Resist top coating composition and method of forming pattern using the same

Abstract

A resist top coating composition and a method of forming a pattern using the same, the resist top coating composition including a copolymer and a solvent, the copolymer comprises a first structural unit represented by a chemical formula M-1, a second structural unit represented by a chemical formula M-2, and a third structural unit represented by at least one of a chemical formula M-3A, a chemical formula M-3B or a chemical formula M-3C; wherein the copolymer has an OHV (OH value) of from about 5 mgKOH / g to about 100 mgKOH / g.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2024 - 0001128, filed with the Korean Intellectual Property Office on January 3, 2024, the entire content of which is incorporated herein by reference. Technical Field

[0003] The embodiments described in the present disclosure relate to a resist top - coat composition and a method of forming a pattern using the composition. Background Art

[0004] Recently, the semiconductor industry has advanced (i.e., progressed to adopt) ultra - fine technologies (i.e., technologies capable of creating patterns ranging in size from a few nanometers to dozens of nanometers) with patterns having sizes from a few nanometers to dozens of nanometers. Such ultra - fine technologies inherently require or desire an effective lithography process.

[0005] Some lithography processes involve forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing to form a photoresist pattern, and then etching the material layer using the photoresist pattern as a mask.

[0006] As the lithography process develops, the pattern integration degree is increasing, and materials and technologies are desired or required to solve one or more appropriate problems that arise in this process. That is, improving the materials and technologies used in the lithography process may help to address some of the challenges of increasing pattern integration.

[0007] For example, if (e.g., when) extreme ultraviolet light (EUV) irradiates a photoresist, due to the large energy of each photon, there may be a region randomly irradiated with a large or small amount of light, which is a kind of photon shot noise, or the EUV absorption difference between the top and bottom of the photoresist may cause pattern distribution deterioration, such as pattern roughness (line edge roughness: LER, line width roughness: LWR) or in - point uniformity (IPU). To improve such pattern distribution deterioration, technology development may be desired or required. That is, when EUV light is exposed to a photoresist, the high energy of each photon may cause photon shot noise, resulting in regions receiving different amounts of light. This randomness may reduce the pattern quality due to factors such as EUV absorption differences in the photoresist depth, leading to problems such as roughness - especially line edge roughness (LER) and line width roughness (LWR) - or in - point uniformity (IPU) of the pattern. To mitigate these effects and improve pattern uniformity, further technological progress may be needed or desired. Summary of the Invention

[0008] Aspects according to one or more embodiments relate to a resist topcoat composition capable of reducing pattern distribution by preventing or reducing pattern deterioration.

[0009] Aspects according to one or more embodiments relate to a method of forming a pattern using a resist topcoat composition.

[0010] According to one or more embodiments, the resist topcoat composition includes a copolymer including a first structural unit represented by Chemical Formula M-1, a second structural unit represented by Chemical Formula M-2, and a third structural unit represented by at least one of Chemical Formula M-3A, Chemical Formula M-3B, or Chemical Formula M-3C; and a solvent,

[0011] wherein the copolymer has an OHV (OH value) of about 5 mgKOH / g to about 100 mgKOH / g.

[0012]

[0013] In Chemical Formula M-1 and Chemical Formula M-2,

[0014] R 1 and R 2 may each independently be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0015] L 1 and L 2 may each independently be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, and / or (for example, any suitable) a combination thereof,

[0016] X 1 is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -NR a -(wherein, R a is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group), and / or (for example, any suitable) a combination thereof,

[0017] R 5 is hydrogen, fluorine, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, and / or (for example, any suitable) a combination thereof,

[0018] R 6 is hydrogen, or C(=O)R b ,

[0019] R b is a substituted or unsubstituted C1 to C10 alkyl group,

[0020] From R 5 、L 1 and L 2 at least one selected from includes fluorine and a hydroxyl group,

[0021] R 7 is hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group, and / or (for example, any suitable) a combination thereof,

[0022] m1 is one of the integers from 1 to 4, and

[0023] * is a point of attachment;

[0024]

[0025] Chemical formula M-3C

[0026]

[0027] wherein, in Chemical formula M-3A to Chemical formula M-3C,

[0028] R 3 、R 4 and R 8 to R 22 may each independently be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0029] n1 and n3 may each independently be one selected from the integers from 1 to 10,

[0030] n2 is one of the integers from 2 to 5,

[0031] n4 is one of the integers from 1 to 5, and

[0032] * is a point of attachment.

[0033] According to one or more embodiments, a method of forming a pattern may include coating and heating a photoresist composition on a substrate to form a photoresist layer, coating and heating the above resist topcoat composition on the photoresist layer to form a topcoat, and exposing and developing the topcoat and the photoresist layer to form a resist pattern.

[0034] According to one or more embodiments, when exposed to extreme ultraviolet light (EUV) (for example), the resist topcoat composition can remove excess activated acid from the top of the photoresist by introducing a structural unit having a functional group capable of reacting with the excess activated acid, to prevent or reduce pattern profile degradation (such as roughness (LER, LWR) or IPU of a columnar pattern) caused by the EUV absorption difference between the top and bottom of the photoresist, thereby improving the pattern profile and significantly improving the IPU of the columnar pattern, which is conducive to forming a fine pattern of the photoresist. That is to say, according to certain embodiments, the resist topcoat composition is designed to eliminate the excess activated acid on the surface of the photoresist. This is achieved by introducing a structural unit equipped with a functional group capable of reacting with the excess activated acid. When exposed to EUV, this reaction helps to prevent, minimize or reduce the reduction of pattern uniformity (such as LER and / or LWR and / or IPU of the pattern). This reduction is usually caused by the differential absorption of EUV light between the top and bottom of the photoresist. Therefore, this improvement in the pattern profile significantly improves the IPU or within-dot uniformity of the columnar pattern, thus facilitating the formation of an accurate photoresist pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is a schematic diagram of a method for forming a pattern using a resist topcoat composition according to one or more embodiments.

[0036] DESCRIPTION OF REFERENCE NUMERALS IN THE DRAWINGS

[0037] 1, 2, 3: Steps;

[0038] 30: Resist topcoat;

[0039] 100: Semiconductor substrate;

[0040] 101: Photoresist layer;

[0041] 102b: Photoresist pattern. DETAILED DESCRIPTION

[0042] Example embodiments of the present disclosure will be described in more detail below and can be easily implemented by those skilled in the art. However, the present disclosure can be implemented in many different forms and should not be construed as limited to the example embodiments described herein.

[0043] In the drawings, for clarity, the thicknesses of layers, films, panels, regions, and / or similar components are exaggerated, and in all the drawings, the same reference numerals represent the same elements and may not be repeated in the specification. It is to be understood that if, for example, when, an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, if, for example, when, an element is referred to as being "directly on" another element, there are no intervening elements.

[0044] Expressions used herein, such as "at least one", "one", and "selected from (e.g., of...)" when preceding a list of elements, modify the entire list of elements and not a single element in the list. For example, "at least one of a, b, or c", "at least one selected from a, b, and c", and / or similar expressions can mean only a, only b, only c, (e.g., simultaneously) a and b, (e.g., simultaneously) a and c, (e.g., simultaneously) b and c, all of a, b, and c, or variations thereof.

[0045] The terms used herein are intended to describe only particular embodiments and are not intended to limit the disclosure. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms, including "at least one", unless the context (e.g., amount) clearly indicates otherwise. "At least one" should not be construed as being limited to the singular. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items. The terms "comprising", "including", "having", and / or "containing" used in the detailed description specify the presence of the stated features, regions, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and / or groups thereof.

[0046] Spatial relative terms such as "beneath", "below", "lower", "above", and "upper" may be used herein for ease of description to describe the relationship of one element or feature to another element or feature. It is to be understood that the spatial relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation shown in the figures. For example, when the device in the figures is flipped, an element described as "beneath" or "below" another element or feature will then be "above" or "over" the other element or feature. In some embodiments, the exemplary term "below" can include both an above and a below orientation. The device may be otherwise oriented (rotated 90 degrees or other orientations), and the spatial relative terms used herein may be interpreted accordingly.

[0047] As used herein, the terms "substantially" and similar terms are used as approximate terms and not terms of degree, and are intended to account for deviations inherent in measured or calculated values as recognized by a person of ordinary skill in the art. Additionally, the terms "about" and similar terms, when used herein in connection with a numerical value or numerical range, include the recited value and values within the acceptable deviation range of the recited specific value as determined by a person of ordinary skill in the art, taking into account the measurements involved and the errors associated with the measurement of a particular quantity (e.g., limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the recited value.

[0048] Furthermore, any numerical range recited herein is intended to include all sub-ranges having the same numerical precision that are contained within the recited range. For example, a range of "1.0 to 10.0" is intended to include all sub-ranges (and including) between the recited minimum value of 1.0 and the recited maximum value of 10.0, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations contained therein, and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations contained therein. Accordingly, the applicant reserves the right to amend this specification (including the claims) to expressly recite any sub-ranges that are contained within the ranges expressly recited herein.

[0049] After viewing the entire content of this disclosure, a person of ordinary skill in the art will understand that each appropriate feature of the various embodiments of this disclosure can be combined or combined with each other, in whole or in part, and can be interlocked and operated technically in various appropriate ways, and each embodiment can be implemented independently or in combination with each other in any appropriate way, unless otherwise stated or implied.

[0050] In the context of this application, unless otherwise defined, the terms "use", "using", and "used" may be considered synonymous with the terms "utilize", "utilizing", and "utilized", respectively.

[0051] Furthermore, the use of "may" when describing embodiments of the inventive concept refers to "one or more embodiments of the inventive concept". Meanwhile, the term "example" is intended to indicate an example or illustration.

[0052] As used herein, if (e.g., when) no other definition is provided, "substituted" means replacing a hydrogen atom of a compound with a substituent selected from a halogen atom (e.g., F, Br, Cl, or I), a hydroxyl group, a thiol group, a nitro group, a cyano group, an amino group, a substituted or unsubstituted C1-C30 amino group, an azide group, an amide group, a hydrazine group, a hydrazone group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or its salt, a sulfonic acid group or its salt, a phosphoric acid group or its salt, a vinyl group, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C30 aryl group, a C7-C30 aralkyl group, a C6-C30 allyl group, a C1-C30 alkoxy group, a C1-C30 sulfide group, a C1-C20 heteroalkyl group, a C3-C20 heteroaralkyl group, a C3-C30 cycloalkyl group, a C3-C15 cycloalkenyl group, a C6-C15 cycloalkynyl group, a C3-C30 heterocycloalkyl group, and / or (e.g., any suitable) a combination thereof.

[0053] As used herein, if (e.g., when) no other definition is provided, "alkyl" means a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group can be a "saturated alkyl" without any double or triple bonds.

[0054] The alkyl group can be a C1-C20 alkyl group. For example, the alkyl group can be a C1-C10 alkyl group or a C1-C6 alkyl group. For example, a C1-C5 alkyl group means an alkyl chain having 1 to 5 carbon atoms and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0055] The alkyl group means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and / or the like.

[0056] In the chemical formulas described herein, t-Bu means tert-butyl.

[0057] As used herein, if (e.g., when) no other definition is provided, "cycloalkyl" means a monovalent cyclic aliphatic hydrocarbon group.

[0058] The cycloalkyl group means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and / or the like.

[0059] The cycloalkyl group can be a C3-C10 cycloalkyl group, for example, a C3-C8 cycloalkyl group, a C3-C7 cycloalkyl group, or a C3-C6 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but the present disclosure is not limited thereto.

[0060] As used herein, unless otherwise defined, "alkenyl" means an aliphatic unsaturated alkenyl group containing at least one double bond as a straight-chain or branched-chain aliphatic hydrocarbon group.

[0061] As used herein, unless otherwise defined, "alkynyl" refers to an aliphatic unsaturated alkynyl group containing at least one triple bond as a straight-chain or branched-chain aliphatic hydrocarbon group.

[0062] As used herein, "aryl" refers to a substituent in which all atoms in the cyclic substituent have p orbitals and these p orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0063] As used herein, if (e.g., when) no other definition is provided, "hetero" refers to containing 1 to 10 heteroatoms selected from N, O, S, and P.

[0064] In the present disclosure, if (e.g., when) no other definition is provided, "heterocycloalkyl" refers to a cycloalkyl group containing at least one heteroatom selected from N, O, S, P, and Si.

[0065] In the present disclosure, "heteroaryl" refers to an aryl group containing at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryls are directly connected by a σ bond, or if (e.g., when) the heteroaryl contains two or more rings, these two or more rings may be fused. When the heteroaryl is a fused ring, each ring may contain 1 to 3 heteroatoms.

[0066] Unless otherwise specified in this specification, the weight-average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF), and then using a 1200 series Gel Permeation Chromatography (GPC) of Agilent Technologies (the column is LF-804 of Showa Denko K.K., and the standard sample is polystyrene of Showa Denko K.K.).

[0067] In addition, unless otherwise defined in the specification, "*" represents the connection point of the structural unit or compound moiety of the compound.

[0068] The following describes a resist topcoat composition according to one or more embodiments.

[0069] The present disclosure relates to a photoresist topcoat composition and a method of forming a photoresist pattern using the topcoat. The resist topcoat composition can improve the sensitivity of the photoresist during the formation of lithographic fine patterns using high-energy rays such as extreme ultraviolet (EUV; wavelength: about 13.5 nm) and / or similar rays, and simultaneously (e.g., synchronously) selectively reduce the acid concentration in the upper part of the photoresist, thereby improving the in-pit uniformity (IPU) of contact hole (C / H) patterns, the line edge roughness (LER) / line width roughness (LWR) of line and space (L / S) patterns, and the IPU of columnar patterns.

[0070] A resist topcoat composition according to one or more embodiments includes a copolymer including a first structural unit represented by Chemical Formula M-1, a second structural unit represented by Chemical Formula M-2, and a third structural unit represented by at least one of Chemical Formula M-3A, Chemical Formula M-3B, or Chemical Formula M-3C; and a solvent, wherein the copolymer has an OHV (OH value) of about 5 mgKOH / g to about 100 mgKOH / g.

[0071]

[0072] In Chemical Formula M-1 and Chemical Formula M-2,

[0073] R 1 and R 2 may each independently be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0074] L 1 and L 2 may each independently be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, and / or (for example, any suitable) a combination thereof,

[0075] X 1 is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -NR a -(wherein, R a is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group), and / or (for example, any suitable) a combination thereof,

[0076] R 5 is hydrogen, fluorine, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, and / or (for example, any suitable) a combination thereof,

[0077] R 6 is hydrogen, or C(=O)R b ,

[0078] R b is a substituted or unsubstituted C1 to C10 alkyl group,

[0079] At least one selected from R 5 , L 1 or L 2 includes fluorine and a hydroxyl group,

[0080] R 7is hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group, and / or (for example, any suitable) a combination thereof,

[0081] m1 is one of the integers from 1 to 4, and

[0082] * is a connection point;

[0083]

[0084] Chemical formula M-3C

[0085]

[0086] wherein, in Chemical formula M-3A to Chemical formula M-3C,

[0087] R 3 、R 4 and R 8 to R 22 can each independently be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0088] n1 and n3 can each independently be one selected from the integers from 1 to 10,

[0089] n2 is one of the integers from 2 to 5,

[0090] n4 is one of the integers from 1 to 5, and

[0091] * is a connection point.

[0092] According to one or more embodiments, the photoresist topcoat composition can be coated on top of the photoresist layer to significantly improve the LER / LWR of the L / S pattern, the IPU of the C / H pattern and the IPU of the column pattern, and increase the sensitivity of the photoresist.

[0093] The first structural unit contained in the copolymer of the composition has the characteristics of having little reactivity with the photoresist but being well soluble in the solvent, so it can protect the photoresist while minimizing or reducing the impact on the photoresist, while the second structural unit can increase EUV absorption to improve the sensitivity. The third structural unit includes a functional group capable of reacting with an acid, thereby reacting with the excessive acid generated by exposure in the upper part of the photoresist layer, reducing the acid concentration, and changing the circular profile of the upper layer of the photoresist into a rectangular shape to improve the IPU or LWR of the pattern.

[0094] In contrast, if (for example, when) the photoresist topcoat composition still remains after development, it may cause residual glue defects in the L / S pattern or non-opening defects in the C / H pattern, resulting in a reduction in product yield.

[0095] However, the photoresist topcoat composition according to one or more embodiments can be removed during the development process and thus does not cause defects in one or more suitable patterns. That is, the photoresist topcoat composition according to one or more embodiments of the present disclosure can be more easily removed, which helps to reduce or prevent defects in one or more suitable patterns.

[0096] OHV (hydroxyl value) refers to the amount of hydroxyl groups (-OH) in every 100 grams of a sample, expressed in milligrams of KOH, and the analysis method can be found in ASTM and / or similar standards. For example, in the context of the present disclosure, OHV or hydroxyl value represents the hydroxyl value. The hydroxyl value is a measure of the amount of hydroxyl groups (-OH) in a sample, usually expressed in milligrams of potassium hydroxide per gram (mgKOH / g).

[0097] The OHV according to one or more embodiments can be measured by the following method.

[0098] A certain amount of the copolymer is added to a container containing a phthalic acid hydrate solution, reacted at a high temperature, titrated with a 0.5N NaOH (or KOH) aqueous solution, the pH value is observed, and the amount of NaOH (or KOH) desired or required to reach the inflection point is measured. In addition, a blank test is performed separately to measure the amount of NaOH (or KOH) desired or required to reach the pH inflection point as described above. Then, based on the measured values, the OHV of the copolymer is calculated by Formula 1.

[0099] Formula 1

[0100] Milligrams of KOH per gram (mgKOH / g) / OH equivalent = 56,100 / OH equivalent

[0101] As an example, the OHV (hydroxyl value) of the copolymer is from about 5 to about 90 mgKOH / g, specifically from about 5 mgKOH / g to about 80 mgKOH / g, more specifically from about 5 to about 70 mgKOH / g, and most specifically from about 5 mgKOH to about 68 mgKOH.

[0102] In Chemical Formula M-2, if (for example, when) m1 is 2 or greater, each O-R 6 can be the same or different from each other.

[0103] In Chemical Formula M-2, if (for example, when) 5 - m1 is 2 or greater, each R 7 can be the same or different from each other.

[0104] In Chemical Formula M-3A, if (for example, when) n1 is 2 or greater, each R 10 can be the same or different from each other.

[0105] In the chemical formula M-3A, when (for example) n1 is 2 or greater, each R 11 may be the same as or different from one another.

[0106] In the chemical formula M-3B, when (for example) n2 is 2 or greater, each R 19 may be the same as or different from one another.

[0107] In the chemical formula M-3B, when (for example) n2 is 2 or greater, each R 20 may be the same as or different from one another.

[0108] In the chemical formula M-3B, when (for example) n2 is 2 or greater, each R 21 may be the same as or different from one another.

[0109] In the chemical formula M-3B, when (for example) n2 is 2 or greater, each R 22 may be the same as or different from one another.

[0110] In the chemical formula M-3C, when (for example) n3 is 2 or greater, each R 17 may be the same as or different from one another.

[0111] In the chemical formula M-3C, when (for example) n3 is 2 or greater, each R 18 may be the same as or different from one another.

[0112] The term "at least one selected from R 5 , L 1 and L 2 and including fluorine and hydroxyl" may mean (for example, that at least one of R 5 , L 1 or L 2 simultaneously contains fluorine and hydroxyl may mean) the following cases:

[0113] R 5 is a C1-C10 alkyl group substituted by at least one fluorine and at least one hydroxyl, or

[0114] at least one selected from L 1 and L 2 is a C1-C10 alkylene group substituted by one or more fluorine groups and one or more hydroxyl groups, or

[0115] at least one selected from L 1 and L 2 is a C1-C10 alkylene group substituted by one or more fluorine groups, and at least one other is a C1-C10 alkylene group substituted by one or more hydroxyl groups, or

[0116] R5 is fluorine, and at least one selected from L 1 and L 2 is a C1-C10 alkylene group substituted with one or more hydroxyl groups, or

[0117] R 5 is a hydroxyl group, and at least one selected from L 1 and L 2 is a C1-C10 alkylene group substituted with one or more fluorine groups, or

[0118] R 5 is a C1-C10 alkyl group substituted with one or more fluorine groups and one or more hydroxyl groups, or

[0119] R 5 is a C1-C10 alkyl group substituted with one or more hydroxyl groups and one or more C1-C10 fluoroalkyl groups.

[0120] As an example, the first structural unit can be represented by Chemical Formula 1.

[0121] Chemical Formula 1

[0122]

[0123] In Chemical Formula 1,

[0124] R 1 is hydrogen or a substituted or unsubstituted C1-C10 alkyl group,

[0125] R d , R e , R f , R g and R 5 can each independently be hydrogen, fluorine, a hydroxyl group, a substituted or unsubstituted C1-C20 alkyl group, and / or (for example, any suitable) a combination thereof,

[0126] m2 and m3 can each independently be a number selected from the integers from 1 to 10,

[0127] X 1 is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -NR a -(wherein, R a is hydrogen, deuterium or a substituted or unsubstituted C1-C10 alkyl group), and / or (for example, any suitable) a combination thereof,

[0128] From R d , R e , R f, R g and R 5 at least one selected from includes fluorine and a hydroxyl group, and

[0129] * is a connection point.

[0130] In Chemical Formula 1, if (for example, when) m2 is 2 or greater, each R d can be the same as or different from each other.

[0131] In Chemical Formula 1, if (for example, when) m2 is 2 or greater, each R e can be the same as or different from each other.

[0132] In Chemical Formula 1, if (for example, when) m3 is 2 or greater, each R f can be the same as or different from each other.

[0133] In Chemical Formula 1, if (for example, when) m3 is 2 or greater, each R g can be the same as or different from each other.

[0134] This term, namely at least one selected from R d , R e , R f , R g and R 5 includes fluorine and a hydroxyl group, may refer to the following cases:

[0135] At least one selected from R d , R e , R f , R g and R 5 is independently a fluorine group and a hydroxyl group, or

[0136] At least one selected from R d , R e , R f , R g and R 5 independently includes a C1 - C10 alkyl group substituted with one or more fluorine groups and a C1 - C10 alkyl group substituted with one or more hydroxyl groups, or

[0137] At least one selected from R d , R e , R f , R g and R 5 independently includes a C1 - C10 alkyl group substituted with one or more hydroxyl groups and one or more fluorine groups, or

[0138] At least one selected from R d , R e , Rf , R g and R 5 at least one independently selected from R

[0139] is a C1-C10 alkyl group substituted by one or more hydroxyl groups and one or more C1-C10 fluoroalkyl groups, or d , R e , R f , R g and R 5 at least one is fluorine and at least one other is a hydroxyl group, or

[0140] at least one selected from R d , R e , R f , R g and R 5 is fluorine and at least one other includes a C1-C10 alkyl group substituted by one or more hydroxyl groups, or

[0141] at least one selected from R d , R e , R f , R g and R 5 is a hydroxyl group and at least one other includes a C1-C10 alkyl group substituted by one or more fluorine groups, or

[0142] at least one selected from R d , R e , R f , R g and R 5 is a C1-C20 alkyl group substituted by one or more fluorine groups and at least one other is a C1-C20 alkyl group substituted by one or more hydroxyl groups.

[0143] For example, R 1 can be hydrogen or methyl,

[0144] X 1 can be a single bond, O or NR a (where R a is hydrogen, deuterium or a C1-C10 alkyl group), and

[0145] R 5 can be fluorine, a hydroxyl group, a C1-C10 alkyl group substituted by at least one fluorine, or a C1-C10 alkyl group substituted by at least one hydroxyl group.

[0146] As an example, at least one of R f , R g or R 5 in Chemical Formula 1 can include a fluorine group and a hydroxyl group.

[0147] As a specific example, R in Chemical Formula 1 f or R g at least one of which may be fluorine or a C1-C10 alkyl group substituted with at least one fluorine, and R 5 may be a hydroxyl group or a C1-C10 alkyl group substituted with at least one hydroxyl group.

[0148] As a specific example, R in Chemical Formula 1 f or R g at least one of which may be a hydroxyl group or a C1-C10 alkyl group substituted with at least one hydroxyl group, and R 5 may be fluorine or a C1-C10 alkyl group substituted with at least one fluorine.

[0149] As a specific example, R in Chemical Formula 1 f may be a hydroxyl group or a C1-C10 alkyl group substituted with at least one hydroxyl group, R g may be fluorine or a C1-C10 alkyl group substituted with at least one fluorine, R 5 may be a hydroxyl group, fluorine, or a C1-C10 alkyl group substituted with at least one fluorine or hydroxyl group.

[0150] As a specific example, R in Chemical Formula 1 f or R g at least one of which may be fluorine or a C1-C10 alkyl group substituted with at least one fluorine, and R 5 may be a hydroxyl group, or a C1-C5 alkyl group substituted with at least one hydroxyl group or a C1-C5 fluoroalkyl group substituted with fluorine.

[0151] For example, the first structural unit may be any one selected from Group I.

[0152] Group I

[0153]

[0154] In Group I,

[0155] R 1 each independently may be hydrogen or methyl, and * is the point of attachment.

[0156] As a specific example, the second structural unit may be represented by any one selected from Chemical Formulas 2-1 to 2-4.

[0157] Chemical Formula 2-1 Chemical Formula 2-2 Chemical Formula 2-3 Chemical Formula 2-4

[0158]

[0159] In Chemical Formulas 2-1 to 2-4,

[0160] R 2 is hydrogen or methyl,

[0161] R 6 、R 6a and R 6b each independently can be hydrogen, or C(=O)R b ,

[0162] R b is a substituted or unsubstituted C1 to C5 alkyl group,

[0163] R 7a 、R 7b 、R 7c and R 7d each independently can be hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C10 alkyl group, and / or any suitable combination thereof, and

[0164] * is a connection point.

[0165] As an example, at least one R 7 can be halogen.

[0166] As an example, at least one R 7 can be an iodine group.

[0167] If (for example, when) the second structural unit includes an iodine group, the sensitivity can be further improved.

[0168] For example, the second structural unit can be any one selected from Group II.

[0169] Group II

[0170]

[0171]

[0172] In Group II,

[0173] R 2 can each independently be hydrogen or methyl, and * is a connection point.

[0174] For example, L 3 to L 7 can each independently be a single bond, a substituted or unsubstituted C1 to C5 alkylene group, or a substituted or unsubstituted phenylene group,

[0175] R 8 to R 14 can each independently be hydrogen, or a substituted or unsubstituted C1 to C10 alkyl group, and

[0176] n1 can be an integer of 1 or 2.

[0177] As an example, n1 in the chemical formula M-3A can be one of the integers from 1 to 5.

[0178] As an example, n2 in the chemical formula M-3B can be one of the integers from 2 to 4.

[0179] As an example, n3 in the chemical formula M-3C can be one of the integers from 1 to 5.

[0180] For example, the third structural unit can be any one selected from Group Ⅲ.

[0181] Group Ⅲ

[0182]

[0183]

[0184] In Group Ⅲ,

[0185] R 3 、R 4 and R 12 can each independently be hydrogen or methyl, and * is the connection point.

[0186] The copolymer can include about 30 mol% to about 95 mol% of the first structural unit, about 1 mol% to about 20 mol% of the second structural unit, and about 5 mol% to about 50 mol% of the third structural unit.

[0187] For example, the copolymer can include about 55 mol% to about 90 mol% of the first structural unit, about 5 mol% to about 15 mol% of the second structural unit, and about 5 mol% to about 30 mol% of the third structural unit. And in one or more embodiments, the copolymer can include about 60 mol% to about 85 mol% of the first structural unit, about 5 mol% to about 15 mol% of the second structural unit, and about 5 mol% to about 25 mol% of the third structural unit.

[0188] If (for example, when) the molar ratio of each structural unit contained in the copolymer is within the above range, the solubility in an organic solvent is improved, and the pattern can be coated uniformly (for example, substantially uniformly).

[0189] The copolymer may have a weight-average molecular weight (Mw) of from about 1,000 g / mol to about 15,000 g / mol. For example, it may have a weight-average molecular weight of from about 2,000 g / mol to about 15,000 g / mol, such as from about 3,000 g / mol to about 15,000 g / mol, such as from about 4,000 g / mol to about 10,000 g / mol, but the present disclosure is not limited thereto. When the weight-average molecular weight of the copolymer is within the above range, the carbon content (e.g., amount) and solubility in a solvent of the resist topcoat composition including the copolymer can be improved or optimized.

[0190] The copolymer may be included in the resist topcoat composition in an amount of from about 0.1 wt% to about 10 wt%, based on 100 wt% of the total weight of the resist topcoat composition. Within the above range, the resist topcoat can be more easily removed.

[0191] In one or more embodiments, the copolymer may be selected from those listed in Group IV.

[0192] Group IV

[0193]

[0194]

[0195] In Group IV,

[0196] R 1 、R 2 、and R 7 may each independently be hydrogen or methyl,

[0197] x is from about 30 mol% to about 95 mol%, y is from about 2 mol% to about 20 mol%, and z is from about 5 mol% to about 50 mol%.

[0198] For example, x:y:z may be about 73:10:17 or about 76:8:16 or about 77:9:14.

[0199] The solvent may be a solvent of an ether represented by Chemical Formula 4.

[0200] Chemical Formula 4

[0201]

[0202] In Chemical Formula 4,

[0203] R 8 and R 9 may each independently be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group.

[0204] For example, the ether solvent can be selected from diisopropyl ether, dipropyl ether, diisoamyl ether, dipentyl ether, dibutyl ether, diisobutyl ether, di-sec-butyl ether, dihexyl ether, bis(2-ethylhexyl) ether, didecyl ether, heneicosyl ether, docosyl ether, tetracosyl ether, cetyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tert-butyl propyl ether, di-tert-butyl ether, cyclopentyl methyl ether, cyclohexyl methyl ether, cyclopentyl ethyl ether, cyclohexyl ethyl ether, cyclopentyl propyl ether, cyclopentyl-2-propyl ether, cyclohexyl propyl ether, cyclohexyl-2-propyl ether, cyclopentyl butyl ether, cyclopentyl-tert-butyl ether, cyclohexyl butyl ether, cyclohexyl-tert-butyl ether, and / or (for example, any suitable) combinations thereof.

[0205] The ether solvent can have sufficient solubility or dispersibility in the above composition.

[0206] In one or more embodiments, the resist topcoat composition can further include at least one other polymer selected from epoxy resins, phenolic resins, glyoxal urea resins, and melamine resins, but the present disclosure is not limited thereto.

[0207] The resist topcoat composition can further include additives, which include surfactants, thermal acid generators, plasticizers, and / or (for example, any suitable) combinations thereof.

[0208] The surfactant can be, for example, alkylbenzene sulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt, and / or the like, but the present disclosure is not limited thereto.

[0209] The thermal acid generator can be, for example, an acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, and / or benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, but the present disclosure is not limited thereto.

[0210] The amounts of these additives used can be easily adjusted according to the desired or suitable physical properties and may not be provided.

[0211] In one or more embodiments, a method of forming a pattern using the above resist topcoat composition can be provided. For example, the manufactured pattern can be a resist pattern.

[0212] A method of forming a pattern according to one or more embodiments includes coating and heating a photoresist composition on a substrate to form a photoresist layer, coating and heating the above photoresist topcoat composition on the photoresist layer to form a topcoat, and exposing and developing the topcoat and the photoresist layer to form a resist pattern.

[0213] Hereinafter, a method of forming a pattern using the above photoresist topcoat composition will be described in more detail with reference to the accompanying drawings. The accompanying drawings are schematic diagrams of a method of forming a pattern using a photoresist topcoat composition according to the present disclosure.

[0214] Referring to Figure 1 , first, an object to be etched is prepared. Examples of the object to be etched may be a thin film formed on a semiconductor substrate 100. Hereinafter, only the case where the aspect to be etched is a thin film will be described. The surface of the thin film is cleaned to remove contaminants remaining on the thin film. The thin film may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

[0215] A photoresist composition is coated on the thin film and heated to form a photoresist layer 101 (step (e.g., action or task) 1). Subsequently, a photoresist topcoat composition is coated on the photoresist layer and heated to form a photoresist topcoat 30 (step (e.g., action or task) 2).

[0216] The heating can be performed at a temperature of about 80°C to about 500°C.

[0217] Then, the photoresist topcoat and the photoresist layer are exposed to high-energy radiation.

[0218] For example, the high-energy radiation that can be used during the exposure may include light having a high-energy wavelength, such as EUV (extreme ultraviolet light; wavelength: about 13.5 nanometers) and / or E-Beam (electron beam).

[0219] Then, post-exposure bake (PEB) is performed. The post-exposure bake can be performed at a temperature of about 80°C to about 200°C. By performing the post-exposure bake, the exposed area of the photoresist layer, i.e., the area not covered by the patterned mask, is changed to a property soluble in the developer, so that the exposed area has a different solubility from the unexposed area of the photoresist layer.

[0220] A photoresist pattern 102b can be formed by dissolving and removing the photoresist layer and the photoresist topcoat corresponding to the exposed area using a developer (step (e.g., action or task) 3).

[0221] For example, the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter referred to as an organic developer).

[0222] As an alkaline developer, quaternary ammonium salts such as tetramethylammonium hydroxide are usually used, but aqueous alkaline solutions such as inorganic bases, primary to tertiary amines, alkanolamines, and / or cyclic amines can also be used.

[0223] In addition, the alkaline developer can contain an appropriate or suitable amount of alcohol and / or surfactant. The alkali concentration of the alkaline developer can be, for example, about 0.1% by mass to about 20% by mass, and the pH value of the alkaline developer can be, for example, about 10 to about 15.

[0224] The organic developer can be a developer containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0225] Examples of ketone solvents can include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetylacetone alcohol, ionone, diacetone alcohol, acetylmethanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and / or the like.

[0226] Examples of ester solvents can include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyrate, 3-methyl-3-methoxybutyrate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate, and / or the like.

[0227] Suitable solvents that can be used include alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0228] The above-mentioned various solvents can be mixed, or can be mixed with solvents other than the above-mentioned solvents or water. The water content (e.g., amount) of the entire developer can be less than about 50% by weight, less than about 20% by weight, less than about 10% by weight, and in particular, the developer can be substantially free of water.

[0229] Based on 100% by weight of the total amount of the organic developer, the content (e.g., amount) of the organic solvent can be about 50% by weight to about 100% by weight, about 80% by weight to about 100% by weight, about 90% by weight to about 100% by weight, and about 95% by weight to about 100% by weight.

[0230] The organic developer may include a suitable amount of a suitable surfactant as needed or required. That is, the organic developer may include a suitable amount of a suitable surfactant.

[0231] Based on 100% by weight of the total amount of the organic developer, the content (e.g., amount) of the surfactant can generally be from about 0.001% by weight to about 5% by weight, from about 0.005% by weight to about 2% by weight, and from about 0.01% by weight to about 0.5% by weight.

[0232] The organic developer may include an inhibitor.

[0233] Subsequently, the exposed thin film is etched using the photoresist pattern as an etch mask. As a result, the thin film is formed into a thin film pattern.

[0234] The thin film can be etched by, for example, dry etching using an etch gas, which can be, for example, CHF3, CF4, Cl2, BCl3, and / or a mixture thereof (e.g., any suitable mixture).

[0235] In the above exposure process, the thin film pattern formed using the photoresist pattern formed by the exposure process performed using an extreme ultraviolet light source can have a width corresponding to the photoresist pattern. For example, the photoresist pattern can have a width of about 5 nanometers to about 100 nanometers. For example, the thin film pattern formed by the exposure process performed using an extreme ultraviolet light source can have a width of about 5 nanometers to about 90 nanometers, about 5 nanometers to about 80 nanometers, about 5 nanometers to about 70 nanometers, about 5 nanometers to about 60 nanometers, about 5 nanometers to about 50 nanometers, about 5 nanometers to about 40 nanometers, about 5 nanometers to about 30 nanometers, or about 5 nanometers to about 20 nanometers, or can be formed to a width less than or equal to about 20 nanometers, similar to the photoresist pattern (e.g., the pattern can be formed to a maximum width of about 20 nanometers, similar to the photoresist pattern).

[0236] After that, the present disclosure will be described in more detail by examples related to the synthesis of the above polymer and the preparation of the photoresist topcoat composition including the polymer. However, the present disclosure is not technically limited by the following examples.

[0237] Synthesis Examples

[0238] Synthesis Example 1

[0239] In a 250 mL two-necked round-bottom flask, 13.39 g of the compound represented by Chemical Formula 1a (CamOptics), 1.86 g of the compound represented by Chemical Formula 1b (DIHS, Acelachem Bio), hydroxybutyl acrylate (2.16 g of 4-HBA (Oi Chemical Co., Ltd.)), and 71.4 g of diisoamyl ether (DIAE) were added, and the mixture was heated to an internal temperature of 115°C. When the internal temperature reached 115°C, 13.82 g of a 25 wt% V-601 / DIAE solution (3.45 g of V-601) was slowly added. After 6 hours, the reaction solution was cooled to room temperature, and the reaction mixture was concentrated to a solid content of 50% (e.g., amount). After adding 120 g of heptane to the concentrated solution, the resulting polymer was filtered out. The filtered polymer was completely dissolved in 12 g of DIAE, then precipitated by adding 270 g of heptane twice, and finally completely dried to finally prepare copolymer R1 (molecular weight = 5,000).

[0240] Chemical Formula 1a

[0241]

[0242] Chemical Formula 1b

[0243]

[0244] Synthesis Example 2

[0245] The preparation method of copolymer R2 (molecular weight = 5,300) was basically the same as that of Synthesis Example 1, except that 1.74 g of hydroxyl ethyl acrylate (HEA; Oi Chemical Co., Ltd.) was used instead of 4-HBA.

[0246] Synthesis Example 3

[0247] The preparation method of copolymer R3 (molecular weight = 5,500) was basically the same as that of Synthesis Example 1, except that 1.95 g of hydroxyl propyl acrylate (HPA; Oi Chemical Co., Ltd.) was used instead of 4-HBA.

[0248] Synthesis Example 4

[0249] The preparation method of copolymer R4 (molecular weight = 5,900) was basically the same as that of Synthesis Example 1, except that 5.16 g of caprolactone acrylate (Tone M-100; Dow Chemical) was used instead of 4-HBA.

[0250] Synthesis Example 5

[0251] The preparation method of copolymer R5 (molecular weight = 5,500) is basically the same as that of Synthesis Example 1, except that 8.83 g of the compound represented by Chemical Formula 1c (HALOCARBON) is used instead of the compound represented by Chemical Formula 1a.

[0252] Chemical Formula 1c

[0253]

[0254] Synthesis Example 6

[0255] The preparation method of copolymer R6 (molecular weight = 5,500) is basically the same as that of Synthesis Example 1, except that 8.41 g of the compound represented by Chemical Formula 1d (HALOCARBON) is used instead of the compound represented by Chemical Formula 1a.

[0256] Chemical Formula 1d

[0257]

[0258] Synthesis Example 7

[0259] The preparation method of copolymer R7 (molecular weight = 5,300) is basically the same as that of Synthesis Example 1, except that 9.25 g of the compound represented by Chemical Formula 1e (HALOCARBON) is used instead of the compound represented by Chemical Formula 1a.

[0260] Chemical Formula 1e

[0261]

[0262] Comparative Synthesis Example 1

[0263] The preparation method of copolymer R8 (molecular weight = 7,500) is basically the same as that of Synthesis Example 1, except that 8.92 g of the compound represented by Chemical Formula 1a and 3.61 g of 4-HBA are used.

[0264] Comparative Synthesis Example 2

[0265] The preparation method of copolymer R9 (molecular weight = 3,100) is basically the same as that of Synthesis Example 1, except that 5.58 g of the compound represented by Chemical Formula 1b and 3.45 g of 4-HBA are used.

[0266] Comparative Synthesis Example 3

[0267] The preparation method of copolymer R10 (molecular weight = 2,700) is basically the same as that of Synthesis Example 1, except that 11.15 g of the compound represented by Chemical Formula 1a and 9.3 g of the compound represented by Chemical Formula 1b are used, and 4-HBA is not used.

[0268] Comparative Synthesis Example 4

[0269] The preparation method of copolymer R11 (molecular weight = 4,200) was basically the same as that of Synthesis Example 1, except that 5.58 g of the compound represented by Chemical Formula 1b and 5.05 g of 4-HBA were used, and the compound represented by Chemical Formula 1a was not used.

[0270] Comparative Synthesis Example 5

[0271] The preparation method of copolymer R12 (molecular weight = 8,100) was basically the same as that of Synthesis Example 1, except that 13.39 g of the compound represented by Chemical Formula 1a and 2.88 g of Chemical Formula 4-HBA were used, and the compound represented by Chemical Formula 1b was not used.

[0272] Evaluation 1: Solubility evaluation

[0273] 1 g of each copolymer prepared from Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 5 was taken, 50 g of DIAE (2 wt%) was added, and the mixture was stirred for 24 hours. Whether there was precipitation was observed with the naked eye, and the results are shown in Table 1.

[0274] Evaluation criteria

[0275] Solubility ○: No foreign matter, transparent liquid

[0276] Solubility △: No precipitation, somewhat opaque

[0277] Solubility X: Precipitation exists or it is completely turbid.

[0278] Evaluation 2: Developability evaluation

[0279] Each photoresist topcoat composition according to the examples and comparative examples was spin-coated on a silicon substrate and heat-treated on a hot plate at 110 °C for 1 minute to form a photoresist topcoat with a thickness of about 5 nm. The topcoat was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide on the formed substrate, and then heat-treated again on a hot plate at 110 °C for 1 minute, and then the change in the topcoat thickness was measured. The results are shown in Table 1.

[0280] * Residual film after development (%) = [(topcoat thickness before development (nm) - topcoat thickness after development (nm)) × 100 / topcoat thickness before development (nm)]

[0281] Evaluation criteria

[0282] ○: 98% or higher in the above calculation formula

[0283] △: Less than 98% and 90% or higher in the above calculation formula

[0284] X: Less than 90% in the above calculation formula

[0285] Evaluation 3: Patterning Evaluation

[0286] After forming an underlayer resist (thickness: 50 Å) and a photoresist film for electron beam (thickness: 700 Å) on an 8-inch silicon substrate, each photoresist topcoat composition according to the examples and comparative examples was spin-coated and then heat-treated on a hot plate at 110 °C for 1 minute to form a photoresist topcoat with a thickness of about 5 nm.

[0287] On the wafer on which the photoresist topcoat was formed, line and space patterns were formed in a focus-energy matrix (FEM) format using an electron beam apparatus (JEOL JBX-9300FS). Subsequently, the optimum sensitivity capable of forming a 50-nm critical dimension (CD) was examined using an interpolation method, and the results are shown in Table 1. And

[0288] After examining the optimum sensitivity, the line width roughness (LWR) distribution at the corresponding energy exposure was measured using a CD-SEM apparatus manufactured by Hitachi, Ltd. And for the reliability of the distribution, the same pattern was measured at 500 points within the exposure, and the final average value is shown in Table 1.

[0289] Table 1

[0290]

[0291] Referring to Table 1, when (for example) the resist topcoat composition according to one or more embodiments is applied, not only is the sensitivity excellent or appropriate, but the LWR improvement effect is also excellent or appropriate.

[0292] Related apparatuses or components using the resist topcoat composition according to embodiments of the present disclosure can 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 can be formed on an integrated circuit (IC) chip or on separate IC chips. Additionally, one or more suitable components of the apparatus can be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on a substrate. Further, one or more suitable components of the apparatus can be processes or threads 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 described herein. The computer program instructions are stored in a memory, which can be implemented in a computing device using a standard storage device (e.g., random access memory (RAM)). The computer program instructions can also be stored in other non-transitory computer-readable media, such as a CD-ROM, a flash drive, and / or similar devices. Additionally, those skilled in the art should recognize that the functions of one or more suitable computing devices can be combined or integrated into a single computing device, or the functions of a particular computing device can be distributed among one or more other computing devices without departing from the scope of the present disclosure.

[0293] Certain embodiments of the present disclosure have been described and illustrated heretofore. However, it will be apparent to those of ordinary skill in the art that the present disclosure is not limited to the one or more embodiments described, and various modifications and transformations can be made without departing from the spirit and scope of the present disclosure. Accordingly, such modified or transformed embodiments may not be separately understood from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. An anti - resist top - coat composition, comprising: A copolymer comprising a first structural unit represented by Chemical Formula M - 1, a second structural unit represented by Chemical Formula M - 2, and a third structural unit represented by at least one of Chemical Formula M - 3A, Chemical Formula M - 3B, or Chemical Formula M - 3C; and A solvent, wherein the copolymer has an OH value of 5 mgKOH / g to 100 mgKOH / g: wherein, in Chemical Formula M - 1 and Chemical Formula M - 2, R 1 and R 2 each independently is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, L 1 and L 2 each independently is a single bond, a substituted or unsubstituted C1-C10 alkylene group, or a combination thereof, X 1 is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O- -NR a -, or a combination thereof, wherein R a is hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, R 5 is hydrogen, fluorine, hydroxyl, a substituted or unsubstituted C1-C20 alkyl group, or a combination thereof R 6 is hydrogen, or C(=O)R b , R b is a substituted or unsubstituted C1-C10 alkyl group, R 5 、L 1 or L 2 at least one of which comprises fluorine and a hydroxyl group, R 7 is hydrogen, a halogen, a hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof, m1 is one of the integers from 1 to 4, and * is a connection point; wherein, in Chemical Formula M - 3A to Chemical Formula M - 3C, R 3 、R 4 and R 8 to R 22 each independently represents hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, n1 and n3 are each independently one of the integers selected from 1 to 10, n2 is one of the integers from 2 to 5, n4 is one of the integers from 1 to 5, and * is a connection point.

2. The anti - resist top - coat composition according to claim 1, wherein The first structural unit is represented by Chemical Formula 1: Among them, In Chemical Formula 1, R 1 is hydrogen or a substituted or unsubstituted C1-C10 alkyl group, R d 、R e 、R f 、R g and R 5 each independently is hydrogen, fluorine, a hydroxyl group, a substituted or unsubstituted C1-C20 alkyl group, or a combination thereof. m2 and m3 are each independently one of the integers selected from 1 to 10, X 1 is a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O- -NR a -, or a combination thereof, wherein R a is hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl group, and Selected from R d , R e , R f , R g and R 5 at least one of them includes fluorine and hydroxyl groups.

3. The anti - resist top - coat composition according to claim 1, wherein The first structural unit is any one selected from Group I: [Group I] Among them, In Group I, R 1 Each is independently hydrogen or methyl, and * is the point of attachment.

4. The anti - resist top - coat composition according to claim 1, wherein The second structural unit is represented by any one selected from Chemical Formula 2 - 1 to Chemical Formula 2 - 4: [Chemical Formula 2 - 1][Chemical Formula 2 - 2][Chemical Formula 2 - 3][Chemical Formula 2 - 4] Among them, In Chemical Formula 2 - 1 to Chemical Formula 2 - 4, R 2 is hydrogen or methyl, R 6 , R 6a and R 6b are each independently hydrogen or C(=O)R b , R b is a substituted or unsubstituted C1-C5 alkyl group, R 7a 、R 7b 、R 7c and R 7d each independently is hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C10 alkyl, or a combination thereof, and * is a connection point.

5. The anti - resist top - coat composition according to claim 1, wherein At least one R 7 is a halogen.

6. The anti - resist top - coat composition according to claim 1, wherein At least one R 7 is iodine-based.

7. The anti - resist top - coat composition according to claim 1, wherein The second structural unit is any one selected from Group II: [Group II] Among them, In Group II, R 2 Each independently is hydrogen or methyl, and * is the point of attachment.

8. The anti - resist top - coat composition according to claim 1, wherein n1 in Chemical Formula M - 3A is one of the integers selected from 1 to 5.

9. The anti - resist top - coat composition according to claim 1, wherein n2 in Chemical Formula M - 3B is one of the integers selected from 2 to 4.

10. The anti - resist top - coat composition according to claim 1, wherein n3 in Chemical Formula M - 3C is one of the integers selected from 1 to 5.

11. The anti - resist top - coat composition according to claim 1, wherein the third structural unit is any one selected from Group III: [Group III] Among them, In Group III, R 3 、R 4 and R 12 are each independently hydrogen or methyl, and * is the point of attachment.

12. The anti - resist top - coat composition according to claim 1, wherein The copolymer comprises 30 mol% to 95 mol% of the first structural unit, 1 mol% to 20 mol% of the second structural unit, and 5 mol% to 50 mol% of the third structural unit.

13. The anti - resist top - coat composition according to claim 1, wherein The weight - average molecular weight of the copolymer is 1,000 g / mol to 15,000 g / mol.

14. The anti - resist top - coat composition according to claim 1, wherein The copolymer is any one selected from Group IV: [Group Ⅳ] Among them, In Group Ⅳ, R 1 、R 2 and R 7 each independently represents hydrogen or methyl, x is from 30 mol% to 95 mol%, y is from 2 mol% to 20 mol%, and z is from 5 mol% to 50 mol%.

15. The resist topcoat composition according to claim 1, wherein Based on 100 wt% of the total weight of the resist topcoat composition, the content of the copolymer is from 0.1 wt% to 10 wt%.

16. The resist topcoat composition according to claim 1, wherein The solvent is an ether solvent represented by Chemical Formula 4: [Chemical Formula 4] Among them, In Chemical Formula 4, R 8 and R 9 each independently is a substituted or unsubstituted C1-C20 alkyl group or a substituted or unsubstituted C3-C20 cycloalkyl group.

17. A method of forming a pattern, comprising: Coating and heating a photoresist composition on a substrate to form a photoresist layer, Coating and heating the resist topcoat composition according to any one of claims 1 to 16 on the photoresist layer to form a topcoat, and Exposing and developing the topcoat and the photoresist layer to form a resist pattern.

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