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

Abstract

A hard mask composition, a hard mask layer manufactured from the hard mask composition, and a method of forming a pattern by using the hard mask layer manufactured from the hard mask composition, the hard mask composition comprising: a polymer including a structural unit represented by Chemical Formula 1; 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. 10-2024-0035455 filed in the Korean Intellectual Property Office on March 13, 2024, the entire contents of which are 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 ultrafine technology with patterns ranging from several nanometers to tens of nanometers in size, which can utilize efficient photolithography technology.

[0005] Some photolithography techniques 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. Summary of the Invention

[0006] 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,

[0007] [Chemical Formula 1]

[0008]

[0009] Wherein, in Chemical Formula 1, A is a substituted or unsubstituted moiety of Group 1, B is a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene group, R 1 and R 2 are independently deuterium, hydroxyl, halogen, -NR a R b , where R a and R bare each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C20 saturated or unsaturated alicyclic hydrocarbon group, a substituted or unsubstituted C1 to C20 saturated or unsaturated heteroaliphatic hydrocarbon group, a substituted or unsubstituted C2 to C20 saturated or unsaturated heteroaliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a substituted or unsubstituted C6 to C30 heteroaromatic hydrocarbon group, or a combination thereof, n1 and n2 are each independently an integer from 0 to 9, and * is a point of attachment,

[0010] [Group 1]

[0011]

[0012] Among them, in group 1, Ar 1 to Ar 3 are each independently a substituted or unsubstituted C6 to C20 aromatic ring group, X is -CR c R d -、-N(R e )-、-B(R f )-、-P(R g )-, -O- or -S-, and R c to R g Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0013] The embodiment may be implemented by providing a hard mask layer including a cured product of the aforementioned hard mask composition according to the embodiment.

[0014] 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; 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. DETAILED DESCRIPTION

[0015] Example embodiments will now be described more fully hereinafter; however, the embodiments 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 exemplary implementations to those skilled in the art.

[0016] 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 can be directly on the other layer or element, or intervening layers may be present. Furthermore, it should be understood that when a layer is referred to as being "between" two layers, the layer can be the only layer between the two layers, or one or more intervening layers may be present. The term "or" as used herein is not necessarily exclusive; for example, "A or B" would include A, B, or A and B.

[0017] As used herein, when no definition is otherwise provided, "substituted" may refer to a compound in which a hydrogen atom 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 C9 to C30 allylaryl 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.

[0018] 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 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 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, or a C2 to C30 heterocyclyl group may be fused with each other to form a ring.

[0019] When a definition is not otherwise provided, the “aromatic hydrocarbon ring” used herein refers to a group including at least one hydrocarbon aromatic moiety, and includes a form in which the hydrocarbon aromatic moieties are linked by a single bond, a non-aromatic fused ring form in which the hydrocarbon aromatic moieties are directly or indirectly fused, or a combination thereof, as well as a non-fused aromatic hydrocarbon ring or a condensed aromatic hydrocarbon ring.

[0020] More specifically, the substituted or unsubstituted aromatic hydrocarbon ring may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted tetraphenyl 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 The present invention can be any of the following: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 3

[0021] As used herein, "hetero" refers to one or more heteroatoms selected from N, O, S, Se, and P unless otherwise defined.

[0022] When a definition is not otherwise provided, the "heteroaromatic ring" used herein refers to a ring including at least one heteroatom selected from N, O, S, Se and P within an aromatic hydrocarbon ring.

[0023] More specifically, the substituted or unsubstituted heteroaromatic ring may be a substituted or unsubstituted furanyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothienyl, a substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl group), substituted or unsubstituted carbazolyl, pyridoindole, benzopyridooxazinyl, benzopyridothiazinyl, 9,9-dimethyl-9,10-dihydroacridinyl, combinations thereof, or fused rings of the aforementioned groups, but are not limited thereto.

[0024] As used herein, "combination" means mixing or copolymerizing when no definition is otherwise provided.

[0025] When no definition is otherwise provided, "polymer" as used herein may include both oligomers and polymers.

[0026] When no definition is otherwise provided, the weight average molecular weight used herein is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using an Agilent Technologies 1200 series Gel Permeation Chromatography (GPC) (column: Shodex Company LF-804, standard sample: Showa Company polystyrene).

[0027] There is a continuous trend in the semiconductor industry to reduce the size of chips. To cope with this, the line width of the resist patterned in photolithography should be tens of nanometers or less. Therefore, the height of the line width that can be tolerated by the resist pattern may be limited, and there are cases where the resist may not have sufficient 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. This hard mask layer can serve as an intermediate layer, which transfers the fine pattern of the photoresist through 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.

[0028] Some hard mask layers can be formed using chemical or physical deposition methods, which can be economically inefficient due to large-scale equipment and high process costs. Therefore, a method for forming a hard mask layer using spin coating has recently been developed. Spin coating may be easier to process than conventional methods and, in addition, may help ensure excellent gap filling and planarization properties of the hard mask layer formed using spin coating. In hard mask layers formed using spin coating, the desired etch resistance may be slightly reduced. Therefore, spin coating can be used to apply a desired hard mask composition, and the hard mask composition can ensure etch resistance comparable to that of a hard mask layer formed using chemical or physical deposition methods.

[0029] To improve the etch resistance of a hard mask layer, consideration has been given to maximizing the carbon content of the hard mask composition. However, as the carbon content of the polymer included in the hard mask composition is maximized, its solubility in a solvent tends to decrease. Therefore, maximizing the carbon content of the polymer included in the hard mask composition can not only improve the etch resistance of a hard mask layer formed from the hard mask composition, but also ensure high solubility of the polymer in the solvent.

[0030] According to some embodiments, the hard mask composition may include a polymer containing an aromatic hydrocarbon ring or a heteroaromatic ring, thereby maximizing the carbon content in the polymer and ensuring excellent etching resistance of the hard mask layer formed therefrom. In addition, by including a polar functional group in the polymer, the solubility of the polymer in the solvent can be increased, and the film density of the hard mask layer formed therefrom can be improved. In addition, by including tertiary carbon and a phenanthryl group connected thereto in the polymer, not only is the carbon content in the polymer further increased, but also, due to the low extinction coefficient (k) of the phenanthryl group at the exposure wavelength, the hard mask layer formed by the composition including the polymer can be formed to a high thickness.

[0031] In an implementation, 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.

[0032] [Chemical Formula 1]

[0033]

[0034] In Chemical Formula 1, A may be or may include, for example, a substituted or unsubstituted moiety of Group 1.

[0035] B may be or may include, for example, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group.

[0036] R 1 and R 2 can each independently be or include, for example, deuterium, a hydroxyl group, a halogen atom, -NR a R b (where R a and R b and substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl), substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 saturated or unsaturated aliphatic hydrocarbon group, substituted or unsubstituted C3 to C20 saturated or unsaturated alicyclic hydrocarbon group, substituted or unsubstituted C1 to C20 saturated or unsaturated heteroaliphatic hydrocarbon group, substituted or unsubstituted C2 to C20 saturated or unsaturated heteroaliphatic hydrocarbon group, substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, substituted or unsubstituted C6 to C30 heteroaromatic hydrocarbon group, or a combination thereof.

[0037] n1 and n2 can each independently be an integer from 0 to 9. In an embodiment, when n1 or n2 is 0, R 1 and R 2 may be absent, and the phenanthrenyl group may be unsubstituted (and may comprise only hydrogen atoms thereon).

[0038] * is the connection point.

[0039] [Group 1]

[0040]

[0041] In group 1, Ar 1 to Ar 3 Each independently may be, for example, a substituted or unsubstituted C6 to C20 aromatic ring.

[0042] X can be, for example, -CR c R d -、-N(R e )-、-B(R f )-、-P(R g )-, -O-, or -S-, and

[0043] R c to R g Each independently may be, for example, hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0044] In an embodiment, the aromatic hydrocarbon ring or heteroaromatic ring in the structural unit may be substituted with a polar substituent. In this case, the solubility of the polymer in the solvent can be further improved. Examples of polar substituents include hydroxyl groups, alkoxy groups, and amino groups. In addition, the inclusion of polar groups can form polar bonds or hydrogen bonds between polymers, and the hard mask layer formed thereby can have a higher film density and further improved patterning properties.

[0045] In an embodiment, A can be a substituted or unsubstituted moiety, such as from Group 1-1.

[0046] [Group 1-1]

[0047]

[0048] In group 1-1, X may be, for example, -CR c R d -、-N(R e )-, -O- or -S-, for example -CR c R d -or-N(R e )-, for example -N(R e )-. R c to R e Each of them can be, for example, independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof. In an embodiment, A can be, for example, a substituted or unsubstituted moiety of Groups 1-2.

[0049] [Group 1-2]

[0050]

[0051] In an embodiment, R 1 and R 2 can be independently deuterium, hydroxyl, halogen atom, -NR a R b (where R a and R b are each independently hydrogen, deuterium, or substituted or unsubstituted C1 to C10 alkyl), substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C3 to C20 cycloalkenyl, substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C20 heteroaryl, or a combination thereof. In an embodiment, R 1 and R 2 Each independently may be, for example, deuterium, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

[0052] In an embodiment, in Chemical Formula 1, n1 and n2 may each independently be, for example, an integer from 0 to 7, an integer from 0 to 4, 0, or 1.

[0053] In an embodiment, Chemical Formula 1 may be represented by, for example, one of Chemical Formula 1-1 to Chemical Formula 1-4.

[0054] [Chemical Formula 1-1]

[0055]

[0056] [Chemical formula 1-2]

[0057]

[0058] [Chemical formula 1-3]

[0059]

[0060] [Chemical formula 1-4]

[0061]

[0062] In Chemical Formulas 1-1 to 1-4, R11 、R 21 、R 31 , and R 41 Each of n11, n21, n31, and n41 may be, for example, independently an integer greater than or equal to 0 and less than or equal to 0, wherein R 11 、R 21 、R 31 , and R 41 An integer representing the bond valency of a substituted ring.

[0063] In an embodiment, R 11 、R 21 、R 31 , and R 41 Each independently may be, for example, a hydroxyl group or a substituted or unsubstituted C1 to C20 alkoxy group, for example, a hydroxyl group or a substituted or unsubstituted C1 to C10 alkoxy group.

[0064] In an embodiment, n11, n21, n31, and n41 may each independently be an integer of, for example, 0 to 5, 0 to 3, 0, or 1.

[0065] In an embodiment, Chemical Formula 1 may be represented by, for example, one of Chemical Formula 1-5 to Chemical Formula 1-8.

[0066] [Chemical Formula 1-5]

[0067]

[0068] [Chemical formula 1-6]

[0069]

[0070] [Chemical Formula 1-7]

[0071]

[0072] [Chemical Formula 1-8]

[0073]

[0074] The polymer may have a weight average molecular weight of, for example, about 500 g / mol to about 200,000 g / mol. In embodiments, the polymer may have a weight average molecular weight of about 500 g / mol to about 150,000 g / mol, for example, about 500 g / mol to about 100,000 g / mol, about 700 g / mol to about 50,000 g / mol, or about 700 g / mol to about 10,000 g / mol. By adjusting the weight average molecular weight within the above ranges, the carbon content and solubility in a solvent of a hardmask composition containing the above polymer can be adjusted and optimized.

[0075] The polymer may be included in an amount of, for example, about 0.01 wt % to about 30 wt % based on the total weight of the hardmask composition. In embodiments, the polymer may be included in an amount of about 0.02 wt % to about 30 wt %, such as about 0.05 wt % to about 30 wt %, about 0.1 wt % to about 30 wt %, about 0.2 wt % to about 25 wt %, or about 0.5 wt % to about 20 wt %. By including the polymer within the above ranges, the thickness, surface roughness, and planarization degree of the hardmask can be easily adjusted.

[0076] The hardmask composition according to some embodiments may include a solvent. In embodiments, the solvent may include propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, triethylene 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, ethyl 3-ethoxypropionate, or a similar solvent. The solvent may be a suitable solvent having sufficient solubility and / or dispersibility relative to the polymer.

[0077] In embodiments, the hardmask composition may further include additives such as a surfactant, a cross-linking agent, a thermal acid generator, or a plasticizer.

[0078] The surfactant may include, for example, a fluoroalkyl compound, an alkylbenzenesulfonate, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, or the like.

[0079] The crosslinking agent may include, for example, a melamine crosslinking agent, a substituted urea crosslinking agent, or a polymer crosslinking agent. In an embodiment, the crosslinking agent may be a crosslinking agent having at least two crosslinking substituents, such as, for example, methoxymethylated glycouryl, butoxymethylated glycoluryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea.

[0080] In an embodiment, a cross-linking agent having high heat resistance may be used. The cross-linking agent having high heat resistance may include a compound having a cross-linking substituent having an aromatic ring (eg, a benzene ring or a naphthalene ring) in a molecule.

[0081] The thermal acid generator may include, 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 tosylate, 2-nitrobenzyl tosylate, or other organic alkyl sulfonates.

[0082] In an embodiment, a hard mask layer including a cured product of the aforementioned hard mask composition may be provided.

[0083] Hereinafter, a method of forming a pattern using the aforementioned hard mask composition will be described.

[0084] According to some embodiments, a method for forming a pattern may include: providing a material layer on a substrate; applying a hard mask composition comprising 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.

[0085] The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. The material layer is the material to be ultimately patterned, such as a metal layer (e.g., an aluminum layer or a copper layer), a semiconductor layer (e.g., a silicon layer), or an insulating layer (e.g., a silicon oxide layer or a silicon nitride layer). The material layer may be formed by methods such as chemical vapor deposition (CVD).

[0086] The hard mask composition may be the same as described above and may be applied by spin coating from a solution. In an embodiment, the hard mask composition may be applied to a thickness of, for example, about Arrive at the appointment

[0087] The hardmask 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 embodiments, the thermal treatment of the hardmask composition may include a plurality of thermal treatment processes, such as a first thermal treatment process and a second thermal treatment process.

[0088] In embodiments, the heat treatment of the hard mask composition may include, for example, a heat treatment process performed at about 100° C. to about 1000° C. for about 10 seconds to about 1 hour. In embodiments, the 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.

[0089] In an embodiment, the heat treatment of the hard mask composition may include, for example, a first heat treatment process 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 150° C. to about 400° C. for about 30 seconds to about 1 hour, about 30 seconds to about 30 minutes, about 30 seconds to about 10 minutes, or 30 seconds to about 5 minutes.

[0090] In an embodiment, the heat treatment may include a second heat treatment process that is performed 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, about 30 seconds to about 30 minutes, about 30 seconds to about 10 minutes, or about 30 seconds to 5 minutes. In an embodiment, the first heat treatment process and the second heat treatment process may be performed in an air atmosphere or a nitrogen atmosphere, or may be performed in an atmosphere having an oxygen concentration of about 1 wt % or less.

[0091] By performing at least one of the steps of heat-treating the hard mask composition at a high temperature of 200° C. or higher, high etching resistance capable of withstanding etching gas and chemical liquid exposed in subsequent processes including an etching process can be exhibited.

[0092] In embodiments, the formation of the hard mask layer may include an ultraviolet (UV) / visible light (Vis) curing process and / or an infrared ray (IR) curing process.

[0093] In an embodiment, 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.

[0094] In an 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, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiO, SiN, or similar materials.

[0095] In an embodiment, the method may further include forming a bottom antireflective coating (BARC) on the silicon-containing thin layer or on the hard mask layer before forming the photoresist layer.

[0096] In an 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.

[0097] In an 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 include, for example, N2 / O2, CHF3, CF4, Cl2, BCl3, or a mixture thereof.

[0098] The etched material layer may be formed into a plurality of patterns, and the plurality of patterns may include metal patterns, semiconductor patterns, insulating patterns, or the like, such as various patterns of a semiconductor integrated circuit device.

[0099] The following examples and comparative examples are provided to highlight the features of one or more embodiments, but it should be understood that the examples and comparative examples should not be construed as limiting the scope of the embodiments, nor should the comparative examples be construed as exceeding the scope of the embodiments. Furthermore, it should be understood that the embodiments are not limited to the specific details set forth in the examples and comparative examples.

[0100] Polymer synthesis

[0101] Comparative Synthesis Example 1

[0102] 36.0g (0.2mol) of phenanthrene and 20.2g (0.1mol) of terephthaloyl chloride are added to a 500ml two-necked flask equipped with a mechanical stirrer and a cooling tube, and then dissolved in 435g of dichloroethane. After 15 minutes, 15g (0.25mol) of aluminum chloride is slowly added thereto, and the mixed solution is reacted for 3 hours at 10°C to 15°C. When the reaction is complete, after removing the aluminum chloride with water, an evaporator is used to concentrate. Subsequently, 270g of tetrahydrofuran is added to the obtained compound, thereby obtaining a solution. Then, an aqueous solution of 14.9g (0.42mol) of sodium borohydride is slowly added to the solution, and then stirred at ambient temperature for 24 hours. When the reaction is complete, the resulting product is acidified to pH 5 using 1% hydrogen chloride solution and extracted with ethyl acetate, and the organic solvent is removed under reduced pressure, thereby obtaining the compound A represented by chemical formula A.

[0103] [Chemical Formula A]

[0104]

[0105] Comparative Synthesis Example 2

[0106] Compound B represented by Chemical Formula B was obtained in the same manner as in Comparative Synthesis Example 1, except that 0.1 mol of 2,6-naphthalene dicarboxylic acid chloride was used instead of terephthaloyl chloride.

[0107] [Chemical Formula B]

[0108]

[0109] Synthesis example 1

[0110] 50 g (0.11 mol) of compound A, 23.8 g (0.11 mol) of 1-hydroxypyrene, 0.14 g (0.02 mol) of p-toluenesulfonic acid, and 172 g of 1,4-dioxane were added to a 500 ml two-necked flask equipped with a mechanical stirrer and a cooling tube, and then stirred thoroughly. After the temperature was raised to 100°C, the mixture was stirred again for 20 hours. When the reaction was complete, after the internal temperature was lowered to ambient temperature, 300 g of tetrahydrofuran was added thereto to prevent the compound from hardening, and the pH was adjusted to 5 or 6 using a 7% aqueous sodium bicarbonate solution. Subsequently, 1,000 ml of ethyl acetate was poured therein, and the organic layer was separately extracted therefrom using a separatory funnel while continuously stirring. After repeating the process of adding 500 ml of water to the separatory funnel again and shaking it to remove any residual acid and sodium three or more times, the organic layer was finally extracted. Subsequently, the organic solution was concentrated by using an evaporator, and 700 g of tetrahydrofuran was added to the obtained compound to obtain a compound in a solution state. The solution was slowly added dropwise to a beaker containing 3,000 ml of hexane while stirring to form a precipitate, thereby obtaining a polymer 1 including a structural unit represented by Chemical Formula 1-5. The weight average molecular weight (Mw) and polydispersity (PD) of polymer 1 were measured by using gel permeation chromatography (GPC). (Mw: 2,400 g / mol, PD: 1.56)

[0111] [Chemical Formula 1-5]

[0112]

[0113] Synthesis example 2

[0114] Polymer 2 (including the structural unit represented by Chemical Formula 1-6) was obtained in the same manner as in Synthesis Example 1, except that 0.11 mol of Compound B was used instead of Compound A. The weight average molecular weight (Mw) and polydispersity (PD) of Polymer 2 were measured by gel permeation chromatography (GPC). (Mw: 2,510 g / mol, PD: 1.52)

[0115] [Chemical formula 1-6]

[0116]

[0117] Synthesis example 3

[0118] Polymer 3 (including the structural unit represented by Chemical Formula 1-7) was obtained in the same manner as in Synthesis Example 1, except that 0.11 mol of carbazole was used instead of 1-hydroxypyrene. The weight average molecular weight (Mw) and polydispersity (PD) of Polymer 3 were measured by gel permeation chromatography (GPC). (Mw: 2,280 g / mol, PD: 1.47)

[0119] [Chemical Formula 1-7]

[0120]

[0121] Synthesis example 4

[0122] Polymer 4 (including the structural unit represented by Chemical Formula 1-8) was obtained in the same manner as in Synthesis Example 1, except that 0.11 mol of 1-hydroxycarbazole was used instead of 1-hydroxypyrene. The weight average molecular weight (Mw) and polydispersity (PD) of Polymer 4 were measured by gel permeation chromatography (GPC). (Mw: 2,280 g / mol, PD: 1.47)

[0123] [Chemical Formula 1-8]

[0124]

[0125] Preparation of hard mask composition

[0126] Example 1

[0127] 1.2 g of Polymer 1 according to Synthesis Example 1 was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) (7:3 (volume / volume, v / v)), and then filtered using a 0.1 μm Teflon (tetrafluoroethylene) filter to prepare a hard mask composition according to Example 1.

[0128] Example 2

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

[0130] Example 3

[0131] A hard mask composition according to Example 3 was prepared in the same manner as in Example 1, except that Polymer 3 was used instead of Polymer 1.

[0132] Example 4

[0133] A hard mask composition according to Example 4 was prepared in the same manner as in Example 1, except that Polymer 4 was used instead of Polymer 1.

[0134] Comparative Example 1

[0135] 1.5 g of Compound A according to Comparative Synthesis Example 1 was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3 (v / v)), and then filtered using a 0.1 μm Teflon (tetrafluoroethylene) filter to prepare a hard mask composition according to Comparative Example 1.

[0136] Comparative Example 2

[0137] A hard mask composition was prepared in the same manner as in Comparative Example 1, except that Compound B according to Comparative Synthesis Example 2 was used instead of Compound A.

[0138] Evaluation 1: Etching resistance evaluation

[0139] Each of the hard mask compositions of Examples 1 to 4 and Comparative Examples 1 to 2 was spin-coated on a silicon wafer, and then heat-treated on a hot plate at 400° C. for 2 minutes to form A film of 100 mm thick was obtained. Subsequently, the thickness of the film was measured using a film thickness measuring device manufactured by K-MAC. Subsequently, the film was dry-etched for 100 seconds using a mixed gas of CF4 / CHF3, and the thickness was then measured again. The bulk etch rate (BER) was calculated using the thickness before and after dry etching of the film and the etching time according to Equation 1, and the results are shown in Table 1.

[0140] [Calculation Equation 1]

[0141]

[0142] [Table 1]

[0143] Referring to Table 1, the hard mask layers formed from the hard mask compositions according to Examples 1 to 4, respectively, exhibited a low etching rate for the mixed gas of CF4 / CHF3, and thus exhibited excellent etching resistance, compared to the hard mask layers formed from the hard mask compositions according to Comparative Examples 1 to 2, respectively.

[0144] Assessment 2: Solubility Assessment

[0145] Polymers 1 to 4 according to Synthesis Examples and Comparative Synthesis Examples, as well as Compound A and Compound B, were each added to 20 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to examine solubility. The solubility was evaluated by measuring the amount of each polymer or compound in 20 g of solvent and then converting it into a percentage according to Calculation Equation 2. The results are shown in Table 2.

[0146] [Calculation Equation 2]

[0147] Solubility (%) = {mass of polymer or compound (g) / mass of solvent (20 g)}

[0148] [Table 2]

[0149] Solubility (%) Synthesis example 1 42 Synthesis example 2 45 Synthesis example 3 30 Synthesis example 4 35 Comparative Synthesis Example 1 10 Comparative Synthesis Example 2 19

[0150] Referring to Table 2, the polymer according to the Synthesis Example exhibited greater solubility in PGMEA than the compound according to the Comparative Synthesis Example.

[0151] Assessment 3: Membrane Density Assessment

[0152] The hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 2 were spin-coated on a silicon wafer and then heat-treated on a hot plate at 400° C. for 2 minutes to form hard mask films each having a thickness of The film density of the hard mask layer was measured by using an X-ray diffraction apparatus from PANalytical Ltd., and the results are shown in Table 3.

[0153] [Table 3]

[0154] <![CDATA[Film density (g / cm 3 )]]> Example 1 1.40 Example 2 1.39 Example 3 1.35 Example 4 1.38 Comparative Example 1 1.25 Comparative Example 2 1.26

[0155] Referring to Table 3, the hard mask layers formed from the hard mask compositions of Examples 1 to 4 exhibited greater density and more excellent physical properties than the hard mask layers formed from the hard mask compositions according to Comparative Examples 1 to 2.

[0156] In summary, depending on the small size of the pattern to be formed, it may be difficult to provide a fine pattern with excellent profile by using some photolithography techniques. 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.

[0157] One or more embodiments may provide a hardmask composition that may be effectively applied to a hardmask layer.

[0158] The hard mask composition according to some embodiments may have excellent solubility in a solvent and may be efficiently applied to a hard mask layer.

[0159] A hard mask layer formed of the hard mask composition according to some embodiments may help ensure excellent etch resistance and excellent pattern forming properties.

[0160] A hard mask layer formed of the hard mask composition according to some embodiments may have a high film density, thereby improving physical properties of the film.

[0161] Example embodiments have been disclosed herein, and although specific terms are employed, they are used and should be interpreted in a generic 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 of filing 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. Accordingly, it will be understood by those skilled in the art that various changes in form and details 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 moiety of Group 1, B is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group, R 1 and R 2 are independently deuterium, hydroxyl, halogen, -NR a R b , where R a and R b are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 saturated or unsaturated aliphatic hydrocarbon group, a substituted or unsubstituted C3 to C20 saturated or unsaturated alicyclic hydrocarbon group, a substituted or unsubstituted C1 to C20 saturated or unsaturated heteroaliphatic hydrocarbon group, a substituted or unsubstituted C2 to C20 saturated or unsaturated heteroaliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a substituted or unsubstituted C6 to C30 heteroaromatic hydrocarbon group, or a combination thereof, n1 and n2 are each independently an integer from 0 to 9, and * is the connection point, [Group 1] Among them, in group 1, Ar 1 to Ar 3 are each independently a substituted or unsubstituted C6 to C20 aromatic ring group, X is -CR c R d -、-N(R e )-、-B(R f )-、-P(R g )-, -O-, or -S-, and R c to R g Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

2. The hardmask composition according to claim 1, wherein: A is a substituted or unsubstituted moiety of Group 1-1: [Group 1-1] In group 1-1, X is -CR c R d -、-N(R e )-, -O-, or -S-, and R c to R e Each is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

3. The hardmask composition of claim 1 , wherein A is a substituted or unsubstituted moiety of Group 1-2: [Group 1-2] 4. The hardmask composition according to claim 1, wherein: R 1 and R 2 are independently deuterium, hydroxyl, halogen, -NR a R b , where R a and R b are each independently hydrogen, deuterium, or substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C3 to C20 cycloalkenyl, substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C20 heteroaryl, or a combination thereof, and n1 and n2 are each independently an integer from 0 to 4.

5. The hardmask composition according to claim 1, wherein: R 1 and R 2 are each independently deuterium, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and n1 and n2 are each independently 0 or 1.

6. The hardmask composition according to claim 1, wherein: Chemical Formula 1 is represented by one of Chemical Formulas 1-1 to 1-4: [Chemical Formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] [Chemical formula 1-4] In Chemical Formulas 1-1 to 1-4, R 11 、R 21 、R 31 , and R 41 are each independently deuterium, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof, and n11, n21, n31, and n41 are each independently an integer greater than or equal to 0 and less than or equal to the integer R above 11 、R 21 、R 31 , and R 41 An integer representing the bond valence of the substituted ring.

7. The hardmask composition according to claim 1, wherein Chemical Formula 1 is represented by one of Chemical Formulas 1-5 to 1-8: [Chemical Formula 1-5] [Chemical formula 1-6] [Chemical Formula 1-7] [Chemical Formula 1-8] 8 . The hardmask composition of claim 1 , wherein the polymer has a weight average molecular weight of 500 g / mol to 200,000 g / mol. 9 . The hardmask composition of claim 1 , wherein the polymer is included in an amount of 0.01 wt % to 30 wt % based on the total weight of the hardmask composition.

10. The hardmask 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, methylpyrrolidone, acetylacetone or ethyl 3-ethoxypropionate. 11 . A hard mask layer comprising a cured product of the hard mask composition according to claim 1 .

12. A method for forming a pattern, the method comprising: providing a material layer on a substrate, applying the hard mask composition of 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 The exposed portion of the material layer is etched. 13 . The method of claim 12 , wherein forming the hard mask layer comprises performing a heat treatment at 100° C. to 1,000° C.

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