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

Abstract

A resist topcoat composition and a method of forming a pattern using the composition are provided. 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 Chemical Formula M-3A or Chemical Formula M-3B; and a solvent.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0113816 filed in the Korean Intellectual Property Office on August 29, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure relate to a resist topcoat composition and a method of forming a pattern using the composition. Background Art

[0004] Recently, the semiconductor industry has developed ultra-micro technology that provides patterns with sizes ranging from several nanometers to tens of nanometers. This ultra-micro technology should be accompanied by an efficient photolithography process.

[0005] The existing photolithography process involves 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 photolithography processes develop, the degree of pattern integration is increasing, and research is being conducted on materials and techniques for solving various problems arising in the process.

[0007] For example, if extreme ultraviolet light (EUV) is irradiated onto a photoresist, due to the high energy of each photon of EUV light, there may be areas where a large amount of light or a small amount of light is randomly irradiated (this may be referred to as photo shot noise), or the difference in EUV absorption between the top and bottom of the photoresist may cause pattern distribution degradation such as pattern roughness (e.g., LER: line edge roughness, LWR: line width roughness) and / or IPU (in-point uniformity), so further development of technology to improve such pattern dispersion degradation would be useful. Summary of the invention

[0008] Some embodiments of the present disclosure provide a resist top coating composition capable of reducing pattern scatter by preventing or reducing pattern degradation.

[0009] Some embodiments provide methods of forming patterns using a resist topcoat composition.

[0010] Some embodiments provide a resist top coating composition comprising: 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 Chemical Formula M-3A or Chemical Formula M-3B; and a solvent.

[0011]

[0012] In Chemical Formula M-1 and Chemical Formula M-2,

[0013] R 1 and R 2 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0014] L 1 and L 2 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,

[0015] X 1 is a single bond (e.g., a single covalent bond), -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a -(where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl) or a combination thereof,

[0016] R 5 is hydrogen, fluorine, hydroxy, substituted or unsubstituted C1 to C20 alkyl or a combination thereof,

[0017] R 6 is hydrogen or C(=O)R b ,

[0018] R b is a substituted or unsubstituted C1 to C10 alkyl group,

[0019] Selected from R 5 , L 1 and L 2 at least one of which contains fluorine and hydroxyl,

[0020] R 7 is hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, m1 is an integer from 1 to 4, and

[0021] * is the connection point;

[0022]

[0023]

[0024] In the chemical formula M-3A and the chemical formula M-3B,

[0025] R 3 and R 4 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0026] X 2 Is N or CR c ,

[0027] R c is hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0028] L 3 To L 7 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C12 arylene group, or a combination thereof,

[0029] R 8 To R 14 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof,

[0030] n1 is an integer from 1 to 3, and

[0031] * is the point of attachment (eg, point of attachment to another part of the copolymer).

[0032] Some embodiments provide a method for forming a pattern, comprising coating and heating a photoresist composition on a substrate to form a photoresist layer, coating and heating the above-mentioned resist top coating composition on the photoresist layer to form a top coating layer, and exposing and developing the top coating layer and the photoresist layer to form a resist pattern.

[0033] The resist top coating composition according to some embodiments can remove excess activated acid from the top of the photoresist if exposed to EUV to prevent or reduce pattern dispersion degradation, such as roughness (LER, LWR) and / or IPU of the pattern due to EUV absorption differences between the top and bottom of the photoresist, thereby reducing pattern dispersion, significantly improving the IPU of the columnar pattern and facilitating the formation of a fine pattern of the photoresist. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings, together with the specification, illustrate embodiments of the presently disclosed subject matter, and, together with the description, serve to explain principles of the embodiments of the presently disclosed subject matter.

[0035] Figure 1is a schematic diagram illustrating a method of forming a pattern using a resist top coating composition according to some embodiments.

[0036] Description of Reference Numerals

[0037] 1: Forming a photoresist layer

[0038] 2: Forming a photoresist top coat

[0039] 3: Expose and develop the photoresist layer and photoresist top coat to form a resist pattern

[0040] 30: Photoresist top coating

[0041] 100: Substrate

[0042] 101: Photoresist layer

[0043] 102b: Photoresist pattern DETAILED DESCRIPTION

[0044] Exemplary 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 subject matter of the present disclosure can be embodied in many different forms and should not be construed as being limited to the exemplary embodiments described herein.

[0045] In the accompanying drawings, the thickness of layers, films, panels, regions, etc. may be exaggerated for clarity, and the same reference numerals represent the same elements throughout the text. It will be understood that if an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element, or there may be intervening elements. In some embodiments, if an element is referred to as being "directly on" another element, there are no intervening elements.

[0046] As used herein, if no definition is otherwise provided, "substituted" means that a hydrogen atom of the compound is replaced by a substituent selected from the group consisting of a halogen atom (F, Br, Cl or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazo group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a vinyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C6 to C30 allyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and combinations thereof.

[0047] As used herein, if no definition is otherwise provided, the term "alkyl" refers to a straight or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" without any double or triple bonds (eg, the alkyl group does not include any double or triple bonds).

[0048] The alkyl group may be a C1 to C20 alkyl group. In some embodiments, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, the term C1 to C5 alkyl group may refer to an alkyl chain containing 1 to 5 carbon atoms and is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0049] The alkyl group may include examples such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and the like.

[0050] In the chemical formulas described herein, t-Bu refers to tert-butyl.

[0051] As used herein, if no definition is otherwise provided, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0052] The term cycloalkyl refers to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and / or the like.

[0053] The cycloalkyl group may be a C3 to C10 cycloalkyl group, for example, a C3 to C8 cycloalkyl group, a C3 to C7 cycloalkyl group, or a C3 to C6 cycloalkyl group. For example, the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, but is not limited thereto.

[0054] As used herein, unless otherwise defined, the term "alkenyl" refers to an aliphatic unsaturated alkenyl group that is a straight or branched aliphatic hydrocarbon group containing at least one double bond.

[0055] As used herein, unless otherwise defined, the term "alkynyl" refers to an aliphatic unsaturated alkynyl group that is a straight or branched aliphatic hydrocarbon group containing at least one triple bond.

[0056] As used herein, the term "aryl" refers to a substituent in which all atoms in a cyclic substituent have p-orbitals and the p-orbitals are conjugated, and may include monocyclic or fused-ring polycyclic functional groups (e.g., rings that share adjacent pairs of carbon atoms).

[0057] As used herein, "hetero" refers to a group including 1 to 10 heteroatoms selected from N, O, S and P if no definition is provided otherwise.

[0058] In the present disclosure, if a definition is not otherwise provided, the term "heterocycloalkyl group" refers to a cycloalkyl group containing at least one heteroatom selected from N, O, S, P and Si.

[0059] In the present disclosure, the term "heteroaryl" refers to an aryl group including at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryl groups are directly connected by a sigma bond, or if the heteroaryl group includes two or more rings, the two or more rings may be fused together. If the heteroaryl group is a fused ring, each ring may include 1 to 3 heteroatoms.

[0060] Unless otherwise specified in this specification, the weight average molecular weight can be measured by dissolving a powder sample in tetrahydrofuran (THF) and then using a 1200 series gel permeation chromatograph (GPC) from Agilent Technologies (the column can be LF-804 from Shodex and the standard sample can be polystyrene from Shodex).

[0061] In some embodiments, unless otherwise defined in the specification, "*" indicates a point of attachment of a structural unit of a compound or a compound moiety.

[0062] Hereinafter, a photoresist topcoat composition according to some embodiments is described.

[0063] The present disclosure relates to a photoresist top coating composition, which is capable of improving the IPU (intra-dot uniformity) of a C / H (contact hole) pattern, the LER (line edge roughness) / LWR (line width roughness) of an L / S (line and space) pattern, and the IPU of a columnar pattern by improving the sensitivity of the photoresist during a fine pattern forming process of a photolithography method using high-energy rays such as EUV (extreme ultraviolet light; wavelength: about 13.5 nm) and / or the like and selectively reducing the acid concentration in an upper portion of the photoresist in parallel (e.g., simultaneously); and a method for forming a photoresist pattern by using the top coating.

[0064] A resist top coating composition according to some 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 Chemical Formula M-3A or Chemical Formula M-3B; and a solvent.

[0065]

[0066] In Chemical Formula M-1 and Chemical Formula M-2,

[0067] R 1 and R 2 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0068] L 1 and L2 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof,

[0069] X 1 is a single bond (e.g., a single covalent bond), -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a -(where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl) or a combination thereof,

[0070] R 5 is hydrogen, fluorine, hydroxy, substituted or unsubstituted C1 to C20 alkyl or a combination thereof,

[0071] R 6 is hydrogen or C(=O)R b ,

[0072] R b is a substituted or unsubstituted C1 to C10 alkyl group,

[0073] Selected from R 5 , L 1 and L 2 at least one of which contains fluorine and hydroxyl,

[0074] R 7 is hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, m1 is an integer from 1 to 4, and

[0075] * is the point of attachment (e.g., the point of attachment to another part of the copolymer);

[0076]

[0077]

[0078] In the chemical formula M-3A and the chemical formula M-3B,

[0079] R 3 and R 4 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0080] X 2 Is N or CR c ,

[0081] R c is hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0082] L 3 To L7 are each independently a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C12 arylene group, or a combination thereof,

[0083] R 8 To R 14 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof,

[0084] n1 is an integer from 1 to 3, and

[0085] * is the point of attachment (eg, point of attachment to another part of the copolymer).

[0086] The photoresist top coating composition according to some embodiments may be coated on an upper portion of a photoresist layer to significantly improve LER / LWR of an L / S pattern, IPU of a C / H pattern, and IPU of a pillar pattern, and improve sensitivity of the photoresist.

[0087] The first structural unit included in the copolymer of the composition has the property of being almost non-reactive with the photoresist but well soluble in the solvent, and thus can protect the photoresist while minimizing or reducing the impact on the photoresist, while the second structural unit can increase EUV absorption to improve sensitivity. The third structural unit generates an amine-containing basic functional group through acid deprotection, thereby reacting with the acid excessively generated by exposure of the upper portion of the photoresist layer, reducing the acid concentration and changing the circular profile of the upper layer of the photoresist to a rectangle to improve the IPU or LWR of the pattern.

[0088] If the photoresist topcoat composition remains after development, it may cause scum defects in the L / S pattern and / or not-open defects in the C / H pattern, thereby resulting in reduced product yield.

[0089] However, the photoresist top coating composition according to some embodiments may be removed during a development process and thus may not (or substantially not) cause defects in various suitable patterns.

[0090] In the chemical formula M-2, if m1 is 2 or greater, each OR 6 May be the same as or different from each other.

[0091] In the chemical formula M-2, if 5-m1 is 2 or greater, each R 7 May be the same as or different from each other.

[0092] Selected from R 5 , L 1 and L2 The description of at least one containing fluorine and hydroxyl may include the following embodiments, wherein:

[0093] R 5 may be a C1 to C20 alkyl group substituted with at least one fluorine group and at least one hydroxyl group, or

[0094] Selected from L 1 and L 2 At least one of may be a C1 to C10 alkylene group substituted with one or more fluorine and one or more hydroxyl groups, or

[0095] Selected from L 1 and L 2 One of the may be a C1 to C10 alkylene group substituted by one or more fluorine groups, and the other may be a C1 to C10 alkylene group substituted by one or more hydroxy groups, or

[0096] R 5 may be fluorine and is selected from L 1 and L 2 At least one of may be a C1 to C10 alkylene group substituted with one or more hydroxyl groups, or

[0097] R 5 may be hydroxyl and is selected from L 1 and L 2 At least one of may be a C1 to C10 alkylene group substituted with one or more fluorines, or

[0098] R 5 may be a C1 to C10 alkyl group substituted with one or more fluorine groups and one or more hydroxy groups, or

[0099] R 5 It may be a C1 to C10 alkyl group substituted with one or more hydroxyl groups and one or more C1 to C10 fluoroalkyl groups.

[0100] As an example, the first structural unit may be represented by Chemical Formula 1.

[0101] [Chemical formula 1]

[0102]

[0103] In Chemical Formula 1,

[0104] R 1 is hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0105] R d , R e , R f , R g and R5 are each independently hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof,

[0106] m2 and m3 are each independently an integer from 1 to 10,

[0107] X 1 is a single bond (e.g., a single covalent bond), -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a -(where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl) or a combination thereof,

[0108] Selected from R d , R e , R f , R g and R 5 At least one of contains fluorine and hydroxyl, and

[0109] * is the point of attachment (eg, * is the point of attachment to another part of the copolymer).

[0110] In Formula 1, if m2 is 2 or greater, each R d May be the same as or different from each other.

[0111] In Formula 1, if m2 is 2 or greater, each R e May be the same as or different from each other.

[0112] In Formula 1, if m3 is 2 or greater, each R f May be the same as or different from each other.

[0113] In Formula 1, if m3 is 2 or greater, each R g May be the same as or different from each other.

[0114] Selected from R d , R e , R f , R g and R 5 The description of at least one containing fluorine and hydroxyl may include the following embodiments, wherein:

[0115] Selected from R d , R e , R f , R g and R 5 At least one of each independently is fluorine and hydroxyl, or

[0116] Selected from Rd , R e , R f , R g and R 5 At least one of each independently comprises a C1 to C10 alkyl group substituted by one or more fluorine groups and a C1 to C10 alkyl group substituted by one or more hydroxy groups, or

[0117] Selected from R d , R e , R f , R g and R 5 At least one of each independently comprises a C1 to C10 alkyl group substituted by one or more hydroxyl groups and one or more fluorine groups, or

[0118] Selected from R d , R e , R f , R g and R 5 At least one of each independently comprises a C1 to C5 alkyl group substituted with one or more hydroxyl groups and one or more C1 to C5 fluoroalkyl groups, or

[0119] Selected from R d , R e , R f , R g and R 5 at least one of is fluorine and at least one of the others is hydroxyl, or

[0120] Selected from R d , R e , R f , R g and R 5 At least one of them is fluorine, and at least one of the others includes a C1 to C10 alkyl group substituted with one or more hydroxyl groups, or

[0121] Selected from R d , R e , R f , R g and R 5 At least one of them is a hydroxyl group, and at least one of the others includes a C1 to C10 alkyl group substituted with one or more fluorine groups, or

[0122] Selected from R d , R e , R f , R g and R 5 At least one of the groups is a C1 to C20 alkyl group substituted by one or more fluorine groups, and at least one of the groups selected from the others is a C1 to C20 alkyl group substituted by one or more hydroxy groups.

[0123] For example, R 1 can be hydrogen or methyl,

[0124] X 1 It can be a single bond (e.g., a single covalent bond), -O-, or -NR a -(where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl), and

[0125] R 5 It may be fluorine, hydroxyl, a C1 to C10 alkyl group substituted by at least one fluorine group, or a C1 to C10 alkyl group substituted by at least one hydroxyl group.

[0126] As an example, in Chemical Formula 1, R f , R g and R 5 At least one of may contain fluorine and hydroxyl groups.

[0127] As an example, in Chemical Formula 1, R f and R g At least one of them may be fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 5 It may be a hydroxy group or a C1 to C10 alkyl group substituted with at least one hydroxy group.

[0128] As an example, in Chemical Formula 1, R f and R g At least one of them may be a hydroxyl group or a C1 to C10 alkyl group substituted with at least one hydroxyl group, and R 5 It may be fluorine or a C1 to C10 alkyl group substituted with at least one fluorine.

[0129] As an example, in Chemical Formula 1, R f It may be a hydroxyl group or a C1 to C10 alkyl group substituted with at least one hydroxyl group, R g may be fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 5 It may be hydroxy, fluorine, or a C1 to C10 alkyl group substituted with at least one selected from fluorine and hydroxy.

[0130] As an example, in Chemical Formula 1, R f and R g At least one of them may be fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 5 It may be a hydroxy group or a C1 to C5 alkyl group substituted with at least one selected from a hydroxy group and a C1 to C5 fluoroalkyl group.

[0131] For example, the first structural unit may be selected from Group I.

[0132] [Group I]

[0133]

[0134] In Group I,

[0135] R 1 Each is independently hydrogen or methyl, and * is the point of attachment (eg, the point of attachment to another part of the copolymer).

[0136] As an example, the second structural unit may be represented by any one selected from Chemical Formula 2-1 to Chemical Formula 2-4.

[0137]

[0138]

[0139] [Chemical formula 2-4]

[0140]

[0141] In Chemical Formula 2-1 to Chemical Formula 2-4,

[0142] R 2 is hydrogen or methyl,

[0143] R 6 , R 6a and R 6b are independently hydrogen or C(=O)R b ,

[0144] R b is a substituted or unsubstituted C1 to C5 alkyl group,

[0145] R 7a , R 7b , R 7c and R 7d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, and

[0146] * is the point of attachment (eg, point of attachment to another part of the copolymer).

[0147] As an example, R 7 At least one of may be a halogen.

[0148] As an example, R 7 At least one of the may be an iodine group.

[0149] If the second structural unit comprises an iodine group, the sensitivity can be further improved.

[0150] For example, the second structural unit may be selected from Group II.

[0151] [Group II]

[0152]

[0153] In Group II,

[0154] R 2 Each is independently hydrogen or methyl, and * is the point of attachment (eg, the point of attachment to another part of the copolymer).

[0155] For example, L 3 and L 7 may each independently be a single bond (eg, a single covalent bond), a substituted or unsubstituted C1 to C5 alkylene group, or a substituted or unsubstituted phenylene group,

[0156] R 8 To R 14 may each independently be hydrogen, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl, and

[0157] n1 can be an integer of 1 or 2.

[0158] The third structural unit may be selected from Group III.

[0159] [Group III]

[0160]

[0161] In Group III,

[0162] R 3 is hydrogen or methyl, and * is the point of attachment (eg, the point of attachment to another part of the copolymer).

[0163] The copolymer may 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 3 mol % to about 50 mol % of the third structural unit.

[0164] For example, the copolymer may include about 55mol% to about 90mol% of the first structural unit, about 5mol% to about 15mol% of the second structural unit, and about 3mol% to about 30mol% of the third structural unit. In some embodiments, the copolymer may include about 60mol% to about 85mol% of the first structural unit, about 5mol% to about 15mol% of the second structural unit, and about 5mol% to about 25mol% of the third structural unit.

[0165] If the molar ratio of each structural unit included in the copolymer is within the above range, solubility in an organic solvent is improved, and a pattern may be uniformly (or substantially uniformly) coated.

[0166] The copolymer may have a weight average molecular weight (Mw) of about 1,000 g / mol to about 50,000 g / mol. For example, the copolymer may have a weight average molecular weight of about 2,000 g / mol to about 30,000 g / mol, such as about 4,000 g / mol to about 10,000 g / mol, but is not limited thereto. If the weight average molecular weight of the copolymer is within the above range, the carbon content of the resist top coating composition containing the copolymer and the solubility in the solvent can be improved.

[0167] The copolymer may be included in an amount of about 0.1 wt % to about 10 wt % based on the total weight of the resist top coating composition.Within the above range, the resist top coating may be easily removed.

[0168] In some embodiments, the copolymer may be selected from those listed in Group IV.

[0169] [Group IV]

[0170]

[0171] In Group IV, x is from about 30 mol% to about 95 mol%, y is from about 1 mol% to about 20 mol%, and z is from about 3 mol% to about 50 mol%.

[0172] For example, x:y:z can be 73:10:17, 76:8:16, or 77:9:14.

[0173] The solvent may be an ether solvent represented by Chemical Formula 4.

[0174] [Chemical formula 4]

[0175]

[0176] In chemical formula 4,

[0177] R 15 and R 16 Each is independently a substituted or unsubstituted C3 to C20 alkyl group.

[0178] For example, the ether solvent can be selected from diisopropyl ether, dipropyl ether, diisoamyl ether, diamyl ether, dibutyl ether, diisobutyl ether, disec-butyl ether, dihexyl ether, bis(2-ethylhexyl) ether, didecyl ether, didedecyl ether, didedecyl ether, didedecyl ether, didetradecyl ether, hexadecyl 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, 2-octanone, 4-heptanone and combinations thereof.

[0179] For the above composition, the ether solvent may have suitable or sufficient solubility and / or dispersibility.

[0180] In some embodiments, the resist top coating composition may further include at least one other polymer selected from the group consisting of epoxy-based resin, novolac resin, glycoluril-based resin, and melamine-based resin, but is not limited thereto.

[0181] The resist top coating composition may further include an additive including a surfactant, a thermal acid generator, a plasticizer, or a combination thereof.

[0182] The surfactant may be, for example, alkylbenzene sulfonate, alkyl pyridinium salt, polyethylene glycol, quaternary ammonium salt, and / or the like, but is not limited thereto.

[0183] The thermal acid generator can be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluene sulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid and / or benzoin tosylate, 2-nitrobenzyl tosylate and / or other organic alkyl sulfonates, but is not limited thereto.

[0184] The amounts of these additives can be easily adjusted and may be omitted depending on the desired physical properties as desired.

[0185] According to some exemplary embodiments, a method of forming a pattern using the above-mentioned photoresist top coating composition may be provided. For example, the fabricated pattern may be a photoresist pattern.

[0186] The method of forming a pattern according to some exemplary embodiments includes coating and heating a photoresist composition on a substrate to form a photoresist layer, coating and heating the above-mentioned photoresist top coating composition on the photoresist layer to form a top coating layer, and exposing and developing the top coating layer and the photoresist layer to form a resist pattern.

[0187] Hereinafter, a method of forming a pattern using the above-mentioned photoresist top coating composition will be described with reference to the accompanying drawings. Figure 1 is a schematic diagram illustrating a method of forming a pattern using a photoresist top coating composition according to the present disclosure.

[0188] Referring to the accompanying drawings, first, an object to be etched is prepared. An example of the object to be etched may be a thin film on a semiconductor substrate. Hereinafter, only the case where the object to be etched is a thin film is 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, and / or a silicon oxide film.

[0189] A photoresist composition is coated on the thin film 100 and heated to form a photoresist layer 101 (stage 1). Subsequently, a photoresist topcoat composition is coated on the photoresist layer and heated to form a photoresist topcoat layer 30 (stage 2).

[0190] The heating may be performed at a temperature of about 80°C to about 500°C.

[0191] The photoresist topcoat and photoresist layer are then exposed to high energy radiation.

[0192] For example, high-energy radiation that may be used in the exposure process may include light having a high-energy wavelength, such as EUV (extreme ultraviolet light; wavelength: 13.5 nm) and / or E-beam (electron beam).

[0193] A post-exposure thermal treatment (PEB) is then performed. The post-exposure thermal treatment may be performed at a temperature of about 80° C. to about 200° C. By performing the post-exposure thermal treatment, the exposed region of the photoresist layer (e.g., the region not covered by the patterned mask) becomes soluble in the developer, so that the exposed region has a different solubility from the unexposed region of the photoresist layer.

[0194] The photoresist pattern 102b may be formed by dissolving and removing the photoresist layer and the photoresist top coat layer corresponding to the exposed area using a developer (stage 3).

[0195] In some embodiments, the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter referred to as an organic-based developer).

[0196] As the alkaline developer, a quaternary ammonium salt such as tetramethylammonium hydroxide may be used, but an alkaline aqueous solution such as an inorganic base, a primary to tertiary amine, an alcoholamine and / or a cyclic amine may also be used.

[0197] In some embodiments, the alkaline developer may include an appropriate amount or a suitable amount of alcohol and / or a surfactant. The alkaline developer may have an alkali concentration of, for example, about 0.1% to about 20% by mass, and a pH of, for example, about 10 to about 15.

[0198] The organic-based developer may be a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent.

[0199] Examples of the ketone solvent may include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

[0200] Examples of the ester solvents may include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl 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-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 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 the like.

[0201] Any suitable solvent generally used in the art may be used as the alcohol solvent, the amide solvent, the ether solvent and / or the hydrocarbon solvent.

[0202] A plurality of the solvents may be mixed together, or may be mixed with a solvent other than the above solvents or water. As the developer as a whole, the water content may be appropriately or desirably less than about 50 wt %, less than about 20 wt %, less than about 10 wt %, or the developer may be substantially free of or completely free of water.

[0203] The organic solvent may be appropriately or desirably included in an amount of about 50 wt % to about 100 wt %, about 80 wt % to about 100 wt %, about 90 wt % to about 100 wt %, or about 95 wt % to about 100 wt %, based on the total amount of the organic developer.

[0204] The organic developer may include any suitable surfactant in a suitable amount or a suitable amount as required.

[0205] The surfactant may be included in an amount of about 0.001 wt % to about 5 wt %, about 0.005 wt % to about 2 wt %, or about 0.01 wt % to about 0.5 wt %, based on the total amount of the developer.

[0206] Organic developers may include inhibitors.

[0207] Subsequently, the exposed thin film is etched by using the photoresist pattern as an etching mask, thereby forming the thin film into a thin film pattern.

[0208] The thin film may be etched, for example, by dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 , or a mixture thereof.

[0209] In the exposure process performed above, the thin film pattern formed by the photoresist pattern formed by the exposure process performed with the EUV light source can have a width corresponding to the photoresist pattern. For example, the photoresist pattern can have a width of about 5nm to about 100nm. For example, the thin film pattern formed by the exposure process performed with the EUV light source can have a width of about 5nm to about 90nm, about 5nm to about 80nm, about 5nm to about 70nm, about 5nm to about 60nm, about 5nm to about 50nm, about 5nm to about 40nm, about 5nm to about 30nm, about 5nm to about 20nm, or can have a width less than or equal to about 20nm, which is similar to the width of the photoresist pattern.

[0210] Hereinafter, embodiments of the present disclosure will be described in more detail through examples involving the synthesis of the above-mentioned polymer and the preparation of a photoresist top coating composition including the polymer. However, the present disclosure is not technically limited to the following examples.

[0211] Synthesis example

[0212] Synthesis Example 1: Synthesis of Compound 1a

[0213] Under nitrogen atmosphere, 20g (59.86mmol) of hexafluoro-2,3-bis (trifluoromethyl) -2,3-butanediol (perfluoropinacol), 7.79g (59.86mmol) of 2- (hydroxyethyl) methacrylate and 18.84g (71.84mmol) of triphenylphosphine (PH3P) were mixed together in 110ml of ether and then stirred. After stirring for 30 minutes, the obtained mixture was cooled to 0°C, and another mixture of 14.52g (71.84mmol) of diisopropyl azodicarboxylate (DIAD) and 35ml of ether was slowly added thereto over 2 hours. Subsequently, the obtained mixture was stirred at room temperature (23°C) for 24 hours and then concentrated. The concentrated mixture was dissolved in dichloromethane and then treated by column chromatography using silica gel to separate the synthesized substance. The separated substance was distilled under reduced pressure to obtain 2-[3,3,3-trifluoro-2-hydroxy-1,1,2-tris(trifluoromethyl)propoxy]ethyl 2-methyl-2-propionate represented by Chemical Formula 1a.

[0214] * 1 H-NMR (acetone-d6): δ1.90 (3H, t), 4.36 (4H, m), 5.63 (1H, t), 6.09 (1H, t), 8.34 (1H, s)

[0215] * 19 F-NMR (acetone-d6):δ-70.12(6F,m),-65.38(6F,m)

[0216] [Chemical formula 1a]

[0217]

[0218] Synthesis Example 2: Synthesis of Compound 1c

[0219] Under nitrogen atmosphere, 20g (100mmol) of tert-butyl-4-hydroxypiperidine-1-carboxylate and 11.1g (110mmol) of triethylamine were mixed together in 120ml of tetrahydrofuran, and the temperature was lowered to -10°C, and then stirred. After stirring for 30 minutes, 11.5g (110mmol) of methacryloyl chloride was slowly added thereto within 10 minutes. After stirring at room temperature (23°C) for 24 hours, the solid content obtained was filtered, and the obtained organic solvent layer was then concentrated. The concentrated mixture was dissolved in 100ml of dichloromethane and washed three times with 100ml of water. After concentrating the washed organic layer, the concentrated mixture was treated by column chromatography using silica gel to separate the synthesized substance. The separated substance was distilled under reduced pressure to obtain 1,1-dimethylethyl 4-[(2-methyl-1-oxo-2-propylene-1-yl)oxy]-1-piperidinecarboxylate represented by chemical formula 1c.

[0220] * 1 H-NMR(CDCl3): δ1.47(9H,s),1.69(2H,m),1.85(2H,m),1.95(3H,t),3,31(2H,m)3.66(2H,m),5.01(1H,m),5.58(1H,s),6.11(1H,s)

[0221] [Chemical formula 1c]

[0222]

[0223] Synthesis Example 3: Synthesis of Compound 2c

[0224] Under nitrogen atmosphere, 18.7g (100mmol) of tert-butyl-4-hydroxypiperidine-1-carboxylate and 11.1g (110mmol) of triethylamine were mixed together in 120ml of tetrahydrofuran, and the temperature was lowered to -10°C, and then stirred. After stirring for 30 minutes, 11.5g (110mmol) of methacryloyl chloride was slowly added thereto within 10 minutes. After stirring at room temperature (23°C) for 24 hours, the solid content obtained was filtered, and the obtained organic solvent layer was then concentrated. The concentrated mixture was dissolved in 100ml of dichloromethane and washed three times with 100ml of water. After concentrating the washed organic layer, the concentrated mixture was treated by column chromatography using silica gel to separate the synthesized substance. The separated substance was distilled under reduced pressure to obtain 1,1-dimethylethyl 3-[(2-methyl-1-oxo-2-propene-1-yl)oxy]-1-pyrrolidinecarboxylate represented by chemical formula 2c.

[0225] * 1H-NMR(CDCl3): δ1.47(9H,s),1.85(2H,m),1.95(3H,t),3,31(2H,m)3.66(2H,m),5.01(1H,m),5.58(1H,s),6.11(1H,s)

[0226] [Chemical formula 2c]

[0227]

[0228] Synthesis Example 4: Synthesis of Compound 3c

[0229] Under nitrogen atmosphere, 23g (100mmol) of tert-butyl 4-(2-hydroxyethyl) piperazine-1-carboxylate and 11.1g (110mmol) of triethylamine were mixed in 120ml of tetrahydrofuran, and the temperature was lowered to -10°C, and then stirred. After stirring for 30 minutes, 11.5g (110mmol) of methacryloyl chloride was slowly added thereto within 10 minutes. After stirring at room temperature (23°C) for 24 hours, the solid content obtained was filtered, and the organic solvent layer obtained was then concentrated. The concentrated mixture was dissolved in 100ml of dichloromethane and washed three times with 100ml of water. After the organic layer was concentrated and washed, the concentrated mixture was treated by column chromatography using silica gel to separate the synthesized substance. The separated material was distilled under reduced pressure to obtain 1,1-dimethylethyl 4-[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl]-1-piperazinecarboxylate represented by Chemical Formula 3c.

[0230] * 1 H-NMR(CDCl3): δ1.46(9H,s),1.95(3H,s),2.48(2H,t),2.70(2H,t),3.43(2H,t),4.30(2H,t),5.58(1H,t),6.10(1H,t)

[0231] [Chemical formula 3c]

[0232]

[0233] Synthesis Example 5: Synthesis of Compound 4c

[0234] Under nitrogen atmosphere, 17.5g (100mmol) of 3-(tert-butoxycarbonylamino)-1-propanol and 11.1g (110mmol) of triethylamine were mixed together in 120ml of tetrahydrofuran, and the temperature was lowered to -10°C, and then stirred. After stirring for 30 minutes, 11.5g (110mmol) of methacryloyl chloride was slowly added thereto within 10 minutes. After stirring at room temperature (23°C) for 24 hours, the solid content obtained was filtered, and the obtained organic solvent layer was then concentrated. The concentrated mixture was dissolved in 100ml of dichloromethane and washed three times with 100ml of water. After concentrating the washed organic layer, the concentrated mixture was treated by column chromatography using silica gel to separate the synthesized substance. The separated substance was distilled under reduced pressure to obtain 3-[[(1,1-dimethylethoxy)carbonyl]amino]propyl 2-methyl-2-propionate represented by chemical formula 4c.

[0235] * 1 H-NMR(CDCl3): δ1.44(9H,s),1.85(2H,m),1.95(3H,s),3.22(2H,m),4.22(2H,t),4.78(1H,b),5.58(1H,t),6.11(1H,t)

[0236] [Chemical formula 4c]

[0237]

[0238] Synthesis Example 6: Preparation of Copolymer (R1)

[0239] In a 250mL 2-necked round-bottom flask, 22.5g of the compound represented by chemical formula 1a, 2.4g of the compound represented by chemical formula 1b (DIVPA, Songwon), 4.3g of the compound represented by chemical formula 1c and 115g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere and then heated to 100°C. When the internal temperature reached 115°C, 26.5g of 25wt% V-601 / DIAE solution (V-601, 6.6g) was slowly added thereto, and after 6 hours, the obtained reaction solution was cooled to room temperature and then concentrated to have a solid content of 50%. 270g of heptane was added to the concentrated solution, and the polymer produced therefrom was filtered. The filtered polymer was completely dissolved in 34g of DIAE, and 270g of heptane was added thereto for precipitation, which was repeated twice to obtain a precipitate, and the precipitate was completely dried to prepare the final copolymer R1 (Mw=7,100).

[0240] [Chemical formula 1b]

[0241]

[0242] Synthesis Example 7: Preparation of Copolymer (R2)

[0243] Copolymer R2 (Mw=6,600) was prepared in the same manner as in Synthesis Example 6, except that 4.1 g of the compound represented by Chemical Formula 2c was used instead of the compound represented by Chemical Formula 1c.

[0244]

[0245] Synthesis Example 8: Preparation of Copolymer (R3)

[0246] Copolymer R3 (Mw=5,400) was prepared in the same manner as in Synthesis Example 6, except that 4.8 g of the compound represented by Chemical Formula 3c was used instead of the compound represented by Chemical Formula 1c.

[0247]

[0248] Synthesis Example 9: Preparation of Copolymer (R4)

[0249] Copolymer R4 (Mw=6,800) was prepared in the same manner as in Synthesis Example 6, except that 3.9 g of the compound represented by Chemical Formula 4c was used instead of the compound represented by Chemical Formula 1c.

[0250]

[0251] Comparative Synthesis Example 1: Preparation of Copolymer (R5)

[0252] Copolymer R5 (Mw=6,000) was prepared in the same manner as in Synthesis Example 6, except that 4.1 g of the compound represented by Chemical Formula 5c (1-(2,2-dimethyl-1-oxopropyl)-4-piperidinyl 2-methyl-2-propionate, Sigma-Aldrich) was used instead of the compound represented by Chemical Formula 1c.

[0253] [Chemical Formula 5c]

[0254]

[0255] Comparative Synthesis Example 2: Preparation of Copolymer (R6)

[0256] Copolymer R6 (Mw = 6,000) was prepared in the same manner as in Synthesis Example 6, except that 4.9 g of the compound represented by Chemical Formula 6c (benzyl-4-[(2-methyl-1-oxo-2-propen-1-yl)oxy]-1-piperidinecarboxylate, Sigma-Aldrich Company) was used instead of the compound represented by Chemical Formula 1c.

[0257] [Chemical formula 6c]

[0258]

[0259] Comparative Synthesis Example 3: Preparation of Copolymer (R7)

[0260] Copolymer R7 (Mw=5,500) was prepared in the same manner as in Synthesis Example 6, except that 4.8 g of the compound represented by Chemical Formula 7c (3-[[(4-methylphenyl)sulfonyl]amino]propyl 2-methyl-2-propionate, Sigma-Aldrich) was used instead of the compound represented by Chemical Formula 1c.

[0261] [Chemical Formula 7c]

[0262]

[0263] Comparative Synthesis Example 4: Preparation of Copolymer (R8)

[0264] Copolymer R8 (Mw=7,000) was prepared in the same manner as Synthesis Example 6 except that 3.2 g of the compound represented by Chemical Formula 8c (2-ethylhexyl methacrylate, Daejeong Chemical Co., Ltd.) was used instead of the compound represented by Chemical Formula 1c.

[0265] [Chemical formula 8c]

[0266]

[0267]

[0268] Preparation of resist topcoat composition

[0269] Examples 1 to 4 and Comparative Examples 1 to 4

[0270] 0.5 wt % of the copolymers R1 to R8 according to Synthesis Examples 6 to 9 and Comparative Synthesis Examples 1 to 4 were dissolved in 100 g of diisoamyl ether (DIAE: diisoamyl ether), then stirred at room temperature (23° C.) for 24 hours, and filtered through a TEFLON filter having a pore size of 0.45 μm to prepare the anti-corrosion top coating compositions according to Examples 1 to 4 and Comparative Examples 1 to 4.

[0271] Evaluation: Evaluation of sensitivity and LWR

[0272] A resist lower layer (thickness: ) and photoresist films for electron beams (thickness: ), each of the photoresist top coating compositions 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 top coating layer of about 5 nm in thickness.

[0273] On the wafer on which the photoresist top coating was formed, line and space patterns were formed in a focused energy matrix (FEM) form using an electron beam apparatus (JEOL JBX-9300FS). Subsequently, the best sensitivity capable of forming a critical dimension (CD) of 50 nm was examined in an interpolation method, and the results are shown in Table 1, and

[0274] After checking the optimal sensitivity, the line width roughness (LWR) dispersion under the corresponding energy shot was measured by using a CD-SEM device manufactured by Hitatchi Ltd., and the same pattern at 500 points within the beam was measured to obtain the reliability of the dispersion, and the final average value thereof is shown in Table 1.

[0275] Table 1

[0276] Copolymer <![CDATA[Sensitivity (μC / cm 2 )]]> LWR(nm) Example 1 R1 2000 2.12 Example 2 R2 2100 2.15 Example 3 R3 1900 2.10 Example 4 R4 2100 2.19 Comparative Example 1 R5 2200 2.31 Comparative Example 2 R6 2200 2.28 Comparative Example 3 R7 2300 2.33 Comparative Example 4 R8 2500 2.55

[0277] Referring to Table 1, if the resist top coating composition according to an embodiment of the present disclosure is applied, not only excellent sensitivity is achieved but also excellent LWR improvement effect is obtained.

[0278] In the above, exemplary embodiments of the present disclosure have been described and illustrated, but it is clear to those skilled in the art that the present disclosure is not limited to the described embodiments, and they can be changed and transformed differently without departing from the spirit and scope of the present disclosure. Therefore, the embodiments thus changed or transformed cannot be understood separately from the technical ideas and aspects of the present disclosure, and the changed embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. A resist top coating composition comprising: A copolymer, comprising: The first structural unit represented by the chemical formula M-1, a second structural unit represented by the chemical formula M-2, and a third structural unit represented by Chemical Formula M-3A or Chemical Formula M-3B; and Solvents, In Chemical Formula M-1 and Chemical Formula M-2, R 1 and R 2 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl, L 1 and L 2 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a combination thereof, X 1 Is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a - or a combination thereof, wherein R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl, R 5 is hydrogen, fluorine, hydroxy, substituted or unsubstituted C1 to C20 alkyl or a combination thereof, R 6 is hydrogen or C(=O)R b , R b is a substituted or unsubstituted C1 to C10 alkyl group, Selected from R 5 , L 1 and L 2 at least one of which contains fluorine and hydroxyl, R 7 is hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, m1 is an integer from 1 to 4, and * is the connection point; In the chemical formula M-3A and the chemical formula M-3B, R 3 and R 4 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl, X 2 Is N or CR c , R c is hydrogen or substituted or unsubstituted C1 to C10 alkyl, L 3 To L 7 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C12 arylene group, or a combination thereof, R 8 To R 14 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C20 aryl, or a combination thereof, n1 is an integer from 1 to 3, and * is the connection point.

2. The resist top coating composition according to claim 1, wherein The first structural unit is represented by Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, R 1 is hydrogen or substituted or unsubstituted C1 to C10 alkyl, R d , R e , R f , R g and R 5 are each independently hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof, m2 and m3 are each independently an integer from 1 to 10, X 1 Is a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -(CO)O-, -O(CO)-, -O(CO)O-, -NR a - or a combination thereof, wherein R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl, and Selected from R d , R e , R f , R g and R 5 At least one of the above mentioned compounds contains fluorine and hydroxyl groups.

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

4. The resist top coating 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 2-4] In Chemical Formula 2-1 to Chemical Formula 2-4, R 2 is hydrogen or methyl, R 6 , R 6a and R 6b are independently hydrogen or C(=O)R b , R b is a substituted or unsubstituted C1 to C5 alkyl group, R 7a , R 7b , R 7c and R 7d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, and * is the connection point.

5. The resist top coating composition according to claim 1, wherein R 7 At least one of them is a halogen.

6. The resist top coating composition according to claim 1, wherein R 7 At least one of the groups is an iodine group.

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

8. The resist top coating composition according to claim 1, wherein L 3 and L 7 are each independently a single bond, a substituted or unsubstituted C1 to C5 alkylene group, or a substituted or unsubstituted phenylene group, R 8 To R 14 are each independently hydrogen or substituted or unsubstituted C1 to C10 alkyl, and n1 is an integer of 1 or 2.

9. The resist top coating composition according to claim 1, wherein The third structural unit is at least one selected from Group III: [Group III] In Group III, R 3 is hydrogen or methyl, and * is the point of attachment.

10. The resist top coating composition according to claim 1, wherein The copolymer includes 30 mol % to 95 mol % of the first structural unit, 1 mol % to 20 mol % of the second structural unit, and 3 mol % to 50 mol % of the third structural unit.

11. The resist top coating composition according to claim 1, wherein The weight average molecular weight of the copolymer is 1,000 g / mol to 50,000 g / mol.

12. The resist top coating composition according to claim 1, wherein The copolymer is selected from those listed in Group IV: [Group IV] In Group IV, x is 30 mol% to 95 mol%, y is 1 mol% to 20 mol%, and z is 3 mol% to 50 mol%.

13. The resist top coating composition according to claim 1, wherein The copolymer is included in an amount of about 0.1 wt % to about 10 wt % based on the total weight of the resist top coating composition.

14. The resist top coating composition according to claim 1, wherein The solvent is an ether solvent represented by Chemical Formula 4: [Chemical formula 4] In chemical formula 4, R 15 and R 16 Each is independently a substituted or unsubstituted C3 to C20 alkyl group.

15. A method for forming a pattern, comprising: coating and heating a photoresist composition on a substrate to form a photoresist layer, coating and heating the resist top coating composition according to any one of claims 1 to 14 on the photoresist layer to form a top coating layer, and The top coating layer and the photoresist layer are exposed and developed to form a resist pattern.

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