Resist underlayer composition and method of forming pattern using the same

Abstract

The invention provides a resist underlayer composition, a method for forming a pattern by using the resist underlayer composition, a system for forming a pattern by using the resist underlayer composition, and a resist underlayer of the resist underlayer composition. The resist underlayer composition may include a polymer including a structural unit represented by Chemical Formula 1 and a structural unit represented by Chemical Formula 2, and a solvent. Chemical formula 1 and chemical formula 2

Description

[0001] Cross-reference of related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2024-0117149, filed on August 29, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to a resist underlayer composition and a method for forming patterns using the resist underlayer composition. Background Technology

[0004] The semiconductor industry has recently advanced to ultra-fine patterning technology, with pattern sizes ranging from several nanometers to tens of nanometers. These ultra-fine technologies require highly efficient lithography processes.

[0005] Lithography, or lithography, is a process that includes coating a photoresist film onto a semiconductor substrate (e.g., a silicon wafer) to form a thin film; irradiating the photoresist film with activation radiation (e.g., ultraviolet light (UV)) through a mask that carries a device pattern; developing the exposed film to form a photoresist pattern; and using the photoresist pattern as a mask to etch the substrate to form a fine pattern on the substrate surface.

[0006] As semiconductor patterns continue to shrink, thinner photoresist layers are required. Therefore, the resist underlayer should also be thinner. Despite the reduced thickness, the resist underlayer must maintain sufficient mechanical strength to support the photoresist pattern, exhibit good adhesion to the photoresist, and form at a uniform thickness. Furthermore, the resist underlayer should have a high refractive index and low extinction coefficient for the light used in lithography, as well as a faster etching rate than the photoresist layer. Summary of the Invention

[0007] One or more aspects of the embodiments of this disclosure are directed to a resist underlayer composition that provides a resist underlayer in which pattern collapse of the resist does not occur (or the degree or rate of pattern collapse of the resist is reduced) even in fine patterning processes, and the sensitivity to exposure light sources is improved or enhanced, thereby improving or enhancing patterning performance and energy efficiency.

[0008] One or more aspects of the embodiments of this disclosure are related to a method for forming patterns using a resist underlayer composition.

[0009] Other aspects of the embodiments will be set forth in part in the description which follows, and in part will be obvious from the description or may be learned by practice of the embodiments presented in this disclosure.

[0010] A resist underlayer composition according to one or more embodiments includes a polymer including structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2, and a solvent:

[0011] Chemical Formula 1

[0012]

[0013] wherein, in Chemical Formula 1,

[0014] m is one of integers from 1 to 4,

[0015] n is one of integers from 1 to 4,

[0016] m+n is an integer less than or equal to 5, and

[0017] * is a connecting point;

[0018] Chemical Formula 2

[0019]

[0020] wherein, in Chemical Formula 2,

[0021] L 1 is a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene, a substituted or unsubstituted C2 to C10 alkenylene, a substituted or unsubstituted C2 to C10 alkynylene, a substituted or unsubstituted C3 to C20 cycloalkylene, a substituted or unsubstituted C3 to C20 heterocycloalkylene, a substituted or unsubstituted C6 to C20 arylene, or a combination thereof,

[0022] X 1 and X 2 are each independently a single bond (e.g., a single covalent bond), -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(CO)O-, -O(CO)O-, -C(=O)NH-, -NR a -(wherein, R a is hydrogen, deuterium, or C1 to C10 alkyl), or a combination thereof,

[0023] Y 1 is a group represented by Chemical Formula 3,

[0024] R 1 to R 3 are each independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl, and

[0025] * is a connecting point:

[0026] Chemical Formula 3

[0027]

[0028] wherein, in Chemical Formula 3,

[0029] M 1 is a single bond (e.g., a single covalent bond), substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C2 to C20 alkenylene, -O-, -NH-, or a combination thereof,

[0030] Z 1 and Z 2 are each independently -C(=O)- or -CH(OH)-,

[0031] M 2 is a single bond (e.g., a single covalent bond), a double bond (e.g., a carbon-carbon double bond), *-C(R b )=* (wherein R b is hydrogen, deuterium, or C1 to C5 alkyl, and * is a point of attachment to Z 1 or Z 2 ), or substituted or unsubstituted C1 to C3 alkylene,

[0032] M 3 is hydroxyl, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, or substituted or unsubstituted C6 to C20 aryl,

[0033] M 1 and M 3 or M 2 and M 3 are optionally linked (e.g., attached) to each other to form a ring, and

[0034] * is a point of attachment.

[0035] In Chemical Formula 1, m and n can each independently be 1 or 2.

[0036] In Chemical Formula 3, L 1 may be a single bond (e.g., a single covalent bond) or substituted or unsubstituted C1 to C10 alkylene, and X 1 and X 2 may each independently be a single bond (e.g., a single covalent bond) or -(CO)O-.

[0037] In the polymer, the structural unit represented by Chemical Formula 1 and the structural unit represented by Chemical Formula 2 can be present in a molar ratio of about 9:1 to about 1:9.

[0038] The polymer can further comprise a structural unit represented by Chemical Formula 4:

[0039] Chemical Formula 4

[0040]

[0041] wherein, in Chemical Formula 4,

[0042] L 2 may be a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene, a substituted or unsubstituted C2 to C10 alkenylene, a substituted or unsubstituted C2 to C10 alkynylene, a substituted or unsubstituted C3 to C20 cycloalkylene, a substituted or unsubstituted C2 to C20 heterocycloalkylene, a substituted or unsubstituted C6 to C20 arylene, or a combination thereof,

[0043] X 3 and X 4 may each independently be a single bond (e.g., a single covalent bond), -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(CO)O-, -O(CO)O-, -C(=O)NH-, -NR c -(wherein, R c is hydrogen, deuterium, or C1 to C10 alkyl), or a combination thereof,

[0044] Y 2 may be hydroxyl, a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C2 to C10 alkenyl, a substituted or unsubstituted C2 to C10 alkynyl, a substituted or unsubstituted C3 to C20 cycloalkyl, a substituted or unsubstituted C2 to C20 heterocycloalkyl, or a substituted or unsubstituted C6 to C20 aryl,

[0045] R 4 to R 6 may each independently be hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl, and

[0046] *may be a point of attachment.

[0047] In Chemical Formula 4, L 2 may be a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene, or a substituted or unsubstituted C6 to C10 arylene, X 3 and X 4 may each independently be a single bond (e.g., a single covalent bond) or -(CO)O-, and Y 2 may be hydroxyl, a substituted or unsubstituted C1 to C10 alkyl, a substituted or unsubstituted C2 to C20 heterocycloalkyl, or a substituted or unsubstituted C6 to C20 aryl.

[0048] Chemical Formula 2 can be represented by one or more selected from Chemical Formula 2-1 to Chemical Formula 2-8:

[0049] Chemical Formula 2-1

[0050]

[0051] Chemical Formula 2-2

[0052]

[0053] Chemical Formula 2-3

[0054]

[0055] Chemical Formula 2-4

[0056]

[0057] Chemical Formula 2-5

[0058]

[0059] Chemical Formula 2-6

[0060]

[0061] Chemical Formula 2-7

[0062] and

[0063] Chemical Formula 2-8

[0064]

[0065] The weight average molecular weight (Mw) of the polymer can be about 1,000 g / mol to about 300,000 g / mol. w

[0066] The polymer can be included in an amount of about 0.1 wt% to about 50 wt% based on the total weight of the resist underlayer composition (e.g., based on 100 wt%).

[0067] The composition can further include one or more polymers selected from an acrylic resin, an epoxy resin, a novolak resin, a glycoluril resin, and a melamine resin.

[0068] The composition can further include an additive of a surfactant, a thermal acid generator, a photoacid generator, a plasticizer, or a combination thereof.

[0069] ​According to one or more embodiments, a method of forming a pattern includes forming an etch target layer on a substrate, forming a resist underlayer by applying a resist underlayer composition according to one or more embodiments on the etch target layer, forming a photoresist pattern on the resist underlayer, and sequentially etching the resist underlayer and the etch target layer using the photoresist pattern as an etch mask.

[0070] According to one or more embodiments, a system of forming a pattern includes means for forming an etch target layer on a substrate, means for forming a resist underlayer by applying a resist underlayer composition according to one or more embodiments on the etch target layer, means for forming a photoresist pattern on the resist underlayer, and means for sequentially etching the resist underlayer and the etch target layer using the photoresist pattern as an etch mask.

[0071] One or more embodiments of the present disclosure provide a resist underlayer of a resist underlayer composition as described in one or more embodiments.

[0072] A resist underlayer composition according to one or more embodiments can provide a resist underlayer that does not experience (or experiences a reduced degree of) resist pattern collapse even in fine patterning processes and can improve or enhance sensitivity to exposure light sources, thus enabling improved or enhanced patterning performance and energy efficiency. For example, the resist underlayer can effectively or suitably inhibit or prevent pattern collapse of a photoresist even during fine patterning processes involving sub-10 nanometer features. This is achieved through the tailored design of the polymer structure, which includes specific functional groups and linkages that enhance mechanical strength, film uniformity, and interfacial adhesion. Furthermore, the composition can exhibit improved or enhanced sensitivity to exposure light sources, thus enabling reduced exposure dose and enhanced energy efficiency. These properties contribute to improved or enhanced lithography performance, including better critical dimension control, reduced line edge roughness, and higher pattern fidelity.

[0073] In addition, the resist underlayer composition can be formulated to exhibit a high refractive index and low extinction coefficient at the exposure wavelength, which enhances the optical contrast and resolution of the photoresist pattern. The composition can also be designed to have a higher etch rate than the photoresist, facilitating selective removal during the pattern transfer process. These properties make the composition suitable for use in advanced semiconductor manufacturing. BRIEF DESCRIPTION OF DRAWINGS

[0074] The accompanying drawings are included to provide a further understanding of embodiments of the present disclosure, and are incorporated in and constitute a part of this specification.

[0075] Figure 1 A cross-sectional view illustrating a method of forming a pattern using a resist underlayer composition according to one or more embodiments.

[0076] Explanation of icon numbers

[0077] 100: Substrate;

[0078] 102: Film;

[0079] 104: Resist underlayer;

[0080] 106a: Exposure area;

[0081] 106b: Unexposed area;

[0082] 106: Photoresist film;

[0083] 108: Photoresist pattern;

[0084] 110: Exposure mask;

[0085] 112: Organic thin film pattern;

[0086] 114: Thin film pattern. Detailed Implementation

[0087] The objects of this disclosure will be described more fully below with reference to the accompanying drawings, which illustrate embodiments of the disclosure. As those skilled in the art will recognize, the embodiments may be modified in one or more suitable different ways without departing from the spirit or scope of this disclosure. The drawings and descriptions should be considered illustrative in nature and not restrictive.

[0088] When describing embodiments of this disclosure, the word "may" means "one or more embodiments of this disclosure".

[0089] As used herein, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well. Unless the context clearly indicates otherwise, singular expressions include plural expressions.

[0090] As used herein, the terms “and / or” or “or” include any and all combinations of one or more of the associated enumerated items. Throughout this disclosure, expressions such as “at least one,” “one of,” and “selected from” modify the entire list of elements without modifying individual elements of the list when they precede it (e.g., when). For example, “at least one of a, b, or c,” “selected from at least one of a, b, and c,” or “selected from at least one of a to c,” and / or similar expressions indicate only a, only b, only c, both a and b (e.g., simultaneously), both a and c (e.g., simultaneously), both b and c (e.g., simultaneously), all a, b, and c, or variations thereof.

[0091] In this disclosure, the terms “comprise(s) / comprising,” “include(s) / including,” or “have / has / having” specify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Furthermore, the terms “comprise(s) / comprising,” “include(s) / including,” “have / has / having,” or similar terms include or support the terms “consisting of” and “consisting essentially of,” indicating the presence of the stated features, integers, steps, operations, elements, and / or components, with no or substantially no other features, integers, steps, operations, elements, components, and / or groups thereof.

[0092] In the context of this application and unless otherwise defined, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively.

[0093] In the accompanying drawings, the thickness of layers, films, panels, areas and / or the like may be enlarged for clarity, and the same reference numerals denote the same components throughout the drawings and written description, and their repeated description may be omitted in the specification.

[0094] It should be understood that if (for example, when) a component, such as a layer, film, region, or substrate, is referred to as "on" or "on top of" another component, it may be directly on or above the other component, or an intervening component may also be present therein. Conversely, if (for example, when) a component is referred to as "directly on" or "directly on top of" another component, there is no intervening component therein.

[0095] As used herein, the terms “substantially,” “about,” or similar terms are used as approximate terms rather than terms of degree and are intended to describe inherent deviations in measured or calculated values ​​that would be recognized by a person skilled in the art. As used herein, “about” includes the stated value and refers to a specific value within an acceptable deviation range determined by a person skilled in the art, taking into account the measurement in question and errors associated with the measurement of the specific quantity (e.g., limitations of the measurement system). For example, “about” may mean within one or more standard deviations or within ±30%, ±20%, ±10%, or ±5% of the stated value. Furthermore, it should be understood that even if (e.g., when) the terms “about,” “approximately,” or “substantially” are not explicitly stated in a given component (e.g., a component of the claim), the scope of such a component is intended to include non-substantialtive variations or variations understood by a person skilled in the art. For example, the numerical values ​​and ranges provided herein are intended to include tolerances and measurement uncertainties that would be recognized by a person skilled in the art, and components (e.g., components of the claim) should be interpreted accordingly to cover such equivalents.

[0096] Any numerical range described herein is intended to include all subranges containing the same numerical precision within the described range. For example, the range “1.0 to 10.0” is intended to include all subranges between (and including) the described minimum value of 1.0 and the described maximum value of 10.0, such as having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this disclosure is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to modify the disclosure (including the application) to explicitly describe any subranges contained within the explicitly described range herein.

[0097] As used herein, unless otherwise defined, “substituted” means by substituting a hydrogen atom of a compound by a substituent selected from deuterium, halogen (e.g., F, Br, Cl, or I), hydroxyl, nitro, cyano, amino, azide, amido, hydrazine, hydrazone, carbonyl, carbamoyl, thiol, ester, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphate or a salt thereof, C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 aralkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C3 to C20 heteroaralkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocyclic, and combinations thereof.

[0098] Furthermore, two adjacent substituents of substituted halogen atoms (e.g., F, Br, Cl, or I), hydroxyl, nitro, cyano, amino, azide, amido, hydrazine, hydrazone, carbonyl, carbamoyl, 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 aralkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C3 to C20 heteroaralkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, or C2 to C30 heterocyclic groups may fuse with each other to form a ring.

[0099] As used herein, "heterocyclic group" includes heteroaryl groups and cyclic groups containing at least one heteroatom selected from N, O, S, P, and Si, rather than carbon (C) of a cyclic compound, such as aryl, cycloalkyl, their fused rings, or combinations thereof. If (for example, when) the heterocyclic group is fused, each ring or the entire ring of the heterocyclic group may contain at least one heteroatom.

[0100] For example, substituted or unsubstituted aryl and / or substituted or unsubstituted heterocyclic groups can be substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraceneyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrene, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted trefyl, substituted or unsubstituted benzotriphenyl, substituted or unsubstituted peryl, substituted... Or unsubstituted indole, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrrole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted Triazine, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxolinyl, substituted or unsubstituted naphthidyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridineyl, substituted or unsubstituted phenazinyl, substituted... The substituted or unsubstituted phenothiazine group, substituted or unsubstituted phenotoxazine group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene group, substituted or unsubstituted carbazole group, substituted or unsubstituted pyridinodolyl group, substituted or unsubstituted benzopyridoxazine group, substituted or unsubstituted benzopyridhiazine group, substituted or unsubstituted 9,9-dimethyl-9,10-dihydroacridinyl group, combinations thereof, or combinations of the foregoing groups are fused rings, but the embodiments of this disclosure are not limited thereto.

[0101] As used herein, the term “combination” refers to a mixture or copolymerization unless otherwise specifically defined.

[0102] Furthermore, as used herein, “polymer” may (e.g., simultaneously) include both oligomers and polymers.

[0103] Unless otherwise specified in this disclosure, the weight average molecular weight (M) wThe measurement was performed by dissolving the 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) to measure the sample.

[0104] In addition, unless otherwise defined in the specification, "*" indicates the connection point of a structural unit or part of the polymer.

[0105] In the semiconductor industry, there is a desire to reduce chip size. To meet this requirement, it is desirable to reduce the linewidth of patterned resist in lithography to the tens of nanometers level, and the pattern formed in this way can be transferred to the underlying material by an etching process on the underlying substrate. However, as the resist pattern size decreases, the resist height (e.g., aspect ratio) that can accommodate the linewidth is limited, and therefore, the resist may not have sufficient or suitable impedance during the etching step. Therefore, this deficiency has been compensated for when using thin resist materials, when the substrate to be etched is thick, and / or when deep patterns are desired or required.

[0106] As the resist thickness decreases, the resist substrate is expected to become thinner, and even with a thinner resist substrate, the photoresist pattern is expected not to collapse. For this purpose, the resist substrate is expected to have excellent or suitable adhesion to the photoresist. Furthermore, when forming a thin resist substrate, it is desirable to improve or enhance the coating uniformity of the resist substrate composition and the flatness of the resulting resist substrate, and to improve or enhance the sensitivity to the exposure light source to improve or enhance patterning capability and energy efficiency.

[0107] According to one or more embodiments, the resist underlayer composition may include a polymer comprising structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2, and a solvent:

[0108] Chemical Formula 1

[0109]

[0110] In chemical formula 1,

[0111] m can be any integer from 1 to 4.

[0112] n can be any integer from 1 to 4.

[0113] m+n can be an integer less than or equal to 5, and

[0114] *Can be a connection point;

[0115] Chemical formula 2

[0116]

[0117] In chemical formula 2,

[0118] L 1 It may be a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 ynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 heteroalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

[0119] X 1 and X 2 They can each independently be single bonds (e.g., monocovalent bonds), -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(CO)O-, -O(CO)O-, -C(=O)NH-, -NR a -(where R) a (which may be hydrogen, deuterium, or C1 to C10 alkyl), or combinations thereof,

[0120] Y 1 It can be a group represented by chemical formula 3.

[0121] R 1 To R 3 Each can be independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group, and

[0122] *Can be a connection point:

[0123] Chemical formula 3

[0124]

[0125] In chemical formula 3,

[0126] M 1 It can be a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenyl group, -O-, -NH-, or a combination thereof.

[0127] Z 1 and Z 2 They can each be independently -C(=O)- or -CH(OH)-.

[0128] M 2 It can be a single bond (e.g., a single covalent bond), a double bond (e.g., a carbon-carbon double bond), or a *-C(R) bond.b ) = *(where R b It is hydrogen, deuterium, or C1 to C5 alkyl, and * is related to Z. 1 or Z 2 (the junction point), or substituted or unsubstituted C1 to C3 alkylene groups,

[0129] M 3 It can be hydroxyl, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, or substituted or unsubstituted C6 to C20 aryl.

[0130] M 1 and M 3 Or M 2 and M 3 They can be selectively connected to each other (e.g., connected to each other) to form a loop, and

[0131] *Can be a connection point.

[0132] The polymer included in the resist underlayer composition according to one or more embodiments may include structural units represented by Chemical Formula 1 and structural units represented by Chemical Formula 2. The structural unit represented by Chemical Formula 1 may include a benzene ring and an iodine (I) atom, which may have high light absorption efficiency and may improve or enhance the polymer's sensitivity when exposed to light (e.g., when). The structural unit represented by Chemical Formula 2 may include a group represented by Chemical Formula 3 at its end, and the group represented by Chemical Formula 3 may include two or more -(C=O)- or -CH(OH)- groups at adjacent positions, thus enabling it to form coordination bonds with inorganic materials in the photoresist. Therefore, the close contact properties between the resist underlayer formed from the composition including the polymer and the photoresist film may be increased or enhanced.

[0133] In chemical formula 1, m can be, for example, one of the integers from 1 to 4, such as one of the integers from 1 to 3, 1 or 2, or 1. In one or more embodiments, n can be, for example, one of the integers from 1 to 4, such as one of the integers from 1 to 3, 2 or 3, or 2. In one or more embodiments, m+n can be less than or equal to 5, and can be, for example, one of the integers from 2 to 4, such as 3.

[0134] In chemical formula 2, X 1 and X 2 Each of these bonds can be, for example, a single bond (e.g., a single covalent bond), -O-, -C(=O)-, or -(CO)O-, but the embodiments of this disclosure are not limited thereto.

[0135] In chemical formula 2, L 1It may be, for example, a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C2 to C10 alkenyl group, such as a single bond (e.g., a single covalent bond) or a substituted or unsubstituted C1 to C10 alkylene group, such as a single bond (e.g., a single covalent bond) or a substituted C1 to C10 alkylene group, such as a single bond (e.g., a single covalent bond) or a hydroxyl-substituted C1 to C5 alkylene group, but the embodiments of this disclosure are not limited thereto.

[0136] In chemical formula 2, R 1 To R 3 It may be, for example, hydrogen, deuterium, or substituted or unsubstituted C1 to C5 alkyl, and may be, for example, hydrogen, methyl, or ethyl, but the embodiments disclosed herein are not limited thereto.

[0137] In chemical formula 3, M 1 It may be, for example, a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenyl group, -O-, -NH-, or a combination thereof, such as a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenyl group, -O-, -NH-, or a combination thereof, such as a substituted or unsubstituted C1 to C5 alkylene group, -NH-, such as a combination of -O- and C1 to C5 alkylene groups, such as a combination of -O- and C2 to C5 alkenyl groups, but the embodiments of this disclosure are not limited thereto.

[0138] In chemical formula 3, Z 1 and Z 2 They can each be independently -C(=O)- or -CH(OH)-, for example, Z. 1 and Z 2 Each can be -C(=O)-, for example, Z 1 and Z 2 Each can be -CH(OH)-, for example, from Z 1 and Z 2 One of the choices can be -C(=O)- and the other can be -CH(OH)-.

[0139] In chemical formula 3, M 2 It can be a single bond (e.g., a single covalent bond), a double bond (e.g., a carbon-carbon double bond), or a *-C(R) bond. b ) = *(where R bThe methylene group is hydrogen, deuterium, or a C1 to C5 alkyl group, or a substituted or unsubstituted C1 to C3 alkylene group, and is, for example, a single bond (e.g., a monocovalent bond), a double bond (e.g., a carbon-carbon double bond), *-CH=*, *-C(CH3)=*, or a substituted or unsubstituted methylene group, but the embodiments of this disclosure are not limited thereto. In *-C(R b In the equation ) = *, * can be related to Z. 1 or Z 2 The connection point.

[0140] If (for example, when) M 2 When Z has more carbon atoms than the number of carbon atoms described in one or more embodiments, 1 and Z 2 The distance between them can become larger, making it difficult to form effective or appropriate coordination bonds with the inorganic materials in the photoresist, thus the close contact between the photoresist film and the resist substrate may be poor. For example, if (e.g., when) M 2 For single bonds (e.g., monocovalent bonds), double bonds (e.g., carbon-carbon double bonds), *-C(R) b When )=*, or substituted or unsubstituted C1 to C3 alkylene groups, the close contact between the resist underlayer made of polymer and the photoresist film can be effectively or appropriately increased or enhanced.

[0141] In chemical formula 3, M 3 It may be hydroxyl, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, or substituted or unsubstituted C6 to C20 aryl, such as hydroxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, or substituted or unsubstituted C6 to C10 aryl, such as hydroxyl, substituted or unsubstituted C1 to C5 alkyl, substituted or unsubstituted C2 to C5 alkenyl, or substituted or unsubstituted phenyl, but the embodiments disclosed herein are not limited thereto.

[0142] M of chemical formula 3 1 and M 3 Or M 2 and M 3 They can independently connect with each other to form a ring. For example, M of chemical formula 3. 1 and M 3 They can be selectively connected to form a loop, or M 2 and M 3 They can be selectively connected to each other to form a loop. For example, M 1 and M 3 They can exist independently, and M 1 and M3 They can be connected to form a loop, and M 2 and M 3 They can exist independently, and M 2 and M 3 They can be connected to each other to form a ring.

[0143] In the polymer, the molar ratio of the structural unit represented by Formula 1 to the structural unit represented by Formula 2 can be from about 9:1 to about 1:9, for example, from about 8:2 to about 2:8, from about 7:3 to about 2:8, from about 6:4 to about 2:8, from about 5:5 to about 2:8, from about 8:2 to about 3:7, from about 8:2 to about 4:6, or from about 8:2 to about 5:5, but the embodiments of this disclosure are not limited thereto. By including the aforementioned structural units in the polymer in the aforementioned proportions, the light absorption efficiency and / or sensitivity of the resist underlayer composition according to one or more embodiments can be easily or appropriately controlled or selected, and the surface roughness and planarization of the resist underlayer thus produced can be improved (or enhanced) or optimized.

[0144] According to one or more embodiments, the resist underlayer composition may further comprise structural units represented by chemical formula 4:

[0145] Chemical Formula 4

[0146]

[0147] In chemical formula 4,

[0148] L 2 It may be a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 ynynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof.

[0149] X 3 and X 4 They can each independently be single bonds (e.g., monocovalent bonds), -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(CO)O-, -O(CO)O-, -C(=O)NH-, -NR c -(where R) c (which may be hydrogen, deuterium, or C1 to C10 alkyl), or combinations thereof,

[0150] Y 2It can be hydroxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, or substituted or unsubstituted C6 to C20 aryl.

[0151] R 4 To R 6 Each can be independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group, and

[0152] *Can be a connection point.

[0153] In chemical formula 4, L 2 It can be, for example, a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C6 to C10 aryl group, for example, a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C10 aryl group, for example, a single bond (e.g., a single covalent bond) or a substituted or unsubstituted C1 to C5 alkylene group, but the embodiments disclosed herein are not limited thereto.

[0154] In chemical formula 4, X 3 and X 4 Each can be independently, for example, a single bond (e.g., a single covalent bond), -O-, -C(=O)-, -S-, -S(=O)-, -S(=O)2-, or -(CO)O-, for example, a single bond (e.g., a single covalent bond) or -(CO)O-, but the embodiments of this disclosure are not limited thereto.

[0155] In chemical formula 4, Y 2 It can be, for example, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C20 heterocyclic alkyl, or substituted or unsubstituted C6 to C20 aryl, for example, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C20 heterocyclic alkyl, or substituted or unsubstituted C6 to C20 aryl, for example, hydroxyl, substituted or unsubstituted C1 to C5 alkyl, or substituted or unsubstituted C2 to C10 heterocyclic alkyl, but the embodiments disclosed herein are not limited thereto.

[0156] In chemical formula 4, R 4 To R 6 Each of them may be hydrogen, deuterium, or substituted or unsubstituted C1 to C10 alkyl groups, for example, hydrogen, deuterium, or substituted or unsubstituted C1 to C5 alkyl groups, but the embodiments disclosed herein are not limited thereto.

[0157] For example, chemical formula 2 can be represented by one or more of chemical formulas 2-1 to 2-8:

[0158] Chemical formula 2-1

[0159]

[0160] Chemical formula 2-2

[0161]

[0162] Chemical formula 2-3

[0163]

[0164] Chemical formula 2-4

[0165]

[0166] Chemical formula 2-5

[0167]

[0168] Chemical formula 2-6

[0169]

[0170] Chemical formula 2-7

[0171] as well as

[0172] Chemical formula 2-8

[0173]

[0174] The polymer may have a weight average molecular weight (M0.05) of about 1,000 g / mol to about 300,000 g / mol. w Examples of molecular weights in the present disclosure are approximately 3,000 g / mol to approximately 200,000 g / mol, approximately 3,000 g / mol to approximately 100,000 g / mol, approximately 3,000 g / mol to approximately 90,000 g / mol, approximately 3,000 g / mol to approximately 70,000 g / mol, approximately 3,000 g / mol to approximately 50,000 g / mol, approximately 5,000 g / mol to approximately 50,000 g / mol, and approximately 5,000 g / mol to approximately 30,000 g / mol, but the embodiments disclosed are not limited thereto. By having a weight-average molecular weight within the foregoing range, the carbon content (e.g., amount) and solubility of the resist underlayer composition comprising the polymer in the solvent can be adjusted and modified (or enhanced) or optimized.

[0175] Based on the total weight of the resist underlayer composition (e.g., based on 100 wt%), the polymer may be included in an amount from about 0.1 wt% to about 50 wt%. For example, based on the total weight of the resist underlayer composition (e.g., based on 100 wt%), the polymer may be included in an amount from about 0.05 wt% to about 40 wt%, from about 0.05 wt% to about 30 wt%, from about 0.05 wt% to about 20 wt%, from about 0.1 wt% to about 40 wt%, for example, from about 0.1 wt% to about 30 wt%, for example, from about 0.1 wt% to about 20 wt%, for example, from about 0.2 wt% to about 20 wt%, but the embodiments of this disclosure are not limited thereto. By including the polymer in the composition within the foregoing range, the thickness, surface roughness, and planarization degree of the resist underlayer can be adjusted and improved (or enhanced) or optimized.

[0176] The resist underlayer composition according to one or more embodiments may contain a solvent. The solvent is not specifically limited, provided it has sufficient or suitable solubility and / or dispersibility for the polymers and compounds according to one or more embodiments, but may be, for example, propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methyl 2-hydroxyisobutyrate, acetylacetone, ethyl 3-ethoxypropionate, or combinations thereof, but the embodiments disclosed herein are not limited thereto.

[0177] In addition to the polymers and solvents described in one or more embodiments, the resist underlayer composition according to one or more embodiments may further include one or more polymers selected from acrylic resins, epoxy resins, phenolic resins, urea resins and melamine resins, but the embodiments disclosed herein are not limited thereto.

[0178] According to one or more embodiments, the resist underlayer composition may further include additives, said additives comprising surfactants, hot acid generators, plasticizers, or combinations thereof.

[0179] If (for example, when) a resist underlayer is formed, a surfactant may be used to improve coating defects caused by an increase in solid content (e.g., amount) (or to reduce the degree or occurrence of coating defects), and may be, for example, alkylbenzene sulfonates, alkylpyridinium salts, polyethylene glycol, quaternary ammonium salts and / or the like, but the embodiments disclosed herein are not limited thereto.

[0180] The hot acid generator may be an acidic compound, such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid pyridinium, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carbonate or / and benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate and other organic alkyl sulfonates may be used, but the embodiments disclosed herein are not limited thereto.

[0181] Plasticizers are not specifically limited, and one or more suitable plasticizers may be used. Examples of plasticizers may include low molecular weight compounds such as phthalates, adipates, phosphates, trimellitic esters, citrates and / or the like, polyether compounds, polyester compounds, polyacetal compounds and / or the like.

[0182] The additive may be included in an amount from about 0.001 parts by weight to about 40 parts by weight, based on 100 parts by weight of the resist underlayer composition. Within the above range, solubility can be improved without altering the optical properties of the resist underlayer composition.

[0183] According to one or more embodiments, a resist underlayer manufactured using the resist underlayer composition as described in one or more embodiments is provided. The resist underlayer can be formed by applying the resist underlayer composition as described in one or more embodiments onto, for example, a substrate and then curing it by a heat treatment process.

[0184] In the following text, refer to Figure 1 (a) to Figure 1 (f) describes in more detail a method for forming a pattern using a resist underlayer composition as described in one or more embodiments. Figure 1 (a) to Figure 1 (f) is a cross-sectional view illustrating the method of forming a pattern using a resist underlayer composition according to the present disclosure.

[0185] refer to Figure 1 (a) An etching target can be prepared. The etching target may be a thin film 102 formed on a semiconductor substrate 100. Hereinafter, the etching target may be limited to the thin film 102. The surface of the thin film 102 may be cleaned to remove impurities and / or similar substances remaining thereon. The thin film 102 may be, for example, a silicon nitride layer, a polysilicon layer, and / or a silicon oxide layer.

[0186] Subsequently, the resist underlayer composition as described in one or more embodiments can be applied to the surface of the cleaned film 102 by spin coating.

[0187] The coated composition is then dried and baked to form a resist underlayer 104 on the film 102. Baking may be performed at approximately 100 degrees Celsius to approximately 500 degrees Celsius, for example, at approximately 100 degrees Celsius to approximately 300 degrees Celsius. For example, the resist underlayer composition is described in more detail herein and will therefore not be provided.

[0188] refer to Figure 1 (b) A photoresist film 106 can be formed by coating a photoresist substrate 104.

[0189] Examples of photoresists may include positive photoresists comprising naphthoquinone diazide compounds and / or phenolic varnish resins; chemically amplified positive photoresists comprising acid-generating agents capable of dissociating acids upon exposure; compounds and / or alkali-soluble resins that decompose in the presence of acid to increase or enhance solubility in alkaline aqueous solutions (e.g., water-soluble solutions); chemically amplified positive photoresists and / or the like comprising acid-generating agents and / or alkali-soluble resins having groups capable of imparting solubility to resins that decompose in the presence of acid to increase or enhance solubility in alkaline aqueous solutions (e.g., water-soluble solutions).

[0190] Next, a first baking process can be performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking process can be performed at a temperature of about 90 degrees Celsius to about 120 degrees Celsius.

[0191] refer to Figure 1 (c) The photoresist film 106 can be selectively exposed. Exposure of the photoresist film 106 can be performed, for example, by positioning an exposure mask having a set or predetermined pattern on the mask stage of an exposure apparatus and aligning the exposure mask 110 onto the photoresist film 106. Subsequently, the set or predetermined areas of the photoresist film 106 on the substrate 100 can be selectively reacted with light passing through the exposure mask by radiating light into the exposure mask 110.

[0192] For example, the light used during exposure may include short-wavelength light, such as an i-line with a wavelength of about 365 nanometers, a KrF excimer laser with a wavelength of about 248 nanometers, and / or an ArF excimer laser with a wavelength of about 193 nanometers. In one or more embodiments, EUV (extreme ultraviolet) with a wavelength of about 13.5 nanometers, corresponding to extreme ultraviolet light, may be used.

[0193] Compared to the photoresist film in the unexposed region 106b, the photoresist film in the exposed region 106a can become relatively hydrophilic. Therefore, the photoresist films in the exposed region 106a and the unexposed region 106b can have different solubilities.

[0194] Next, a second baking process can be performed on the substrate 100. The second baking process can be performed at a temperature of about 90 degrees Celsius to about 150 degrees Celsius. By performing the second baking process, the photoresist film corresponding to the exposed area can be easily or appropriately dissolved in a specific solvent.

[0195] refer to Figure 1(d) For example, by using tetra-methyl ammonium hydroxide (TMAH) and / or similar substances to dissolve and then remove the photoresist film corresponding to the exposure area 106a, the remaining photoresist film after development can form a photoresist pattern 108.

[0196] Subsequently, the photoresist pattern 108 can be used as an etching mask to etch the resist underlayer 104. For example... Figure 1 The organic thin film pattern 112 shown in (e) can be formed by an etching process as described in one or more embodiments. Etching can be, for example, dry etching using an etching gas, and the etching gas can be, for example, CHF3, CF4, Cl2, O2, and mixtures thereof. As described in one or more embodiments, a smooth etching process can be performed in a short time because the resist underlayer formed by the resist underlayer composition according to one or more embodiments has a fast etching rate.

[0197] Reference Figure 1 (f) The photoresist pattern 108 can be applied as an etching mask to etch the exposed thin film 102. As a result, the thin film can be formed into a thin film pattern 114. In previously performed exposure processes, the thin film pattern 114 formed by exposure processes performed using short-wavelength light sources (e.g., i-line (wavelength of about 365 nm), KrF excimer laser (wavelength of about 248 nm), and / or ArF excimer laser (wavelength of about 193 nm)) can have a width of tens to hundreds of nanometers (nm), and the thin film pattern 114 formed by exposure processes performed using EUV light sources can have a width of less than or equal to about 20 nm.

[0198] The following describes one or more embodiments of the present disclosure in more detail by way of examples relating to polymer synthesis and the preparation of resist underlayer compositions comprising polymers. However, the embodiments of the present disclosure are not limited to the following examples.

[0199] Polymer Synthesis

[0200] Synthesis Example 1

[0201] In a 500 mL three-necked round-bottom flask, 42.77 g of 2,6-diiodo-4-vinylphenol, 24.64 g of (2-acetylacetoxy)ethyl methacrylate (TCI), 1.9 g of dimethyl 2,2'-azobis(2-methylpropionic acid) (V-601; TCIInc.), and 70 g of propylene glycol methyl ether acetate (PGMEA) were added to prepare a reaction solution, and a condenser was connected to it. The reaction solution was heated at 100 °C for 5 hours to allow the reaction to proceed, and then cooled to room temperature. Subsequently, the reaction solution was added dropwise to a beaker containing 450 g of heptane while stirring to produce a gel-like substance dissolved in 90 g of PGMEA. Finally, a polymer composed of structural units represented by chemical formulas 1-1 and 2-1 was obtained. (Mw: 4,400 g / mol)

[0202] Chemical Formula 1-1

[0203]

[0204] Chemical formula 2-1

[0205]

[0206] Synthesis Example 2

[0207] In a 100 mL two-necked round-bottom flask, 42.77 g of 2,6-diiodo-4-vinylphenol, 27.17 g of 2-hydroxybenzoic acid 2-[(1-oxo-2-propenyl)oxy]ethyl ester (Angene Chemical), 1.9 g of 2,2'-azobis(2-methylpropionic acid) dimethyl ester (V-601; TCI), and 70 g of propylene glycol methyl ether acetate (PGMEA) were added to prepare a reaction solution, and a condenser was connected to it. The reaction solution was heated at 100 °C for 5 hours to allow the reaction to proceed, and then cooled to room temperature. Subsequently, the reaction solution was added dropwise to a beaker containing 450 g of heptane while stirring to produce a gel-like substance dissolved in 90 g of PGMEA. Finally, a polymer composed of structural units represented by chemical formulas 1-1 and 2-2 was obtained. (Mw: 6,100 g / mol)

[0208] Chemical Formula 1-1

[0209]

[0210] Chemical formula 2-2

[0211]

[0212] Synthesis Example 3

[0213] In a 250 mL two-necked round-bottom flask, 19.65 g of 3-chloro-2-hydroxypropyl methacrylate, 16.1 g of 5-methylindigo, 0.02 g of butylated hydroxytoluene (BHT), and 50 g of DMF were added to prepare a reaction solution, which was then reacted at 90 °C. The reaction solution was stirred for 5 hours, and then quenched with NH4Cl to complete the reaction. The resulting product was purified with water to complete the process, yielding the synthetic product composed of structural units represented by chemical formulas 2-5.

[0214] Subsequently, in a 500 mL two-necked round-bottom flask, 57.5 g of the monomer represented by chemical formula 2-5, 43 g of 2,6-diiodo-4-vinylphenol, 2 g of dimethyl 2,2'-azobis(2-methylpropionic acid) (V-601; TCIInc.), and 100 g of propylene glycol methyl ether acetate (PGMEA) were added to prepare a reaction solution, and a condenser was also prepared. The reaction solution was heated at 90 °C for 2 hours, and then added dropwise to a beaker containing 450 g of heptane while stirring to produce a gel-like substance dissolved in 100 g of PGMEA, ultimately yielding a polymer composed of structural units represented by chemical formulas 1-1 and 2-5. (Mw: 7,600 g / mol)

[0215] Chemical Formula 1-1

[0216]

[0217] Chemical formula 2-5

[0218]

[0219] Synthesis Example 4

[0220] In a 500 mL three-necked round-bottom flask, 42.8 g of 2,6-diiodo-4-vinylphenol, 24.6 g of (2-acetylacetoxy)ethyl methacrylate (TCI), 16.4 g of glycidyl methacrylate (TCI), 2 g of dimethyl 2,2'-azobis(2-methylpropionic acid) (V-601; TCI Inc.), and 85 g of propylene glycol methyl ether acetate (PGMEA) were added to prepare a reaction solution, and a condenser was connected to it. The reaction solution was heated at 90 °C for 1 hour to allow the reaction to proceed, and then cooled to room temperature. Subsequently, the reaction solution was added dropwise to a beaker containing 450 g of heptane while stirring to produce a gel-like substance dissolved in 90 g of PGMEA. Finally, a polymer composed of structural units represented by chemical formulas 1-1, 2-1, and 4-1 was obtained. (Mw: 8,800 g / mol)

[0221] Chemical Formula 1-1

[0222]

[0223] Chemical formula 2-1

[0224]

[0225] Chemical formula 4-1

[0226]

[0227] Comparative Synthesis Example 1

[0228] In a 250 mL three-necked round-bottom flask, 20 g of methyl methacrylate, 3.5 g of dimethyl 2,2'-azobis(2-methylpropionic acid) (V-601; TCI Inc.), and 75 g of propylene glycol methyl ether acetate (PGMEA) were added to prepare a reaction solution, and a condenser was attached to it. The reaction solution was heated at 75 °C for 3 hours to allow the reaction to proceed, and then cooled to room temperature. Subsequently, the reaction solution was added dropwise to a beaker containing 450 g of heptane while stirring to produce a gel-like substance dissolved in 90 g of PGMEA. Finally, a polymer composed of structural units represented by Formula 5 was obtained. (Mw: 3,000 g / mol)

[0229] Chemical formula 5

[0230]

[0231] Comparative Synthesis Example 2

[0232] In a 250 mL three-necked round-bottom flask, 28 g of glycidyl methacrylate (TCI), 3.2 g of dimethyl 2,2'-azobis(2-methylpropionic acid) (V-601; TCI Inc.), and 30 g of propylene glycol methyl ether acetate (PGMEA) were added to prepare a reaction solution, and a condenser was connected to it. The reaction solution was heated at 85 °C for 2 hours to allow the reaction to proceed, and then cooled to room temperature. Subsequently, the reaction solution was added dropwise to a beaker containing 450 g of heptane while stirring to produce a gel-like substance dissolved in 90 g of PGMEA. Finally, a polymer composed of structural units represented by chemical formula 4-1 was obtained. (Mw: 3,500 g / mol)

[0233] Chemical formula 4-1

[0234]

[0235] Comparative Synthesis Example 3

[0236] In a 250 mL three-necked round-bottom flask, 75 g of 2,6-diiodo-4-vinylphenol, 3.3 g of dimethyl 2,2'-azobis(2-methylpropionic acid) (V-601; TCIInc.), and 75 g of propylene glycol methyl ether acetate (PGMEA) were added to prepare a reaction solution, and a condenser was connected to it. The reaction solution was heated at 90 °C for 3 hours to allow the reaction to proceed, and then cooled to room temperature. Subsequently, the reaction solution was added dropwise to a beaker containing 450 g of heptane while stirring to produce a gel-like substance dissolved in 90 g of PGMEA. Finally, a polymer composed of structural units represented by chemical formula 1-1 was obtained. (Mw: 3,400 g / mol)

[0237] Chemical Formula 1-1

[0238]

[0239] Preparation of resist underlayer composition

[0240] Examples 1 to 4 and Comparative Examples 1 to 3

[0241] Each resist underbody composition according to Examples 1 to 4 and Comparative Examples 1 to 3 was prepared by completely dissolving 1.2 g of each polymer, 0.4 g of PL1174 (crosslinking agent), and 0.04 g of ammonium trifluoromethanesulfonate (AOTf) in 15 g of propylene glycol monomethyl ether and diluting the solution with an additional solvent to include 0.45 wt% polymer based on the total weight of the resist underbody composition (e.g., based on 100 wt%).

[0242] Evaluation 1: Exposure Characteristics Evaluation

[0243] The compositions according to Examples 1 to 4 and Comparative Examples 1 to 3 were spin-coated, and then heat-treated on a heated plate at 205°C for 60 seconds to form a 50 angstrom thick resist underlayer. Subsequently, each photoresist solution was spin-coated onto this underlayer, and then heat-treated on a heated plate at 110°C for 1 minute to form a photoresist layer. The photoresist layer was exposed using an electron beam lithography device (accelerating voltage 100 kEV, Elinkens Nanotechnology Co., Ltd.) with a line width of 30 nm and a line spacing of 30 nm. The photoresist layer was then developed in a 2.38% (w / w) TMAH aqueous solution and rinsed with pure water for 15 seconds to form a 50 nm line and space (L / S) photoresist pattern. The photoresist pattern was then evaluated for optimal energy.

[0244] Evaluation 2: Linewidth Roughness (LWR) Evaluation

[0245] Each component of Examples 1 to 4 and Comparative Examples 1 to 3 was spin-coated and then heat-treated on a heated plate at 205°C for 60 seconds to form a 50 Å thick resist underlayer. Subsequently, a photoresist solution was spin-coated onto the underlayer and then heat-treated on a heated plate at 110°C for 1 minute to form a photoresist layer. The resist layer was exposed using an electron beam lithography machine (accelerating voltage: 100 kEV, manufactured by Elinker Nanotechnology Co., Ltd.) with a line width of 30 nm and a line spacing of 30 nm. The exposed resist layer was then heat-treated at 95°C for 60 seconds, developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with pure water for 15 seconds to form a resist pattern.

[0246] The formed pattern was examined with a scanning electron microscope (SEM) S-9260 (Hitachi Ltd.). If pattern collapse was observed (e.g., when), an X was given in Table 1, and if pattern collapse was not observed (e.g., when), an O was given.

[0247] A 30 nm wide pattern was examined using a scanning electron microscope (SEM) S-9260 (Hitachi, Ltd.) to examine the linewidth roughness (LWR) of the edge, measuring the distance from the baseline, where the edge should be within 2 μm along the pattern length. The results are shown in Table 1, where a smaller LWR indicates better properties.

[0248] The exposure dose evaluation examples and comparative examples were converted to a ratio based on 100% of Comparative Example 3. Furthermore, the LWR of the examples and comparative examples were converted to a ratio based on 100% of Comparative Example 2. The results are shown in Table 1. Lower exposure dose and linewidth roughness (LWR) result in better pattern formation and sensitivity.

[0249] Table 1

[0250] Exposure dose (Eop, %) Collapse of pattern LWR (nm) Example 1 95％ X 82％ Example 2 94％ X 89％ Example 3 91％ X 91％ Example 4 96％ X 87％ Comparative Example 1 107％ ○ 108％ Comparative Example 2 104％ ○ 100％ Comparative Example 3 100％ △ 115％

[0251] Referring to Table 1, compared with Comparative Examples 1 to 3, the resist substrates of Examples 1 to 4 exhibited excellent or suitable fine patterning (50 nm L / S) formation and sensitivity. Furthermore, the resist substrates of Examples 1 to 4 had a smaller LWR than Comparative Examples 1 to 3, resulting in a more substantially uniform pattern.

[0252] The pattern forming apparatus, semiconductor forming apparatus, and / or any other related apparatus or component according to one or more embodiments of this disclosure may be implemented using any suitable hardware, firmware (e.g., application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, one or more suitable components of the apparatus may be formed on an integrated circuit (IC) chip or on a discrete IC chip. Furthermore, one or more suitable components of the apparatus may be implemented on a flexible printed circuit film, a tape-on-a-package (TCP), a printed circuit board (PCB), or formed on a substrate. Additionally, one or more suitable components of the apparatus may be a process or thread running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components to perform one or more suitable functions as described herein. The computer program instructions may be stored in memory, which may be implemented in the computing device using standard memory devices, such as random access memory (RAM). The computer program instructions may also be stored in other non-transitory computer-readable media, such as CD-ROMs, flash drives, and / or the like. Furthermore, those skilled in the art will recognize that the functions of one or more suitable computing devices can be combined or integrated into a single computing device, or that the functions of a particular computing device can be distributed across one or more other computing devices without departing from the scope of this disclosure.

[0253] In the foregoing, certain embodiments of this disclosure have been described and illustrated. However, it will be apparent to those skilled in the art that this disclosure is not limited to the embodiments as described, and that suitable modifications and transformations may be made without departing from the spirit and scope of this disclosure. Therefore, modified or transformed embodiments may not be understood solely from the technical conception and aspects of one or more embodiments of this disclosure, and the modified embodiments are within the scope of the appended claims and their equivalents.

Claims

1. A resist underlayer composition comprising: a polymer comprising: a structural unit represented by Chemical Formula 1; and a structural unit represented by Chemical Formula 2; and a solvent: Chemical Formula 1 wherein, in Chemical Formula 1, m is one of an integer from 1 to 4, n is one of an integer from 1 to 4, m+n is an integer less than or equal to 5, and * is a linking point; Chemical Formula 2 wherein, in Chemical Formula 2, L 1 is a single bond, substituted or unsubstituted Ci to C10alkylene, substituted or unsubstituted C2to C10alkenylene, substituted or unsubstituted C2to C10alkynylene, substituted or unsubstituted C3to C20cycloalkylene, substituted or unsubstituted C3to C20heterocycloalkylene, substituted or unsubstituted C6to C20arylene, or a combination thereof, X 1 and X 2 each independently is a single bond, -0-, -S-, -S(=0)-, -S(=0)2-, -C(=0)-, -(CO)0-, -0(CO)0-, -C(=0)NH-, -NR a -, wherein R a is hydrogen, deuterium, or C1to C10alkyl, or a combination thereof, Y 1 is a group represented by Chemical Formula 3, R 1 to R 3 each independently is hydrogen, deuterium, or substituted or unsubstituted C1to C10alkyl, and * is a linking point: Chemical Formula 3 and wherein, in Chemical Formula 3, M 1 R1is a single bond, substituted or unsubstituted C1to C20alkylene, substituted or unsubstituted C2to C20alkenylene, -O-, -NH-, or a combination thereof, Z 1 and Z 2 each independently is -C(=O)- or -CH(OH)-, M 2 is a single bond, a double bond, *-C(R b )=*, or a substituted or unsubstituted C1to C3alkylene, wherein R b is hydrogen, deuterium, or C1to C5alkyl, and * is the point of attachment to Z 1 or Z 2 , M 3 hydrogen, halogen, -CN, -NO2, -SF5, -NHOH, -OH, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, or substituted or unsubstituted C6 to C20 aryl, M 1 and M 3 or M 2 and M 3 are optionally connected to each other to form a ring, and * is a linking point.

2. The resist underlayer composition of claim 1, wherein, in Chemical Formula 1, m and n are each independently 1 or 2.

3. The resist underlayer composition of claim 1, wherein, in Chemical Formula 3, L 1 is a single bond or substituted or unsubstituted C1to C10alkylene, and X 1 and X 2 each independently is a single bond or -(CO)0-.

4. The resist underlayer composition of claim 1, wherein, in the polymer, a molar ratio of the structural unit represented by Chemical Formula 1 to the structural unit represented by Chemical Formula 2 is 9: 1 to 1:

9.

5. The resist underlayer composition of claim 1, wherein the polymer further comprises a structural unit represented by Chemical Formula 4: Chemical Formula 4 and wherein in Chemical Formula 4, L 2 is a single bond, substituted or unsubstituted C1to C10alkylene, substituted or unsubstituted C2to C10alkenylene, substituted or unsubstituted C2to C10alkynylene, substituted or unsubstituted C3to C20cycloalkylene, substituted or unsubstituted C2to C20heterocycloalkylene, substituted or unsubstituted C6to C20arylene, or a combination thereof, X 3 and X 4 each independently is a single bond, -0-, -S-, -S(=0)-, -S(=0)2-, -C(=0)-, -(CO)0-, -0(CO)0-, -C(=0)NH-, -NR c -, wherein R c is hydrogen, deuterium, or Ci to C10alkyl, or a combination thereof, Y 2 hydrogen, halogen, -CN, -NO2, -SF5, -OCF3, -OH, -ORi, -SRi, -NRiRj, -C(O)ORi, -C(O)NRiRj, -C(O)H, -C(O)Ri, -C(O)OH, -C(O)2Ri, -C(O)H, -C(=N-Ri)Rj, -N=C(Ri)2, -N=N-Ri, -N=CRiRj, -NRiC(O)Rj, -NRiC(O)ORj, -NRiC(O)NHRj, -NRiC(O)NRjRk, -NRiS(O)Rj, -NRiS(O)2Rj, -NRiS(O)2H, -NRiS(O)NRjRk, -NRiP(O)(Rj)2, -NRiP(O)(OH)2, -NRiP(O)(ORj)2, -NRiP(O)(Rj)2, R 4 to R 6 each independently is hydrogen, deuterium, or substituted or unsubstituted C1 to C10 alkyl, and * is a linking point.

6. The resist underlayer composition of claim 5, wherein, in Chemical Formula 4, L 2 is a single bond, substituted or unsubstituted C1to C10alkylene, or substituted or unsubstituted C6to C10arylene, X 3 and X 4 are each independently a single bond or -(CO)0-, and Y 2 is hydroxyl, substituted or unsubstituted C1to C10alkyl, substituted or unsubstituted C2to C20heterocycloalkyl, or substituted or unsubstituted C6to C20aryl.

7. The resist underlayer composition of claim 1, wherein Chemical Formula 2 is represented by one or more selected from the group consisting of Chemical Formula 2-1 to Chemical Formula 2-8: Chemical Formula 2-1 Chemical Formula 2-2 Chemical Formula 2-3 Chemical Formula 2-4 Chemical Formula 2-5 Chemical Formula 2-6 Chemical Formula 2-7 and Chemical Formula 2-8 8. The resist underlayer composition of claim 1, wherein the polymer has a weight average molecular weight of 1,000 g / mol to 300,000 g / mol.

9. The resist underlayer composition of claim 1, wherein the polymer is contained in an amount of 0.1 wt% to 50 wt% based on 100 wt% of the resist underlayer composition.

10. The resist underlayer composition of claim 1, further comprising one or more polymers selected from the group consisting of an acrylic resin, an epoxy resin, a phenolic resin, a glycoluril resin, and a melamine resin.

11. The resist underlayer composition of claim 1, further comprising an additive of a surfactant, a thermal acid generator, a photoacid generator, a plasticizer, or a combination thereof.

12. A method of forming a pattern, comprising: forming an etching target layer on a substrate; forming a resist underlayer by applying the resist underlayer composition of claim 1 on the etching target layer; forming a photoresist pattern on the resist underlayer; and sequentially etching the resist underlayer and the etching target layer using the photoresist pattern as an etching mask.

13. The method of claim 12, wherein, in Chemical Formula 1, m and n are each independently 1 or 2.

14. The method of claim 12, wherein, in Chemical Formula 3, L 1 is a single bond or substituted or unsubstituted C1to C10alkylene, and X 1 and X 2 each independently is a single bond or -(CO)0-.

15. The method of claim 12, wherein, in the polymer, a molar ratio of the structural unit represented by Chemical Formula 1 to the structural unit represented by Chemical Formula 2 is 9: 1 to 1:

9.

16. The method of claim 12, wherein the polymer further comprises structural units represented by Chemical Formula 4: Chemical Formula 4 and wherein, in Chemical Formula 4, L 2 is a single bond, substituted or unsubstituted C1to C10alkylene, substituted or unsubstituted C2to C10alkenylene, substituted or unsubstituted C2to C10alkynylene, substituted or unsubstituted C3to C20cycloalkylene, substituted or unsubstituted C2to C20heterocycloalkylene, substituted or unsubstituted C6to C20arylene, or a combination thereof, X 3 and X 4 each independently is a single bond, -0-, -S-, -S(=0)-, -S(=0)2-, -C(=0)-, -(CO)0-, -0(CO)0-, -C(=0)NH-, -NR c -, wherein R c is hydrogen, deuterium, or Ci to C10alkyl, or a combination thereof, Y 2 hydrogen, halogen, -CN, -NO2, -SF5, -OCF3, -OH, -ORi, -SRi, -NRiRj, -C(O)ORi, -C(O)NRiRj, -C(O)H, -C(O)Ri, -C(O)OH, -C(O)2Ri, -C(=NRI)RJ, -NHC(=NHRi)-NH2, -N3, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C2 to C10 alkenyl, substituted or unsubstituted C2 to C10 alkynyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 heterocycloalkyl, or substituted or unsubstituted C6 to C20 aryl, R 4 to R 6 each independently is hydrogen, deuterium, or substituted or unsubstituted C1to C10alkyl, and * is a point of attachment.

17. The method of claim 16, wherein in Chemical Formula 4, L 2 is a single bond, substituted or unsubstituted C1to C10alkylene, or substituted or unsubstituted C6to C10arylene, X 3 and X 4 are each independently a single bond or -(CO)0-, and Y 2 is hydroxyl, substituted or unsubstituted C1to C10alkyl, substituted or unsubstituted C2to C20heterocycloalkyl, or substituted or unsubstituted C6to C20aryl.

18. The method of claim 13, wherein Chemical Formula 2 is represented by one or more selected from the group consisting of Chemical Formulae 2-1 to 2-8: Chemical Formula 2-1 Chemical Formula 2-2 Chemical Formula 2-3 Chemical Formula 2-4 Chemical Formula 2-5 Chemical Formula 2-6 Chemical Formula 2-7 and Chemical Formula 2-8 19. A system for forming a pattern, comprising: means for forming an etching target layer on a substrate; means for forming a resist underlayer by applying the resist underlayer composition of claim 1 on the etching target layer; means for forming a photoresist pattern on the resist underlayer; and means for sequentially etching the resist underlayer and the etching target layer using the photoresist pattern as an etching mask.

20. A resist underlayer of the resist underlayer composition of claim 1.

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