Hardmask composition, hardmask layer, and method of forming patterns

Abstract

A rigid mask composition, a rigid mask layer made from the rigid mask composition, and a method of forming a pattern using the rigid mask layer made from the rigid mask composition, the rigid mask composition comprising: a polymer including structural units represented by chemical formula 1; and a solvent.

Description

Technical Field

[0001] The embodiments relate to a rigid mask composition, a rigid mask layer comprising a cured product of the rigid mask composition, and a method of forming a pattern using the rigid mask composition. Cross-reference of related applications

[0002] This application claims priority and benefits to Korean Patent Application No. 10-2024-0035455, filed on March 13, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Prior Technology

[0003] Recently, the semiconductor industry has developed ultra-fine technology with patterns ranging from several nanometers to tens of nanometers in size. This ultra-fine technology can utilize efficient photolithography techniques.

[0004] 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 using the photoresist pattern as a mask to etch the material layer. Summary of the Invention

[0005] An embodiment can be achieved by providing a rigid mask composition comprising: a polymer including structural units represented by chemical formula 1; and a solvent.

[0006] [Chemical Formula 1]

[0007] In chemical formula 1, A is the substituted or unsubstituted portion of group 1, B is the substituted or unsubstituted pentylenyl or the substituted or unsubstituted pentylenyl naphthyl, and R1 and R2 are each independently deuterium, hydroxyl, halogen atom, or -NR aR b, wherein Ra and R b is independently hydrogen, deuterium, 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, substituted or unsubstituted C3 to C20 saturated or unsaturated alicyclic hydrocarbon, substituted or unsubstituted C1 to C20 saturated or unsaturated heteroaliphatic hydrocarbon, substituted or unsubstituted C2 to C20 saturated or unsaturated heteroaliphatic hydrocarbon, substituted or unsubstituted C6 to C30 aromatic hydrocarbon, substituted or unsubstituted C6 to C30 heteroaromatic hydrocarbon, or combinations thereof; n1 and n2 are independently integers from 0 to 9, and * is a connecting point.

[0008] [Group 1]

[0009] In Group 1, Ar 1 to Ar 3 are each independently a substituted or unsubstituted C6 to C20 aromatic cycloalgide, X is -CR cR d-, -N(R e)-, -B(R f)-, -P(R g)-, -O- or -S-, and R c to R g are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl or a combination thereof.

[0010] An embodiment can be implemented by providing a rigid mask layer comprising a cured product of the rigid mask composition described above according to the embodiment.

[0011] 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. Simple Explanation of the Diagram

[0012] none. Implementation

[0013] Exemplary embodiments will now be set forth more fully below; however, 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 exemplary implementation methods to those skilled in the art.

[0014] It should also be understood that when a layer or element is said to be "on" another layer or element, the layer or element may be directly on the other layer or element, or there may be intermediate layers. Furthermore, it should be understood that when a layer is said to be "between" two layers, the layer may be the only layer between the two layers, or there may be one or more intermediate layers. The term "or" as used herein is not necessarily an exclusive term; for example, "A or B" would include A, B, or A and B.

[0015] Unless otherwise defined, “substituted” as used herein may mean that the hydrogen atom of a compound is substituted by a substituent selected from the following: halogen atom (F, Br, Cl, or I), hydroxyl, alkoxy, nitro, cyano, amino, azide, amido, hydrazine, hydrazine, carbonyl, aminomethyl, thiol, ester, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphate or a salt thereof, vinyl, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 arylalkyl, C9 to C30 allylaryl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C3 to C30 heterocycloalkyl, or combinations thereof.

[0016] Additionally, two adjacent substituents from the substituted halogen atom (F, Br, Cl, or I), hydroxyl, nitro, cyano, amino, azide, amidine, hydrazine, hydrazine, carbonyl, aminomethyl, thiol, ester, carboxyl or its salt, sulfonic acid or its salt, phosphoric acid or its salt, C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 arylalkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, or C2 to C30 heterocyclic group can fused together to form a ring.

[0017] Unless otherwise defined, "aromatic hydrocarbon ring" as used herein means a group comprising at least one aromatic hydrocarbon moiety, including forms in which the aromatic hydrocarbon moiety is linked by a single bond, non-aromatic fused rings in which the aromatic hydrocarbon moiety is directly or indirectly fused, or combinations thereof, and non-fused aromatic hydrocarbon rings or condensed aromatic hydrocarbon rings.

[0018] More specifically, the substituted or unsubstituted aromatic hydrocarbon ring can be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthraquinone, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted tetraphenyl, a substituted or unsubstituted pyrene, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted tetraphenyl, or a substituted or unsubstituted ring. The group may include, but is not limited to, substituted or unsubstituted triphenyl, substituted or unsubstituted peryl, substituted or unsubstituted indole, combinations thereof, or combinations of the foregoing groups in a fused ring.

[0019] Unless otherwise defined, "hetero" as used herein refers to one or more heteroatoms selected from N, O, S, Se, and P.

[0020] Unless otherwise defined, "heteroaromatic ring" as used herein refers to a ring containing at least one heteroatom selected from N, O, S, Se and P within an aromatic hydrocarbon ring.

[0021] More specifically, the substituted or unsubstituted heteroaromatic ring can be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophene group, a substituted or unsubstituted pyrrole group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophene group, or a substituted... Or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthidyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridineyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenthiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl (group), substituted or unsubstituted zozazolyl, pyridoindolyl, benzopyridooxazinyl, benzopyridothiazinyl, 9,9-dimethyl-9,10-dihydroacridinyl, combinations thereof, or combinations of the foregoing groups in a fused ring, but not limited to these.

[0022] Unless otherwise defined, “combination” as used in this document means blending or copolymerization.

[0023] Unless otherwise defined, the term "polymer" as used herein may include both oligomers and polymers.

[0024] Unless otherwise defined, the weight-average molecular weight used herein is measured by dissolving the powder sample in tetrahydrofuran (THF) and then using an Agilent Technologies Series 1200 gel permeation chromatography (GPC) system (Shodex Company LF-804 column, Showa Company polystyrene standard).

[0025] Reducing wafer size is a continuous trend in the semiconductor industry. To address this, the linewidth of the patterned resist in photolithography should be tens of nanometers or smaller. Therefore, the height of the linewidth that can withstand the resist pattern may be limited, and there are situations 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 that selectively etches the fine pattern of the photoresist, and thus, the hard mask layer can possess etch resistance and cross-linking properties to withstand the etching process required for pattern transfer.

[0026] Some hard mask layers can be formed using chemical or physical deposition methods, which can be inefficient due to large-scale equipment and high process costs. Therefore, a method for forming hard mask layers using spin coating technology has recently been developed. Spin coating technology is likely easier to process than conventional methods and, in addition, helps ensure excellent gap-filling and planarization properties of the hard mask layers formed therefrom. The required etch resistance may be slightly reduced in hard mask layers formed using spin coating technology. Therefore, spin coating technology can be used to apply a desired hard mask composition that ensures etch resistance comparable to that of hard mask layers formed using chemical or physical deposition methods.

[0027] To improve the etch resistance of hard mask layers, maximizing the carbon content of the hard mask composition has been considered. However, as the carbon content of the polymer contained in the hard mask composition is maximized, its solubility in solvents tends to decrease. Therefore, maximizing the carbon content of the polymer contained in the hard mask composition should not only improve the etch resistance of the hard mask layer formed from the hard mask composition, but also ensure high polymer solubility in solvents.

[0028] According to some embodiments, the hard mask composition may include a polymer containing aromatic or heteroaromatic rings, thereby maximizing the carbon content in the polymer and ensuring excellent etch resistance of the hard mask layer formed therefrom. Furthermore, by including polar functional groups in the polymer, the solubility of the polymer in solvents can be improved, and the film density of the hard mask layer formed therefrom can be enhanced. Additionally, by including tertiary carbon and phenanthrene groups attached 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 phenanthrene groups at the exposure wavelength, the hard mask layer formed from the composition containing said polymer can be formed to a high thickness.

[0029] In some embodiments, the rigid masking composition may include, for example, a polymer comprising structural units represented by chemical formula 1, and a solvent.

[0030] [Chemical Formula 1]

[0031] In chemical formula 1, A may be or may include, for example, the substituted or unsubstituted portion of group 1.

[0032] B may be, or may include, for example, substituted or unsubstituted pentylenyl or substituted or unsubstituted pentylenyl.

[0033] R1 and R2 may each independently be or include, for example, deuterium, hydroxyl, halogen atom, -NR aR b (where Ra and R b are each independently hydrogen, deuterium, 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 combinations thereof.

[0034] n1 and n2 can each be an integer, for example, from 0 to 9. In an implementation, when n1 or n2 is 0, R1 and R2 may not exist, and the phenanthrene group may be unsubstituted (may only include the hydrogen atoms thereon).

[0035] * indicates a connection point.

[0036] [Group 1]

[0037] In group 1, Ar 1 to Ar 3 can each be independently, for example, substituted or unsubstituted C6 to C20 aromatic rings.

[0038] X can be, for example, -CR cR d-, -N(R e)-, -B(R f)-, -P(R g)-, -O-, or -S-, and Rc to Rg can each independently be, for example, hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0039] In this embodiment, the aromatic or heteroaromatic rings in the structural unit may be replaced by polar substituents. In this case, the solubility of the polymer in the solvent can be further improved. Examples of polar substituents may include hydroxyl, alkoxy, and amino groups. In addition, by including polar groups, polar bonds or hydrogen bonds can be formed between polymers, and the resulting hard mask layer can have higher film density and further improved patterning properties.

[0040] In an implementation, A may be, for example, the substituted or unsubstituted portion of group 1-1.

[0041] [Group 1-1]

[0042] In group 1-1, X can be, for example, -CR cR d-, -N(Re)-, -O-, or -S-, for example -CR cR d- or -N(Re)-, for example -N(Re)-. Rc to Re can each independently be, for example, hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, or combinations thereof. In embodiments, A can be, for example, a substituted or unsubstituted portion of group 1-2.

[0043] [Groups 1-2]

[0044] In embodiments, R1 and R2 may each be independently, for example, deuterium, hydroxyl, halogen atom, -NR aR b (wherein Ra 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 combinations thereof. In the embodiments, R1 and R2 may each be independently, for example, deuterium, hydroxyl, halogen atom, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof.

[0045] In the implementation, in chemical formula 1, n1 and n2 can each be an integer from 0 to 7, an integer from 0 to 4, or 0 or 1, respectively.

[0046] In an embodiment, chemical formula 1 may be represented by, for example, one of chemical formulas 1-1 to 1-4.

[0047] [Chemical Formula 1-1]

[0048] [Chemical Formula 1-2]

[0049] [Chemical Formulas 1-3]

[0050] [Chemical Formulas 1-4]

[0051] In chemical formulas 1-1 to 1-4, R11, R21, R31, and R41 can each independently be, for example, deuterium, hydroxyl, halogen atom, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C20 aryl, or combinations thereof. n11, n21, n31, and n41 can each independently be, for example, an integer greater than or equal to 0 and an integer less than or equal to the bond valency of the ring in which R11, R21, R31, and R41 are substituted.

[0052] In the embodiments, R11, R21, R31, and R41 may each be independently, for example, hydroxyl, or substituted or unsubstituted C1 to C20 alkoxy, for example, hydroxyl or substituted or unsubstituted C1 to C10 alkoxy.

[0053] In the implementation, n11, n21, n31, and n41 can each be an integer, for example, 0 to 5, 0 to 3, 0, or 1.

[0054] In an embodiment, chemical formula 1 may be represented by, for example, one of chemical formulas 1-5 to 1-8.

[0055] [Chemical Formulas 1-5]

[0056] [Chemical Formulas 1-6]

[0057] [Chemical Formulas 1-7]

[0058] [Chemical Formulas 1-8]

[0059] The polymer may have a weight-average molecular weight, for example, from about 500 g / mol to about 200,000 g / mol. In embodiments, the polymer may have a weight-average molecular weight from about 500 g / mol to about 150,000 g / mol, for example, from about 500 g / mol to about 100,000 g / mol, from about 700 g / mol to about 50,000 g / mol, or from about 700 g / mol to about 10,000 g / mol. By keeping the weight-average molecular weight within the above ranges, the carbon content and solubility in solvents of the hard-mask composition comprising the above polymers can be adjusted and optimized.

[0060] The polymer may be included in an amount from, for example, about 0.01% by weight to about 30% by weight, based on the total weight of the rigid mask components. In embodiments, the polymer may be included in an amount from about 0.02% by weight to about 30% by weight, for example, about 0.05% by weight to about 30% by weight, about 0.1% by weight to about 30% by weight, about 0.2% by weight to about 25% by weight, or about 0.5% by weight to about 20% by weight. By including the polymer within the above ranges, the thickness, surface roughness, and planarization degree of the rigid mask can be easily adjusted.

[0061] The rigid masking 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, 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, acetoacetone, ethyl 3-ethoxypropionate, or similar solvents. The solvent may be a suitable solvent having sufficient solubility and / or dispersibility relative to the polymer.

[0062] In embodiments, the rigid mask composition may also include additives such as surfactants, crosslinking agents, thermal acid generators, or plasticizers.

[0063] Surfactants may contain, for example, fluoroalkyl compounds, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts, or similar compounds.

[0064] Crosslinking agents may include, for example, melamine crosslinking agents, substituted urea crosslinking agents, or polymer crosslinking agents. In embodiments, the crosslinking agent may be a crosslinking agent having at least two crosslinking substituents, such as (for example) methoxymethylated glycoruryl, butoxymethylated glycoruryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea.

[0065] In this embodiment, a crosslinking agent with high heat resistance may be used. A crosslinking agent with high heat resistance may include compounds containing crosslinking substituents having aromatic rings (e.g., benzene rings or naphthalene rings) in their molecules.

[0066] The hot acid generator may include, for example, acid compounds (such as 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-tetrabromocyclohexadienone, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate or other organic alkyl sulfonates.

[0067] In one embodiment, a rigid mask layer comprising a cured product of the aforementioned rigid mask composition may be provided.

[0068] The method of forming patterns using the aforementioned rigid masking components will be described below.

[0069] A method for forming a pattern according to some embodiments may include: providing a material layer on a substrate; applying a hard mask composition comprising the aforementioned polymer and solvent 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.

[0070] The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. The material layer is the material to be finally patterned, such as a metal layer (e.g., aluminum and copper layers), a semiconductor layer (e.g., silicon layer), or an insulating layer (e.g., silicon oxide and silicon nitride layers). The material layer may be formed by methods such as chemical vapor deposition (CVD).

[0071] The rigid mask composition can be the same as described above and can be applied by spin coating in solution form. In embodiments, the applied thickness of the rigid mask composition can be, for example, from about 50 Å to about 200,000 Å.

[0072] The rigid masking components can be heat-treated, for example, at a temperature of about 100°C to about 1,000°C for about 10 seconds to about 1 hour. In embodiments, the heat treatment of the rigid masking components may include multiple heat treatment processes, such as a first heat treatment process and a second heat treatment process.

[0073] In one embodiment, the heat treatment of the rigid cover composition may include, for example, a heat treatment process performed at about 10 seconds to about 1 hour at about 100°C to about 1000°C. In another embodiment, the heat treatment may be performed in an air atmosphere, or a nitrogen atmosphere, or an atmosphere with an oxygen concentration of about 1% by weight or less than 1% by weight.

[0074] In an embodiment, the heat treatment of the rigid cover assembly may include, for example, a first heat treatment process, which is carried out at about 100°C to about 1,000°C, about 100°C to about 800°C, about 100°C to about 500°C, or about 150°C to about 400°C for about 30 seconds to about 1 hour, about 30 seconds to about 30 minutes, about 30 seconds to about 10 minutes, or about 30 seconds to about 5 minutes.

[0075] In an embodiment, the heat treatment may include a continuously performed second heat treatment process, which is carried out, 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 and second heat treatment processes may be carried out in an air atmosphere or a nitrogen atmosphere, or in an atmosphere with an oxygen concentration of about 1% by weight or less than 1% by weight.

[0076] By performing at least one of the steps of heat treatment on the hard masking components at a high temperature of 200°C or above, high etch resistance can be demonstrated, which can withstand etching gases and chemical liquids exposed in subsequent processes, including etching processes.

[0077] In this embodiment, the formation of the rigid mask layer may include an ultraviolet (UV) / visible light (Vis) curing process and / or an infrared (IR) curing process.

[0078] In an embodiment, the formation of the rigid 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 consecutive processes.

[0079] In an embodiment, the method may further include forming a silicon-containing thin layer on the rigid mask layer. The silicon-containing thin layer may be formed of, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiO, SiN, or similar materials.

[0080] In an embodiment, the method may further include: forming a bottom antireflective coating (BARC) on a silicon-containing thin layer or on a rigid mask layer before forming the photoresist layer.

[0081] In this implementation, the photoresist layer can be exposed using, for example, ArF, KrF, or extreme ultraviolet (EUV). After exposure, heat treatment can be performed at approximately 100°C to approximately 700°C.

[0082] In one embodiment, the etching process of the exposed portion of the material layer can be carried out by using a dry etching process with an etching gas, and the etching gas may include, for example, N2 / O2, CHF3, CF4, Cl2, BCl3 or a mixture thereof.

[0083] The etched material layer can be formed into multiple patterns, and the multiple patterns may include metal patterns, semiconductor patterns, insulating patterns or similar patterns, such as various patterns of semiconductor integrated circuit devices.

[0084] The following examples and comparative examples are provided to highlight the features of one or more embodiments. However, it should be understood that the examples and comparative examples should not be construed as limiting the scope of the embodiments, nor should they 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.

[0085] Polymer Synthesis

[0086] Comparative Synthesis Example 1

[0087] 36.0 g (0.2 mol) of phenanthrene and 20.2 g (0.1 mol) of terephthalic acid chloride were added to a 500 ml double-necked flask equipped with a mechanical stirrer and a cooling tube, and then dissolved in 435 g of dichloroethane. After 15 minutes, 15 g (0.25 mol) of aluminum trichloride was slowly added, and the mixture was allowed to react at 10°C to 15°C for 3 hours. When the reaction was complete, the aluminum trichloride was removed with water, and the mixture was concentrated using an evaporator. Subsequently, 270 g of tetrahydrofuran was added to the obtained compound to obtain a solution. Then, an aqueous solution of 14.9 g (0.42 mol) of sodium borohydride was slowly added to the solution, and the mixture was stirred at ambient temperature for 24 hours. When the reaction was complete, the product was acidified to pH 5 with 1% hydrogen chloride solution and extracted with ethyl acetate, and the organic solvent was removed under reduced pressure to obtain compound A represented by chemical formula A.

[0088] [Chemical Formula A]

[0089] Comparative Synthesis Example 2

[0090] Except that 0.1 mol of 2,6-naphthodimethyl chloride was used instead of terephthalic chloride, compound B, represented by chemical formula B, was obtained in the same manner as in Comparative Synthesis Example 1.

[0091] [Chemical Formula B]

[0092] Synthesis example 1

[0093] 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 double-necked flask equipped with a mechanical stirrer and a cooling tube. The mixture was then stirred thoroughly and the temperature was raised to 100 °C and stirred again for 20 hours. When the reaction was complete, the internal temperature was lowered to ambient temperature, and 300 g of tetrahydrofuran was added to prevent the compound from hardening. The pH was adjusted to 5 or 6 using a 7% sodium bicarbonate aqueous solution. Subsequently, 1,000 ml of ethyl acetate was added, and the organic layer was extracted separately using a separatory funnel while continuously stirring. The organic layer was finally extracted after repeating the process of adding 500 ml of water to the separatory funnel and shaking to remove any residual acid and sodium three or more times. The organic solution was then concentrated using an evaporator, and 700 g of tetrahydrofuran was added to the obtained compound to obtain a solution. While stirring, the solution was slowly added dropwise to a beaker containing 3,000 ml of hexane to form a precipitate, thus obtaining polymer 1 comprising structural units represented by chemical formulas 1-5. The weight-average molecular weight (Mw) and polydispersity (PD) of polymer 1 were measured using gel permeation chromatography (GPC). (Mw: 2,400 g / mol, PD: 1.56)

[0094] [Chemical Formulas 1-5]

[0095] Synthesis example 2

[0096] Polymer 2 (comprising structural units represented by chemical formulas 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)

[0097] [Chemical Formulas 1-6]

[0098] Synthesis example 3

[0099] Polymer 3 (comprising structural units represented by chemical formulas 1-7) was obtained in the same manner as in Synthesis Example 1, except that 0.11 mol thioazole 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)

[0100] [Chemical Formulas 1-7]

[0101] Synthesis example 4

[0102] Polymer 4 (comprising structural units represented by chemical formulas 1-8) was obtained in the same manner as in Synthesis Example 1, except that 0.11 mol of 1-hydroxychloroazole 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)

[0103] [Chemical Formulas 1-8]

[0104] Preparation of rigid screen components

[0105] Example 1

[0106] 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 the rigid mask composition according to Example 1.

[0107] Example 2

[0108] Except that polymer 2 is used instead of polymer 1, the rigid mask composition according to Example 2 is prepared in the same manner as in Example 1.

[0109] Example 3

[0110] Except that polymer 3 is used instead of polymer 1, the rigid mask composition according to Example 3 is prepared in the same manner as in Example 1.

[0111] Example 4

[0112] Except that polymer 4 is used instead of polymer 1, the rigid mask composition according to Example 4 is prepared in the same manner as in Example 1.

[0113] Comparative Example 1

[0114] 1.5 g of compound A according to Comparative Synthesis Example 1 was dissolved in a mixed solvent of 10 g propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7:3 (v / v)) and then filtered through a 0.1 μm Teflon (tetrafluoroethylene) filter to prepare the hard screen composition according to Comparative Example 1.

[0115] Comparative Example 2

[0116] Except that compound B according to Comparative Synthesis Example 2 was used instead of compound A, the rigid mask composition was prepared in the same manner as in Comparative Example 1.

[0117] Assessment 1: Etching Resistance Assessment

[0118] Each of the hard mask compositions of Examples 1 to 4 and Comparative Examples 1 to 2 was spin-coated onto a silicon wafer and then heat-treated on a hot plate at 400°C for 2 minutes to form a 4,000 Å thick film. The film thickness was then measured using a film thickness measuring device manufactured by K-MAC. Subsequently, the film was dry-etched for 100 seconds using a CF4 / CHF3 mixed gas, and the thickness was measured again. The bulk etch rate (BER) was calculated using the thickness before and after dry etching of the film relative to the etching time, according to Equation 1, and the results are shown in Table 1.

[0119] [Calculate Equation 1]

[0120] Etching rate (Å / s) = (Initial film thickness - Post-etched film thickness) / Etching time

[0121] [Table 1] Bulk etching rate (Å / s) CF x / CHF x Etching Example 1 24.2 Example 2 23.7 Example 3 24.6 Example 4 25.0 Comparative Example 1 27.2 Comparative Example 2 26.8

[0122] Referring to Table 1, compared with the hard masking layers formed from the hard masking compositions according to Comparative Examples 1 to 2, the hard masking layers formed from the hard masking compositions according to Examples 1 to 4 exhibit a low etch rate to the CF4 / CHF3 mixed gas and therefore exhibit excellent etch resistance.

[0123] Assessment 2: Solubility Assessment

[0124] Polymers 1 to 4, as well as compounds A and B, according to the synthesis examples and comparative synthesis examples, were added to 20 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to examine solubility. Solubility was assessed by measuring the amount of each polymer or compound in 20 g of solvent and then converting it to a percentage according to calculation equation 2. The results are shown in Table 2.

[0125] [Calculate Equation 2]

[0126] Solubility (%) = {Mass of polymer or compound (g) / Mass of solvent (20 g)}

[0127] [Table 2] 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

[0128] Referring to Table 2, the polymers of the synthetic examples exhibit greater solubility in PGMEA than the compounds of the comparative synthetic examples.

[0129] Assessment 3: Membrane density assessment

[0130] The hard mask compositions according to Examples 1 to 4 and Comparative Examples 1 to 2 were spin-coated onto silicon wafers and then heat-treated on a hot plate at 400°C for 2 minutes to form hard mask layers with a thickness of 1,000 Å. The film density of the hard mask layers was measured using an X-ray diffraction apparatus from PANalytical Ltd., and the results are shown in Table 3.

[0131] [Table 3] Film density (g / cm³) 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

[0132] Referring to Table 3, the rigid masking layers formed from the rigid masking compositions of Examples 1 to 4 exhibit greater density and superior physical properties than the rigid masking layers formed from the rigid masking compositions of Comparative Examples 1 to 2.

[0133] In summary, given the small size of the patterns to be formed, it may be difficult to provide fine patterns with excellent contours using some photolithography techniques. Therefore, an auxiliary layer called a hard mask layer can be formed between the material layer and the photoresist layer to provide fine patterns.

[0134] One or more embodiments may provide a rigid masking composition that can be effectively applied to a rigid masking layer.

[0135] The rigid mask composition according to some embodiments has excellent solubility in solvents and can be effectively applied to the rigid mask layer.

[0136] According to some embodiments, a rigid mask layer formed from a rigid mask composition can help ensure excellent etch resistance and excellent patterning properties.

[0137] According to some embodiments, a rigid mask layer formed from a rigid mask composition can have a high film density, thereby improving the physical properties of the film.

[0138] Exemplary embodiments have been disclosed herein, and although specific terminology has been used, it is used in a general and illustrative sense only and should be interpreted in a general and illustrative sense, and is not intended to be limiting. In some cases, it will be apparent to those skilled in the art at the time of filing of this application that, unless otherwise specifically stated, features, characteristics, and / or elements set forth in connection with particular embodiments may be used alone or in combination with features, characteristics, and / or elements set forth in connection with other embodiments. Therefore, those skilled in the art will understand that various changes in form and detail may be made without departing from the spirit and scope of the invention as described in the foregoing claims.

[0139] none

Claims

1. A rigid mask composition comprising: a polymer including structural units represented by Chemical Formula 1; and a solvent, [Chemical Formula 1] wherein, In Formula 1, A is the substituted or unsubstituted portion of group 1-1, B is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, R1 and R2 are each independently deuterium, hydroxyl group, halogen atom, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C1 to C20 saturated or unsaturated aliphatic hydrocarbon group or combination thereof, n1 and n2 are each independently integers from 0 to 9, and * is a connecting point, [Group 1-1] wherein, in group 1-1, X is -CRcRd-, -N(Re)-, -O- or -S-, and Rc to Re are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C6 to C20 aryl group or combination thereof.

2. The rigid masking assembly as claimed in claim 1, wherein A is the replaced or unreplaced portion of group 1-2: [group 1-2] .

3. The rigid mask assembly as described in claim 1, wherein: R1 and R2 are each independently a deuterium, hydroxyl, halogen atom, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, or combinations thereof, and n1 and n2 are each independently an integer from 0 to 4.

4. The rigid mask assembly as described in claim 1, wherein: R1 and R2 are each independently deuterium, hydroxyl, halogen atom, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl or combinations thereof, and n1 and n2 are each independently 0 or 1.

5. The rigid mask assembly as described in claim 1, wherein: Formula 1 is represented by one of Formulas 1-1 to 1-4: [Formula 1-1] [Formula 1-2] [Formula 1-3] [Formula 1-4] In Formulas 1-1 to 1-4, R11 and R21 are each independently deuterium, hydroxyl, halogen atom, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl or combinations thereof, R31 and R41 are each independently deuterium, hydroxyl, halogen atom, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C20 aryl or combinations thereof, and n11, n21, n31, and n41 are each independently an integer greater than or equal to 0 and an integer less than or equal to the bond valence of the ring to which R11, R21, R31, and R41 are substituted.

6. The rigid masking composition as claimed in 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].

7. The rigid mask composition as claimed in claim 1, wherein the polymer has a weight-average molecular weight of 500 g / mol to 200,000 g / mol.

8. The rigid masking composition as claimed in claim 1, wherein the polymer is contained in an amount from 0.01% by weight to 30% by weight based on the total weight of the rigid masking composition.

9. The rigid mask composition as claimed in 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, acetoacetone, or ethyl 3-ethoxypropionate.

10. A rigid mask layer comprising a cured product of the rigid mask composition as described in claim 1.

11. A method for forming a pattern, the method comprising: A material layer is provided on a substrate, a hard mask composition as described in claim 1 is applied to the material layer, the hard mask composition is heat-treated to form a hard mask layer, a photoresist layer is formed on the hard mask layer, the photoresist layer is exposed and developed to form a photoresist pattern, the hard mask layer is selectively removed using the photoresist pattern to expose a portion of the material layer, and the exposed portion of the material layer is etched.

12. The method of claim 11, wherein forming the rigid cover layer includes heat treatment at 100°C to 1,000°C.

Images