may be thermally treated at, for example, about 100° C. to about 1,000° C. for about 10 seconds to about 1 hour. In one embodiment, the thermal treatment of the hard mask composition may include a plurality of thermal treatment processes, such as a first thermal treatment process and a second thermal treatment process.

[0139] In one embodiment, the heat treatment of the hard mask composition may include, for example, a heat treatment process performed at about 100° C. to about 1,000° C. for about 10 seconds to about 1 hour, and the heat treatment may be performed, for example, in an air atmosphere, a nitrogen atmosphere, or an atmosphere having an oxygen concentration of about 1 wt % or less.

[0140] In one embodiment, the heat treatment of the hard mask composition may include, for example, a first heat treatment process, which is performed 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 100° C. to about 400° C. for about 10 seconds to about 1 hour, such as about 100° C. to about 1,000° C., such as about 300° C. to about 1,000° C., about 500° C. to about 1,000° C., or about 500° C. to about 800° C. for about 10 seconds to about 1 hour. In one embodiment, the first heat treatment and the second heat treatment may be performed in an air atmosphere, a nitrogen atmosphere, or an atmosphere having an oxygen concentration of about 1 wt % or less.

[0141] By performing at least one of the steps of heat-treating the hard mask composition at a high temperature, for example, 200° C. or higher, high etching resistance capable of withstanding etching gas and chemical liquid exposed in subsequent processes including an etching process may be exhibited.

[0142] In one embodiment, the formation of the hard mask layer may include an ultraviolet (UV) / visible light (Vis) curing process or a near infrared ray (IR) curing process.

[0143] In an implementation, the formation of the hard mask layer may include a first heat treatment process, a second heat treatment process, a UV / Vis curing process, or a near IR curing process, or may include two or more processes in succession.

[0144] 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 include, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiO, SiN, etc.

[0145] In one embodiment, the method may further include: before forming the photoresist layer, forming a bottom antireflective coating (BARC) on the silicon-containing thin layer or on the hard mask layer.

[0146] In one embodiment, the exposure of the photoresist layer may be performed using, for example, ArF, KrF, or extreme ultraviolet (EUV). After the exposure, a heat treatment may be performed at about 100° C. to about 700° C.

[0147] 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, and the etching gas may be, for example, N2 / O2, CHF3, CF4, Cl2, BCl3 or a mixture thereof.

[0148] The etched material layer may be formed into a plurality of patterns, and the plurality of patterns may be metal patterns, semiconductor patterns, insulation patterns, or the like, such as various patterns of a semiconductor integrated circuit device.

[0149] The following examples and comparative examples are provided to highlight the characteristics of one or more embodiments, but it should be understood that the examples and comparative examples should not be interpreted as limiting the scope of the embodiments, and the comparative examples should not be interpreted as exceeding the scope of the embodiments. In addition, it should be understood that the embodiments are not limited to the specific details set forth in the examples and comparative examples.

[0150] Synthesis Examples 1 to 3: Synthesis of Polymers

[0151] Synthesis example 1

[0152] 2-Hydroxypyrene (15.8 g, 0.05 mol), 1,1'-biphenyl-4-ol (8.5 g, 0.05 mol) and dimethyl fumaric acid (14.4 g, 0.1 mol) were placed in a 250 ml flask. Subsequently, p-toluenesulfonic acid monohydrate (0.57 g, 0.03 mmol) was dissolved in 100 g of propylene glycol monomethylether acetate (PGMEA), and the solution was added to the flask, and then stirred at 100°C. After taking out samples from the polymerization reactant at intervals of one hour, the reaction was completed when the weight average molecular weight of the sample was 2,000 g / mol to 2,500 g / mol. When the polymerization reaction was completed, the reactant was cooled to ambient temperature and added to 300 g of distilled water and 300 g of methanol, and then vigorously stirred and allowed to stand. After removing the supernatant therefrom, the precipitate thus obtained was dissolved in 100 g of PGMEA, and then stirred in 300 g of methanol and 300 g of distilled water and allowed to stand (primary process). Herein, after removing the supernatant obtained therefrom again, the precipitate thus obtained was dissolved in 80 g of PGMEA (secondary process). The primary process and the secondary process are regarded as a purification process, which is carried out three times in total. After purification, the polymer thus obtained was dissolved in 80 g of PGMEA, and the methanol and distilled water remaining in the solution were removed under reduced pressure, thereby obtaining a polymer comprising the structural units represented by Chemical Formula 1-1-1 to Chemical Formula 1-1-4. In Chemical Formula 1-1-1 to Chemical Formula 1-1-4, A 1 To A 3 Each is independently a moiety derived from 2-hydroxypyrene or 1,1'-biphenyl-4-phenol.

[0153] [Chemical formula 1-1-1]

[0154]

[0155] [Chemical formula 1-1-2]

[0156]

[0157] [Chemical formula 1-1-3]

[0158]

[0159] [Chemical formula 1-1-4]

[0160]

[0161] Synthesis example 2

[0162] A polymer including structural units represented by Chemical Formula 1-2-1 to Chemical Formula 1-2-5 was prepared in the same manner as in Synthesis Example 1 except that 2,2'-biphenol (18.6 g, 0.1 mol), dimethylacetylene dicarboxylate (14.2 g, 0.05 mol) and paraformaldehyde (1.5 g, 0.05 mol) were used as reactants. 4 To A 7 Each is independently a moiety derived from 2,2'-biphenol.

[0163] [Chemical formula 1-2-1]

[0164]

[0165] [Chemical formula 1-2-2]

[0166]

[0167] [Chemical formula 1-2-3]

[0168]

[0169] [Chemical formula 1-2-4]

[0170]

[0171] [Chemical formula 1-2-5]

[0172]

[0173] Synthesis example 3

[0174] A polymer including structural units represented by Chemical Formula 1-3-1 to Chemical Formula 1-3-5 was prepared in the same manner as in Synthesis Example 1 except that 2-hydroxypyrene (15.8 g, 0.05 mol), 2,2'-biphenol (18.6 g, 0.1 mol), fumaric acid (11.6 g, 0.1 mol) and paraformaldehyde (1.5 g, 0.05 mol) were used as reactants. 8 To A 11 Each is independently a moiety derived from 2-hydroxypyrene or 2,2'-biphenol.

[0175] [Chemical formula 1-3-1]

[0176]

[0177] [Chemical formula 1-3-2]

[0178]

[0179] [Chemical formula 1-3-3]

[0180]

[0181] [Chemical formula 1-3-4]

[0182]

[0183] [Chemical formula 1-3-5]

[0184]

[0185] Synthesis example 4

[0186] Naphthalene-1-ol (14.4g, 0.1mol) and dimethyl fumarate (14.4g, 0.1mol) are put into 250 ml flasks. Subsequently, p-toluenesulfonic acid monohydrate (0.57g, 0.03mmol) is dissolved in 100g PGMEA, and this solution is added in the flask, and then stirred at 100 ℃. After taking out the sample from the polymerization reaction thing at intervals of one hour, when the weight average molecular weight of the sample is 2,000g / mol to 2,500g / mol, the reaction is completed. When the polymerization reaction is completed, the reactant is cooled to ambient temperature and added to 300g distilled water and 300g methanol, and then stirred vigorously and allowed to stand. After removing the supernatant therefrom, the precipitate thus obtained is dissolved in 100g PGMEA, and then 300g distilled water and 300g methanol are used to stir, and then stirred vigorously and allowed to stand (primary process). Herein, after removing the supernatant obtained therefrom again, the precipitate thus obtained was dissolved in 80 g of PGMEA (secondary process). The primary process and the secondary process were regarded as one purification process, and the purification process was carried out three times in total. After purification, the polymer thus obtained was dissolved in 80 g of PGMEA, and the methanol and distilled water remaining in the solution were removed under reduced pressure, thereby obtaining a polymer including the structural units represented by Chemical Formula 1-4-1 to Chemical Formula 1-4-4. In Chemical Formula 1-4-1 to Chemical Formula 1-4-4, A 12 To A 15 Each is independently a moiety derived from 1-naphthol.

[0187] [Chemical formula 1-4-1]

[0188]

[0189] [Chemical formula 1-4-2]

[0190]

[0191] [Chemical formula 1-4-3]

[0192]

[0193] [Chemical formula 1-4-4]

[0194]

[0195] Comparative Synthesis Example 1

[0196] Pyrene (20.2g, 0.1mol) and 4-hydroxybenzaldehyde (12.2g, 0.1mol) were placed in a 250 ml flask. Subsequently, p-toluenesulfonic acid monohydrate (0.57g, 0.03mmol) was dissolved in 100g PGMEA, and this solution was added to a flask, and then stirred at 100°C. After taking out samples from the polymerization reaction at intervals of one hour, the reaction was completed when the weight average molecular weight of the sample reached 2,000g / mol to 2,500g / mol. When the polymerization reaction was completed, the reactant was cooled to ambient temperature and added to 300g distilled water and 300g methanol, and then vigorously stirred and allowed to stand. After removing the supernatant therefrom, the precipitate thus obtained was dissolved in 100g PGMEA, then stirred using 300g methanol and 300g distilled water, and then allowed to stand (primary process). Herein, after removing the supernatant obtained therefrom again, the precipitate thus obtained is dissolved in 80g PGMEA (secondary process). The primary process and the secondary process are considered as a purification process, and the purification process is carried out three times in total. After purification, the polymer thus obtained is dissolved in 80gPGMEA, and the methanol and distilled water retained in the solution are removed under reduced pressure, thereby obtaining a polymer comprising the structural unit represented by chemical formula P.

[0197] [Chemical formula P]

[0198]

[0199] Comparative Synthesis Example 2

[0200] A polymer including a structural unit represented by Chemical Formula Q was prepared in the same manner as in Comparative Synthesis Example 1, except that 2-hydroxypyrene (21.8 g, 0.1 mol) was used instead of pyrene and 4-naphthaldehyde (15.6 g, 0.1 mol) was used instead of hydroxybenzaldehyde.

[0201] [Chemical formula Q]

[0202]

[0203] Comparative Synthesis Example 3

[0204] In a 500ml double-necked flask equipped with a mechanical stirrer and a cooling tube, methoxypyrene (40g, 0.172mol) and terephthaloyl chloride (17.48g, 0.086mol) were added to 300g of 1,2-dichloroethane, and then fully stirred. After 15 minutes, trichloroaluminum (25.26g, 0.189mol) was slowly added thereto, and then the reaction solution was reacted at ambient temperature for 5 hours. When the reaction was complete, after using water to remove trichloroaluminum, the residue was concentrated using an evaporator. Subsequently, 1-dodecanethiol (41.78g, 0.21mol), potassium hydroxide (15.46g, 0.27mol) and N,N-dimethylformamide (230g) were added to the compound (40.96g, 0.068mol) obtained in the flask, and then stirred for 8 hours at 120°C. Subsequently, the mixture was cooled, and the mixture was neutralized to pH 7 using 5% hydrogen chloride solution, and then extracted and dried using ethyl acetate. Then, tetrahydrofuran (160g) was added to the obtained compound to obtain a solution. Sodium borohydride (32g, 0.84mol) aqueous solution was slowly added to this solution, and then stirred for 12 hours at ambient temperature. When the reaction was complete, the resulting product was acidified to pH 5 using 7% hydrogen chloride solution, and extracted using ethyl acetate, and the organic solvent was processed under reduced pressure. This synthesized polymer (10g, 0.017mol), bis(triphenylphosphine) palladium (II) dichloride (Pd(PPh3)2Cl2, 0.6g, 0.0008mol), cupric iodide (0.16g, 0.0008mol), triphenylphosphine (0.44g, 0.0016mol) and triethylamine (36mL) were dissolved in 60mL tetrahydrofuran. Subsequently, 3.5 g of ethynyltrimethylsilane was added thereto, and then stirred at 80 ° C for 3 hours. When the reaction was completed, the obtained product was purified by filtering using silica gel. 12.5 g (1 equivalent) of the purified solid was dissolved in 250 ml of MeOH / THF solution (volume ratio = 1 / 2), and 20 g of potassium carbonate (7 equivalents) was added thereto, and then stirred at ambient temperature for 6 hours. When the reaction was completed, the obtained product was extracted with ethyl acetate and treated under reduced pressure to obtain a compound represented by chemical formula R.

[0205] [Chemical formula R]

[0206]

[0207] Preparation of hard mask composition

[0208] Example 1

[0209] 3 g of the polymer according to Synthesis Example 1 was dissolved in 10 g of PGMEA, and then filtered using a 0.1 μm TEFLON (tetrafluoroethylene) filter, thereby preparing a hard mask composition.

[0210] Example 2

[0211] A hard mask composition was prepared in the same manner as in Example 1, except that the polymer of Synthesis Example 2 was used instead of the polymer of Synthesis Example 1.

[0212] Example 3

[0213] A hard mask composition was prepared in the same manner as in Example 1, except that the polymer of Synthesis Example 3 was used instead of the polymer of Synthesis Example 1.

[0214] Example 4

[0215] A hard mask composition was prepared in the same manner as in Example 1, except that the polymer of Synthesis Example 4 was used instead of the polymer of Synthesis Example 1.

[0216] Comparative Example 1

[0217] A hard mask composition was prepared in the same manner as in Example 1, except that the polymer of Comparative Synthesis Example 1 was used instead of the polymer of Synthesis Example 1.

[0218] Comparative Example 2

[0219] A hard mask composition was prepared in the same manner as in Example 1, except that the polymer of Comparative Synthesis Example 2 was used instead of the polymer of Synthesis Example 1.

[0220] Comparative Example 3

[0221] A hard mask composition was prepared in the same manner as in Example 1, except that the polymer of Comparative Synthesis Example 3 was used instead of the polymer of Synthesis Example 1.

[0222] Assessment 1: Assessment of membrane strength

[0223] Each of the hard mask compositions of Examples 1 to 4 and Comparative Examples 1 to 3 was spin-coated onto a silicon wafer. The film was 1000 μm thick and then heat treated on a hot plate at 400° C. for 2 minutes to form a thin film. Subsequently, the hardness (H) and modulus (E) of the film were measured using a nanoindenter (cube corner tip, Pmax=300 μN). The measurement results are shown in Table 1.

[0224] [Table 1]

[0225] Hardness (H, GPa) Modulus (E, GPa) Example 1 7.5 6.3 Example 2 6.9 6.8 Example 3 8.0 6.9 Example 4 7.1 6.5 Comparative Example 1 4.3 4.2 Comparative Example 2 4.1 4.7 Comparative Example 3 4.5 4.1

[0226] Referring to Table 1, the hardmasks formed from the hardmask compositions according to Examples 1 to 4 exhibited much higher hardness and modulus than the hardmasks formed from the hardmask compositions according to Comparative Examples 1 to 3. The hardmasks formed from the hardmask compositions according to the Examples exhibited superior film hardness and superior mechanical properties compared to the film hardness and mechanical properties of the hardmasks formed from the hardmask compositions according to the Comparative Examples.

[0227] Evaluation 2: Evaluation of pattern forming ability

[0228] The chemical vapor deposition (CVD) method is used to form a A thick silicon oxide (SiOx) layer was formed. Subsequently, each of the hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 3 was coated on the silicon oxide layer by a spin coating method, and then heat-treated at 350°C for 120 seconds to form a hard mask layer. Subsequently, a silicon nitride (SiNx) layer was formed on the hard mask layer by a chemical vapor deposition (CVD) method. Subsequently, a photoresist for KrF was spin-coated, and then heat-treated at 110°C for 60 seconds, exposed using an ASML (XT: 1400, NA 0.93) exposure device, and developed in a tetramethylammonium hydroxide (TMAH, 2.38 wt%) aqueous solution. Then, the photoresist patterned by the process was used as a mask, and the silicon nitride (SiNx) layer was dry-etched using a CHF3 / CF4 mixed gas plasma. Subsequently, the silicon nitride (SiNx) layer patterned by the process was used as a mask, and the hard mask layer according to Examples 1 to 4 and Comparative Examples 1 to 3 was dry-etched using N2 / O2 mixed gas plasma. The cross-section of the hard mask pattern was examined using an electron scanning microscope (SEM). The hard mask layer formed by the composition according to the comparative example exhibited pattern collapse, but the hard mask layer formed by the composition according to the example exhibited a good vertical shape and thus had excellent pattern forming ability.

[0229] Therefore, a hard mask formed of the hard mask composition according to some embodiments exhibits excellent coating properties in a solution state, and thus exhibits excellent smoothness and pattern forming ability, as well as excellent hardness and modulus, and thus exhibits excellent mechanical properties (eg, film strength).

[0230] In summary, the ongoing trend in the semiconductor industry is to reduce the size of the chip. For this reason, the line width of the patterned resist in photolithography can have a size of tens of nanometers. Therefore, the height of the line width that can withstand the resist pattern may be limited, and there are situations where the resist may not have sufficient resistance in the etching step. In order 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 be used as an interlayer for transferring the fine pattern of the photoresist by selective etching, and therefore the hard mask layer can have etching resistance and cross-linking properties to withstand the etching process required for pattern transfer.

[0231] Some hard mask layers may be formed using chemical or physical deposition methods, and may have low economic efficiency due to large-scale equipment and high process costs. Therefore, a spin coating technique for forming a hard mask layer has recently been developed. The spin coating technique may be a process that is easier to perform than some other methods, and the hard mask layer formed thereby may exhibit much superior gap filling characteristics and planarization characteristics, and the etching resistance of the hard mask layer may tend to be reduced.

[0232] The hardmask composition can be applied by a spin coating technique and can help ensure etch resistance equivalent to that of a hardmask layer formed in a chemical or physical deposition method. In order to improve the etch resistance of the hardmask layer, research on maximizing the carbon content of the hardmask composition is actively being conducted.

[0233] One or more embodiments may provide a hard mask composition that can form a hard mask without deteriorating etching resistance when a spin coating technique is applied. A composition for forming a hard mask may be provided, in which the etching resistance of the hard mask layer can be improved by increasing the carbon content in the polymer, the cross-linking characteristics can be improved by including a functional group containing a heteroatom and an unsaturated hydrocarbon group in the polymer, and the mechanical properties of the hard mask layer produced thereby are improved.

[0234] One or more embodiments may provide a hard mask composition that may be effectively applied to a hard mask layer.

[0235] A hard mask composition according to some embodiments may have excellent cross-linking characteristics, and a hard mask layer formed of the hard mask composition may help ensure excellent mechanical properties and pattern forming capability.

[0236] Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used and should be interpreted in a general and illustrative sense only, and not for purposes of limitation. In some cases, it will be apparent to one of ordinary skill in the art at the time this application is filed that features, characteristics, and / or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics, and / or elements described in connection with other embodiments, unless otherwise specifically stated. Therefore, it will be understood by one of ordinary skill in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention as set forth in the claims above.

Claims

1. A hard mask composition comprising: A polymer including a structural unit represented by Chemical Formula 1; and Solvents, [Chemical formula 1] in, In Chemical Formula 1, A is a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, X 1 and X 2 are each independently a single bond, -C(=O)-, a substituted or unsubstituted C1 to C30 alkylene group, or a combination thereof, Y is a substituted or unsubstituted C2 to C30 alkenylene group, or a substituted or unsubstituted C2 to C30 alkynylene group, and * is the connection point.

2. The hardmask composition according to claim 1, wherein A is a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that is part of Group 1, [Group 1] 3. The hard mask composition according to claim 2, wherein: A is a substituted C6 to C30 aromatic hydrocarbon group, and The substituent of the substituted C6 to C30 aromatic hydrocarbon group is deuterium, a hydroxyl group, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 heteroalkyl group, a C6 to C20 aryl group, a C3 to C20 heteroaryl group, or a combination thereof.

4. The hard mask composition according to claim 1, wherein X 1 and X 2 Each is independently -C(=O)-, a substituted C1 to C20 alkylene group, or a combination thereof. 5 . The hardmask composition of claim 1 , wherein Y is a substituted or unsubstituted C2 to C10 alkenylene group, or a substituted or unsubstituted C2 to C10 alkynylene group.

6. The hardmask composition according to claim 1, wherein A is a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that is part of group 1-1, [Group 1-1] 7. The hard mask composition according to claim 1, wherein: Chemical Formula 1 is represented by Chemical Formula 1-1 or Chemical Formula 1-2, [Chemical formula 1-1] [Chemical formula 1-2] In Chemical Formula 1-1 and Chemical Formula 1-2, A is a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group which is part of Group 1-1, X 1 and X 2 are each independently a single bond, -C(=O)-, a substituted or unsubstituted C1 to C30 alkylene group, or a combination thereof, and * is the connection point, [Group 1-1] 8. The hard mask composition according to claim 1, wherein: Chemical formula 1 is represented by one of Chemical formula 1-1-1 to Chemical formula 1-1-4 and Chemical formula 1-2-1 to Chemical formula 1-2-4, [Chemical formula 1-1-1] [Chemical formula 1-1-2] [Chemical formula 1-1-3] [Chemical formula 1-1-4] [Chemical formula 1-2-1] [Chemical formula 1-2-2] [Chemical formula 1-2-3] [Chemical formula 1-2-4] In Chemical Formulas 1-1-1 to 1-1-4 and Chemical Formulas 1-2-1 to 1-2-4, A 1 To A 6 Each is independently a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group.

9. The hard mask composition according to claim 8, wherein A 1 To A 6 each independently a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that is part of group 1-1, [Group 1-1] 10. The hard mask composition according to claim 1, wherein: The polymer further includes a structural unit represented by Chemical Formula 2, [Chemical formula 2] In chemical formula 2, B is a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, L is a single bond, or a substituted or unsubstituted C1 to C30 alkylene group, and * indicates the connection point.

11. The hardmask composition according to claim 10, wherein B in Chemical Formula 2 is a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group that is part of Group 2, [Group 2] 12 . The hardmask composition according to claim 10 , wherein L in Chemical Formula 2 is a substituted or unsubstituted methylene group. 13 . The hardmask composition of claim 1 , wherein the polymer has a weight average molecular weight of about 1,000 to about 200,000 g / mol. 14 . The hardmask composition of claim 1 , wherein the polymer is included in an amount of 0.1 wt % to 30 wt % based on the total weight of the hardmask composition.

15. The hardmask composition according to claim 1, wherein the solvent comprises 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, methylpyrrolidone, acetylacetone or ethyl 3-ethoxypropionate. 16 . A hard mask layer comprising a cured product of the hard mask composition according to claim 1 .

17. A method for 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; as well as The exposed portion of the material layer is etched. 18 . The method of claim 17 , wherein forming the hard mask layer comprises performing a heat treatment at 100° C. to 1,000° C.

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