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

Abstract

Provided are a resist top coating composition and a method of forming a pattern using the same. The resist top coating composition includes a copolymer including a first structural unit represented by Chemical Formula M-1 and a second structural unit represented by Chemical Formula M-2; a photoacid generator; and a solvent, in which the photoacid generator is a nonionic compound including an organic sulfonate group or an ionic compound including, as an anion, at least one selected from the group consisting of a conjugated base of an inorganic acid and a conjugated base of an organic sulfonic acid.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0034112, filed on March 11, 2024, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure relate to resist topcoat compositions and methods of forming patterns using the same. Background Art

[0004] Recently, the semiconductor industry is developing ultra-fine technology with patterns ranging from a few nanometers to tens of nanometers in size. This ultra-fine technology benefits from efficient photolithography processes.

[0005] The photolithography process generally involves providing 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] With the development of photolithography processes, pattern integration is increasing, and research is underway on materials and technologies for solving various problems arising in these processes.

[0007] For example, if extreme ultraviolet (EUV) light is irradiated onto a photoresist, regions of randomly varying sizes may appear due to the large energy of each photon. This is photon shot noise, and / or differences 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): line edge roughness, and / or LWR (Line Width Roughness): line width roughness) or in-point uniformity (IPU). In order to improve this pattern distribution degradation, technology development is being researched. Summary of the Invention

[0008] Some embodiments of the present disclosure provide a resist topcoat composition capable of reducing pattern distribution 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 topcoat composition comprising a copolymer comprising a first structural unit represented by Chemical Formula M-1 and a second structural unit represented by Chemical Formula M-2; a photoacid generator; and a solvent, wherein the photoacid generator is a nonionic compound or an ionic compound, the nonionic compound comprising an organic sulfonate group, and the ionic compound comprising at least one selected from a conjugate base of an inorganic acid and a conjugate base of an organic sulfonic acid as an anion.

[0011]

[0012]

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

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

[0015] 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,

[0016] 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 a substituted or unsubstituted C1 to C10 alkyl group), or a combination thereof,

[0017] R 3 is hydrogen, fluorine, hydroxy, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof,

[0018] R 4 is hydrogen, or C(=O)R b ,

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

[0020] From R 3 , L 1 and L 2 at least one selected from among fluorine and hydroxyl groups,

[0021] R 5 is hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof,

[0022] m1 is an integer from 1 to 4, and

[0023] * indicates the connection point.

[0024] Some embodiments provide a method of forming a pattern, which includes coating and heating a photoresist composition on a substrate to form a photoresist layer, coating and heating the above-mentioned resist topcoat composition on the photoresist layer to form a topcoat layer, and exposing and developing the topcoat layer and the photoresist layer to form a resist pattern.

[0025] If the resist topcoat composition according to some embodiments is applied to EUV photoresist, the amount of acid generated in the exposed area increases, enabling patterning with less energy (eg, reducing the energy used to form the pattern), thereby improving the sensitivity of the EUV photoresist. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] 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.

[0027] Figure 1 is a schematic diagram illustrating a method of forming a pattern using a resist topcoat composition according to some embodiments.

[0028] Explanation of Figure Numbers

[0029] 1, 2, 3: action;

[0030] 30: photoresist top coating;

[0031] 100: target;

[0032] 101: photoresist layer;

[0033] 102b: Photoresist pattern. DETAILED DESCRIPTION

[0034] Hereinafter, the embodiments will be described in more detail so that those skilled in the art can easily implement the subject matter of the present disclosure. 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 example embodiments described herein.

[0035] In the drawings, the thickness of layers, films, panels, regions, etc. may be exaggerated for clarity, and the same reference numerals refer to the same elements throughout the specification. It should be understood that if 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 be present. Conversely, if an element is referred to as being "directly on" another element, there are no intervening elements present.

[0036] As used herein, if no definition is otherwise provided, "substituted" refers to a compound whose hydrogen atoms are selected from a halogen atom (F, Br, Cl or I), an oxo group, a hydroxyl group, a thiol group, a nitro group, a cyano group, an amino group, an azido group, an amide group, a hydrazine group, a hydrazine keto 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, The present invention may be substituted with a substituent selected from the group consisting of C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 aralkyl, C6 to C30 allyl, C1 to C30 alkoxy, C1 to C30 sulfide, C1 to C20 heteroalkyl, C2 to C20 heteroaryl, C3 to C20 heteroaralkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C3 to C30 heterocycloalkyl, and combinations thereof.

[0037] As used herein, unless otherwise defined, "alkyl" refers to a linear or branched aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0038] The alkyl group may be a C1 to C8 alkyl group. In an embodiment, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C5 alkyl group means that the alkyl chain contains 1 to 5 carbon atoms and is selected from, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0039] The alkyl group refers to an example including, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group and the like.

[0040] In the chemical formulas described herein, t-Bu refers to tert-butyl.

[0041] As used herein, if no definition is provided otherwise, "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0042] The cycloalkyl group refers to an example including, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

[0043] 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.

[0044] As used herein, unless otherwise defined, "alkenyl" refers to an aliphatically unsaturated alkenyl group containing at least one double bond as a straight-chain or branched aliphatic hydrocarbon group.

[0045] 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 aliphatic hydrocarbon group.

[0046] As used herein, "aryl" refers to a cyclic substituent in which all atoms have p orbitals and these p orbitals are conjugated, and may include monocyclic functional groups, polycyclic functional groups, or fused ring (eg, rings sharing adjacent pairs of carbon atoms) functional groups.

[0047] As used herein, if no definition is provided otherwise, "hetero" refers to a group containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

[0048] In the present disclosure, if no definition is otherwise provided, "heterocycloalkyl" refers to a cycloalkyl group containing at least one heteroatom selected from N, O, S, P and Si.

[0049] In the embodiments of 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 heteroaryl groups may be directly linked 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 contain 1 to 3 heteroatoms.

[0050] In the embodiment, in this specification, the acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer.

[0051] Unless otherwise specified in this specification, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using an Agilent Technologies 1200 Series Gel Permeation Chromatography (GPC) (the column is Showa Denko LF-804 and the standard sample is Showa Denko polystyrene).

[0052] In the Examples, unless otherwise defined in the specification, "*" indicates a point of attachment of a structural unit or a compound moiety of a compound.

[0053] Resist topcoat compositions according to some embodiments are described below.

[0054] Embodiments of the present disclosure relate to a photoresist topcoat composition and a method for forming a photoresist pattern using such a topcoat. The photoresist topcoat composition can improve the sensitivity of the photoresist by maximizing or increasing the amount of acid generated in the exposed area during fine pattern formation using high-energy radiation, such as EUV (extreme ultraviolet radiation; wavelength 13.5 nanometers).

[0055] The resist topcoat composition according to some embodiments includes: a copolymer including a first structural unit represented by Chemical Formula M-1 and a second structural unit represented by Chemical Formula M-2; a photoacid generator; and a solvent, wherein the photoacid generator is a nonionic compound or an ionic compound, the nonionic compound including an organic sulfonate group, and the ionic compound including at least one selected from a conjugate base of an inorganic acid and a conjugate base of an organic sulfonic acid as an anion.

[0056]

[0057] In Chemical Formula M-1 and Chemical Formula M-2,

[0058] R 1 and R 2 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0059] 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,

[0060] 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 a substituted or unsubstituted C1 to C10 alkyl), or a combination thereof,

[0061] R 3 is hydrogen, fluorine, hydroxy, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof,

[0062] R 4 is hydrogen, or C(=O)R b ,

[0063] R b is a substituted or unsubstituted C1 to C10 alkyl group,

[0064] From R 3 , L 1 and L 2 at least one selected from among fluorine and hydroxyl groups,

[0065] R 5 is hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof,

[0066] m1 is an integer from 1 to 4, and

[0067] * is the point of attachment. As used herein, the term "fluorine" may refer to a fluorine atom.

[0068] The photoresist topcoat composition according to some embodiments includes a photoacid generator and may be coated on a photoresist layer to maximize or increase the amount of acid generated during exposure, thereby increasing the sensitivity of the photoresist.

[0069] The photoacid generator is a compound that generates an acid compound when irradiated with light. Examples of the acid generated according to embodiments of the present disclosure include hydrogen halides, sulfonic acids, antimony derivatives, and halogen peroxides.

[0070] In some embodiments, the use of a photoacid generator can increase the amount of acid generated by exposure in the exposed region of the upper portion of the photoresist layer. Thus, by increasing EUV absorption, patterning can be performed using less energy (e.g., patterning can be performed using relatively less energy), thereby improving sensitivity.

[0071] The first structural unit included in the copolymer in the composition has the characteristics of having little reactivity with the photoresist but being well soluble in the solvent, thereby protecting the photoresist while minimizing or increasing the impact on the photoresist, while the second structural unit can increase extreme ultraviolet absorption to improve sensitivity.

[0072] Therefore, the copolymer may have excellent solvent solubility, can be uniformly (eg, substantially uniformly) coated on a pattern, and minimize or reduce the effect on the resist.

[0073] As an example, the copolymer may include a first structural unit represented by Chemical Formula M-1 and a second structural unit represented by Chemical Formula M-2.

[0074] In the chemical formula M-2, if m1 is 2 or greater, each OR 4 Can be the same or different from each other.

[0075] In the chemical formula M-2, if 5-m1 is 2 or greater, each R 5 Can be the same or different from each other.

[0076] R 3 , L 1 and L 2 The meaning of at least one selected one including fluorine and hydroxyl may include the following embodiments, wherein,

[0077] R 3 may be a C1 to C20 alkyl group substituted with at least one fluorine and at least one hydroxyl group, or

[0078] From L 1 and L 2At least one of the following may be a C1 to C10 alkylene group substituted with one or more fluorine groups and one or more hydroxy groups, or

[0079] From L 1 and L 2 At least one of them may be a C1 to C10 alkylene substituted with one or more fluorine radicals, and at least one of the others may be a C1 to C10 alkylene substituted with one or more hydroxy radicals, or

[0080] R 3 Can be fluorine, and from L 1 and L 2 At least one of the following may be a C1 to C10 alkylene group substituted with one or more hydroxyl groups, or

[0081] R 3 Can be hydroxyl, and from L 1 and L 2 At least one of the following may be a C1 to C10 alkylene group substituted with one or more fluorine groups, or

[0082] R 3 It may be a C1 to C10 alkyl group substituted with one or more fluorine and one or more hydroxy groups, or

[0083] R 3 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.

[0084] As an example, the first structural unit may be represented by Chemical Formula 1.

[0085] Chemical formula 1

[0086]

[0087] In Chemical Formula 1,

[0088] R 1 is hydrogen or substituted or unsubstituted C1 to C10 alkyl,

[0089] R k 、R l 、R m 、R n and R 3 are each independently hydrogen, fluorine, hydroxy, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof,

[0090] m2 and m3 are each independently an integer from 1 to 10,

[0091] X 1is 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, and

[0092] From R k 、R l 、R m 、R n and R 3 At least one selected from includes fluorine and hydroxyl.

[0093] In Chemical Formula 1, if m2 is 2 or greater, each R k Can be the same or different from each other.

[0094] In Chemical Formula 1, if m2 is 2 or greater, each R l Can be the same or different from each other.

[0095] In Chemical Formula 1, if m3 is 2 or greater, each R m Can be the same or different from each other.

[0096] In Chemical Formula 1, if m3 is 2 or greater, each R n Can be the same or different from each other.

[0097] From R k 、R l 、R m 、R n and R 3 The meaning of at least one selected from the group consisting of fluorine and hydroxyl groups may include the following examples:

[0098] From R k 、R l 、R m 、R n and R 3 At least one selected from among each independently is fluorine and hydroxyl, or

[0099] From R k 、R l 、R m 、R n and R 3 At least one selected from 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

[0100] From R k 、R l 、R m、R n and R 3 At least one selected from each independently comprises one or more hydroxyl groups and one or more C1 to C10 alkyl groups substituted with fluorine, or

[0101] From R k 、R l 、R m 、R n and R 3 At least one selected from each independently comprises a C1 to C5 alkyl group and one or more C1 to C5 fluoroalkyl group substituted with one or more hydroxyl groups, or

[0102] From R k 、R l 、R m 、R n and R 3 At least one of the selected ones is fluorine, and at least one of the remaining ones is hydroxyl, or

[0103] From R k 、R l 、R m 、R n and R 3 At least one of the selected ones is fluorine, and at least one of the remaining ones comprises a C1 to C10 alkyl group substituted with one or more hydroxyl groups, or

[0104] From R k 、R l 、R m 、R n and R 3 At least one of the selected ones is a hydroxyl group, and at least one of the remaining ones comprises a C1 to C10 alkyl group substituted with one or more fluorine groups, or

[0105] From R k 、R l 、R m 、R n and R 3 At least one of the selected ones is a C1 to C20 alkyl group substituted by one or more fluorine groups, and at least one of the remaining ones is a C1 to C20 alkyl group substituted by one or more hydroxy groups.

[0106] For example, R 1 It can be hydrogen or methyl,

[0107] X 1 It can be a single bond (eg, a single covalent bond), -O-, or -NR a -(where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl), and

[0108] R 3It may be fluorine, hydroxy, 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 hydroxy group.

[0109] As an example, in Chemical Formula 1, from R m 、R n and R 3 At least one selected therefrom may include fluorine and hydroxyl groups.

[0110] As an example, in Chemical Formula 1, from R m and R n At least one of the selected ones 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.

[0111] As an example, in Chemical Formula 1, from R m and R n At least one selected from among may be a hydroxyl group or a C1 to C10 alkyl group substituted with at least one hydroxyl group, and R 3 It may be fluorine or a C1 to C10 alkyl group substituted with at least one fluorine.

[0112] As an example, in Chemical Formula 1, R m It can be a hydroxyl group or a C1 to C10 alkyl group substituted with at least one hydroxyl group, R n may be fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 3 The group may be a hydroxyl group, a fluorine group, or a C1 to C10 alkyl group substituted with at least one selected from the group consisting of a fluorine group and a hydroxyl group.

[0113] As an example, in Chemical Formula 1, from R m and R n At least one of the selected ones may be fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 3 The group 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.

[0114] For example, the first structural unit can be selected from Group I.

[0115] Group I

[0116]

[0117] In Group I,

[0118] R 1 Each is independently hydrogen or methyl, and * is the point of attachment.

[0119] As an example, the second structural unit may be represented by any one selected from Chemical Formula 2-1 to Chemical Formula 2-4.

[0120]

[0121] In Chemical Formula 2-1 to Chemical Formula 2-4,

[0122] R 2 is hydrogen or methyl,

[0123] R 4 、R 4a and R 4b are each independently hydrogen or C(=O)R b ,

[0124] R b is a substituted or unsubstituted C1 to C5 alkyl group,

[0125] R 5a 、R 5b 、R 5c and R 5d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, and

[0126] * indicates the connection point.

[0127] As an example, at least one R 5 It may be a halogen.

[0128] As an example, at least one R 5 It may be an iodine group.

[0129] If the second building block includes an iodine group, the sensitivity may be further improved.

[0130] For example, the second structural unit may be selected from Group II.

[0131] Group II

[0132]

[0133] In Group II,

[0134] R 2 Each is independently hydrogen or methyl, and * is the point of attachment.

[0135] The copolymer may include about 50 mol % to about 99 mol % of the first structural unit, about 1 mol % to about 50 mol % of the second structural unit, and about 1 mol % to about 40 mol % of the third structural unit (e.g., based on 100 mol % of the copolymer).

[0136] For example, the copolymer can include about 70 mol% to about 99 mol% of the first structural unit, about 1 mol% to about 30 mol% of the second structural unit, most specifically about 80 mol% to about 95 mol% of the first structural unit, and about 5 mol% to about 20 mol% of the second structural unit.

[0137] If the molar ratio of each structural unit included in the copolymer is within the above range, solubility in an organic solvent may be improved, and a pattern may be uniformly (eg, substantially uniformly) coated.

[0138] The copolymer may have a weight average molecular weight (Mw) of about 1,000 g / mol to about 50,000 g / mol. For example, it may have a weight average molecular weight of about 2,000 g / mol to about 30,000 g / mol, for example, about 3,000 g / mol to about 20,000 g / mol, or for example, 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 and solubility in a solvent of a resist topcoat composition comprising the copolymer may be optimized or improved.

[0139] The copolymer may be present in an amount of about 0.1 wt % to about 10 wt % based on the total weight of the resist topcoat composition. Within this range, the resist topcoat composition may be easily removed.

[0140] In some embodiments, the copolymer may be selected from those listed in Group III.

[0141] Group III

[0142]

[0143] In Group III, x:y may be from about 99:1 to about 90:10, such as about 90:10, about 91:9, about 95:5, or about 96:4.

[0144] The photoacid generator according to some embodiments may be a non-ionic compound, and the non-ionic compound may be represented by any one selected from Chemical Formula 3 to Chemical Formula 6.

[0145]

[0146] In Chemical Formulas 3 to 6,

[0147] R 6 to R 15each independently represents halogen, hydroxyl, ester, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heterocyclyl, or a combination thereof,

[0148] L 3 To L 8 are each independently a single bond (e.g., a single covalent bond), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, or a combination thereof,

[0149] Q is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C2 to C10 alkenylene group,

[0150] A is a cyclic organic group, and

[0151] n1 is an integer of 0 or 1.

[0152] The cyclic organic group may be a monocyclic compound or a polycyclic compound.

[0153] Examples of the monocyclic compound may include a cycloalkyl group, a cycloalkenyl group, and the like, and examples thereof may be a substituted or unsubstituted C1 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 cycloalkenyl group, and the like.

[0154] Further examples of monocyclic compounds may be substituted or unsubstituted C1 to C10 cycloalkyl groups, or substituted or unsubstituted C2 to C10 cycloalkenyl groups, such as substituted or unsubstituted cyclopentyl groups, substituted or unsubstituted cyclohexyl groups, substituted or unsubstituted cycloheptyl groups, substituted or unsubstituted cyclooctyl groups, and the like.

[0155] An example of the polycyclic compound may be a bicyclic compound.

[0156] Bicyclic compounds can include fused bicyclic compounds (e.g., structures in which only two atoms are shared between the rings, such as decalin), bridged bicyclic compounds (e.g., structures in which two atoms are shared between the rings and are bridged by additional atoms, such as bicyclo[3,2,1]octane), or spirocyclic compounds (e.g., structures in which one carbon atom is shared without a bridge).

[0157] As an example, A can be a substituted or unsubstituted cyclopentyl, a substituted or unsubstituted cyclohexyl, a substituted or unsubstituted cycloheptyl, a substituted or unsubstituted cyclooctyl, a substituted or unsubstituted norbornene, a substituted or unsubstituted norbornene, a substituted or unsubstituted tricyclodecane, a substituted or unsubstituted tetracyclodecane, a substituted or unsubstituted tetracyclododecane, a substituted or unsubstituted adamantane, a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted anthracene, a substituted or unsubstituted furan, a substituted or unsubstituted thiophene, a substituted or unsubstituted benzothiophene, a substituted or unsubstituted dibenzofuran, a substituted or unsubstituted dibenzothiophene, or a substituted or unsubstituted pyridine.

[0158] As an example, A can be a substituted or unsubstituted cyclopentyl, a substituted or unsubstituted cyclohexyl, a substituted or unsubstituted norbornene, a substituted or unsubstituted norbornene, a substituted or unsubstituted benzene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted phenanthrene, or a substituted or unsubstituted anthracene.

[0159] As an example, R 6 to R 15 Each of them may independently be a halogen, a hydroxyl group, an ester group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof.

[0160] As an example, R 6 、R 7 、R 9 and R 10 may each independently be halogen, hydroxyl, ester, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, or substituted or unsubstituted hexyl,

[0161] R 8 and R 11 to R 15and each independently may be halogen, hydroxyl, an ester group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted pyridyl group.

[0162] The nonionic compound may be at least one selected from the compounds listed in Group IV.

[0163] Group IV

[0164]

[0165] According to some embodiments, the photoacid generator may be an ionic compound, and the ionic compound may be represented by Chemical Formula 7 or Chemical Formula 8.

[0166]

[0167] In Chemical Formula 7 and Chemical Formula 8,

[0168] M 1 is F, Cl, Br or I,

[0169] M 2 is O, S, Se or Te,

[0170] R 16 to R 20 are each independently halogen, hydroxyl, ester, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0171] Z - It is an anion derived from the conjugate base of an inorganic acid and / or the conjugate base of an organic sulfonic acid.

[0172] As an example, M 1 It can be 1.

[0173] As an example, M 2 It can be S.

[0174] As an example, R 16 to R 20 Each independently may be a substituted or unsubstituted C6 to C20 aryl group.

[0175] For example, the ionic compound represented by Chemical Formula 7 may be represented by Chemical Formula 7-1, and the ionic compound represented by Chemical Formula 8 may be represented by Chemical Formula 8-1.

[0176] Chemical Formula 7-1

[0177]

[0178] Chemical formula 8-1

[0179]

[0180] In Chemical Formula 7-1 and Chemical Formula 8-1,

[0181] R 26 to R 50 are each independently hydrogen, halogen, hydroxyl, ester, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

[0182] Z - It is an anion derived from the conjugate base of an inorganic acid and / or the conjugate base of an organic sulfonic acid.

[0183] As an example, Z - Can choose from PF6 - 、BF4 - 、SbF6 - and organic sulfonic acid anions.

[0184] The organic sulfonic acid anions may include aliphatic sulfonic acid anions and aromatic sulfonic acid anions.

[0185] In the aliphatic sulfonic acid anion, the aliphatic group may be selected from a substituted or unsubstituted C1 to C30 straight chain or branched alkyl group and a substituted or unsubstituted C3 to C30 cycloalkyl group.

[0186] The substituted or unsubstituted C1 to C30 straight-chain or branched alkyl group and the substituted or unsubstituted C3 to C30 cycloalkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted norbornyl, substituted or unsubstituted norbornenyl, substituted or unsubstituted adamantyl, and / or the like.

[0187] In the aromatic sulfonic acid anion, the aromatic group may be a substituted or unsubstituted C6 to C20 aryl group.

[0188] The substituted or unsubstituted C6-C20 aryl group may be, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted tolyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group.

[0189] As an example, the sulfonic acid anion can be represented by Chemical Formula 9.

[0190] Chemical formula 9

[0191]

[0192] In Chemical Formula 9,

[0193] R 21 is hydrogen, fluorine, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a cyclic organic group, or a combination thereof,

[0194] L 9 is a single bond (e.g., a single covalent bond), O, S, OC(═O), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof,

[0195] R 22 to R 25 are each independently hydrogen, fluorine, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and

[0196] n2 is one of integers from 0 to 10.

[0197] As an example, from R 22 to R25 At least one selected therefrom may be fluorine or a C1 to C10 alkyl group substituted with one or more fluorine groups.

[0198] For example, from R 22 to R 25 At least one selected therefrom may be fluorine or a C1 to C5 alkyl group substituted with one or more fluorine groups.

[0199] For example, the C1 to C5 alkyl group substituted with one or more fluoro groups may include CF3, C2F5, C3F7, C4F9, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9 and / or CH2CH2C4F9.

[0200] The ionic compound may be at least one selected from the compounds listed in Group V.

[0201] Group V

[0202]

[0203] The content of the photoacid generator can be about 0.1 parts by weight to about 40 parts by weight, such as about 0.1 parts by weight to about 30 parts by weight, such as about 0.5 parts by weight to about 30 parts by weight, based on 100 parts by weight of the copolymer. Within the above range, solubility can be optimized or improved, and the pattern LWR improvement effect can be ensured.

[0204] In an embodiment, the resist top coating composition may further include at least one other polymer selected from epoxy-based resins, phenolic resins, glyoxal-urea-based resins, and melamine-based resins, but is not limited thereto.

[0205] The resist topcoat composition may further include an additive comprising a surfactant, a thermal acid generator, a plasticizer, or a combination thereof.

[0206] The surfactant may be, for example, alkylbenzenesulfonate, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt and / or the like, but is not limited thereto.

[0207] The thermal acid generator may be, for example, an acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine p-toluenesulfonic 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.

[0208] The amounts of these additives used can be easily adjusted according to the appropriate or desired physical properties, or these additives can be omitted.

[0209] The solvent may be an ether solvent, for example, which may be represented by Chemical Formula 10.

[0210] Chemical formula 10

[0211]

[0212] In Chemical Formula 10,

[0213] R 51 and R 52 Each is independently a substituted or unsubstituted C3 to C20 alkyl group.

[0214] For example, the ether solvent can be selected from diisopropyl ether, dipropyl ether, diisoamyl ether, dipentyl ether, dibutyl ether, diisobutyl ether, disec-butyl ether, dihexyl ether, bis(2-ethylhexyl) ether, didecyl ether, heneicosyl ether, docosyl ether, tetracosyl 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.

[0215] Ether solvents may have suitable or sufficient solubility and / or dispersibility for the above composition.

[0216] According to some example embodiments, a method of forming a pattern using the above-described photoresist top coating composition may be provided. For example, the fabricated pattern may be a photoresist pattern.

[0217] According to some example embodiments, a method of forming a pattern includes coating and heating a photoresist composition on a substrate to form a photoresist layer, coating and heating the above-described photoresist topcoat composition on the photoresist layer to form a topcoat layer, and exposing and developing the topcoat layer and the photoresist layer to form a resist pattern.

[0218] Hereinafter, a method for forming a pattern using the above-mentioned photoresist top coating composition will be described with reference to the accompanying drawings. The accompanying drawings are schematic diagrams illustrating a method for forming a pattern using the photoresist top coating composition according to an embodiment of the present disclosure.

[0219] Reference Figure 1First, a target 100 to be etched is prepared. An example of the target to be etched may be a thin film on a semiconductor substrate. The following describes only embodiments in which the target to be etched is a thin film, but the present disclosure is not limited thereto. The surface of the thin film is cleaned to remove contaminants remaining on the film. The thin film may be, for example, a silicon nitride film, a polysilicon film, and / or a silicon oxide film.

[0220] A photoresist composition is coated on the thin film and heated to form a photoresist layer 101 (Action 1). Subsequently, a photoresist topcoat composition is coated on the photoresist layer and heated to form a photoresist topcoat layer 30 (Action 2).

[0221] The heating may be performed at a temperature of about 80°C to about 500°C.

[0222] The photoresist topcoat and photoresist layer are then exposed to high energy radiation.

[0223] For example, high-energy radiation that may be used in the exposure process may include light having a high-energy wavelength, such as extreme ultraviolet light (EUV; wavelength: 13.5 nm) and / or an electron beam (E-Beam).

[0224] A post-exposure heat treatment (PEB) is then performed. The PEB can be performed at a temperature of about 80°C to about 200°C. By performing the PEB, exposed regions of the photoresist layer, e.g., regions not covered by the patterned mask, are modified to be soluble in a developer solution, such that the exposed regions have a different solubility than unexposed regions of the photoresist layer.

[0225] The photoresist layer and the photoresist topcoat layer corresponding to the exposed area are dissolved and removed using a developing solution, thereby forming a photoresist pattern 102 b (Act 3 ).

[0226] In an embodiment, the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter referred to as an organic developer).

[0227] As the alkaline developer, a quaternary ammonium salt such as tetramethylammonium hydroxide can be used, but an aqueous alkaline solution of an inorganic base, a primary to tertiary amine, an alcoholamine, and / or a cyclic amine can also be used.

[0228] In an embodiment, the alkaline developer may contain an appropriate amount of alcohol and / or surfactant. The alkaline developer may have an alkali concentration of, for example, about 0.1% by mass to about 20% by mass, and a pH of, for example, about 10 to about 15.

[0229] The organic developer may be a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0230] Examples of ketone solvents 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, acetylacetonol, ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

[0231] Examples of ester solvents may include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate, 3-ethoxypropionic acid ethyl ester, 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 the like.

[0232] Any appropriate solvent commonly used in the art (such as alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents) may be used.

[0233] The above-mentioned multiple solvents can be mixed together, or can be mixed with solvents other than the above-mentioned solvents or water. The water content of the developer as a whole can be suitably or ideally less than about 50% by weight, less than about 20% by weight, less than about 10% by weight, or, for example, the developer can be substantially free of water.

[0234] The content of the organic solvent may suitably or desirably be about 50 wt % to about 100 wt %, about 80 wt % to about 100 wt %, about 90 wt % to about 100 wt %, or, for example, about 95 wt % to about 100 wt %, based on the total amount of the organic developer.

[0235] The organic developer may include any suitable surfactant commonly used in the art in an appropriate or suitable amount as needed or desired.

[0236] 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, for example, about 0.01 wt % to about 0.5 wt %, based on the total amount of the developer.

[0237] The organic developer may include any suitable inhibitor commonly used in the art.

[0238] Then, the exposed thin film is etched using the photoresist pattern as an etching mask. As a result, the thin film is formed into a thin film pattern.

[0239] The thin film may be etched by dry etching using an etching gas, for example, the etching gas may be CHF 3 , CF 4 , Cl 2 , BCl 3 and / or a mixture thereof.

[0240] In the exposure process performed above, the thin film pattern formed using the photoresist pattern formed by the exposure process performed using the EUV light source may have a width corresponding to the photoresist pattern. For example, the photoresist pattern may have a width of about 5 nanometers to about 100 nanometers. For example, the thin film pattern formed by the exposure process performed using the EUV light source may 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, about 5 nanometers to about 20 nanometers, or may be formed to have a width of less than or equal to about 20 nanometers, like the photoresist pattern.

[0241] Hereinafter, embodiments of the present disclosure will be described in more detail through examples related to the synthesis of the above polymer and the preparation of a photoresist topcoat composition including the polymer. However, the present disclosure is not technically limited to the following examples.

[0242] Synthetic Example

[0243] Synthesis Example 1: Synthesis of Compound 1a

[0244] Under a nitrogen atmosphere, 20 g (59.86 mmol) of hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol (perfluoropinacol), 7.79 g (59.86 mmol) of 2-(hydroxyethyl) methacrylate, and 18.84 g (71.84 mmol) of triphenylphosphine (PH3P) were mixed in 110 ml of diethyl ether and stirred. After stirring for 30 minutes, the resulting mixture was cooled to 0°C, and then a mixture consisting of 14.52 g (71.84 mmol) of diisopropyl azodicarboxylate (DIAD) and 35 ml of diethyl ether was slowly added over 2 hours. The resulting mixture was then stirred at room temperature (23°C) for 24 hours and then concentrated. The concentrated mixture was dissolved in dichloromethane and then subjected to column chromatography using silica gel to separate the synthesized material. The separated material was distilled under reduced pressure to obtain 2-[3,3,3-trifluoro-2-hydroxy-1,1,2-tris(trifluoromethyl)propoxy]ethyl 2-methyl-2-acrylate represented by Chemical Formula 1a.

[0245] * 1 H-NMR (acetone-d6): δ 1.90 (3H, t), 4.36 (4H, m), 5.63 (1H, t), 6.09 (1H, t), 8.34 (1H, s)

[0246] * 19 F-NMR (acetone-d6): δ-70.12 (6F, m), -65.38 (6F, m)

[0247] Chemical formula 1a

[0248]

[0249] Synthesis Example 2: Preparation of Copolymer R1

[0250] In a 250 ml two-necked round-bottom flask, a compound represented by Chemical Formula 1a (16.1 g, 36 mmol), a compound represented by Chemical Formula 1b (DIVPA, Songwon) (1.7 g, 4 mmol) and 110 g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere and then heated to 100° C. When the internal temperature reached 85° C., 14.7 g of a 25 wt % V-601 / DIAE solution (V-601, 3.7 g, 16 mmol) was slowly added. After 6 hours, the resulting reaction solution was cooled to room temperature and then concentrated to a solid content of 50%. 270 g of heptane was added to the concentrated solution and the resulting polymer was filtered. The filtered polymer was completely dissolved in 34 g of DIAE, and then 270 g of heptane was added for precipitation. This was repeated twice to obtain a precipitate, which was then completely dried to prepare the final copolymer R1 (Mw=4,000).

[0251] Chemical formula 1b

[0252]

[0253]

[0254] Synthesis Example 3: Preparation of Copolymer R2

[0255] The preparation method of copolymer R2 (Mw=9,000) was basically the same as that of Synthesis Example 2, except that the compound represented by Chemical Formula 2b (1.5 g, 16 mmol) (2,4-diiodo-6-vinylphenol, AccelaChembio Inc.) was used instead of the compound represented by Chemical Formula 1b.

[0256] Chemical formula 2b

[0257]

[0258] Synthesis Example 4: Preparation of Copolymer R3

[0259] The preparation method of copolymer R3 (Mw=5,000) was substantially the same as that of Synthesis Example 2, except that the compound represented by Chemical Formula 2a (10.6 g, 36 mmol) was used instead of the compound represented by Chemical Formula 1b.

[0260] Chemical formula 2a

[0261]

[0262] Synthesis Example 5: Preparation of Copolymer R4

[0263] The preparation method of copolymer R4 (Mw = 6,000) is basically the same as that of Synthesis Example 2, except that the compound represented by Chemical Formula 2a (16.1 g, 36 mmol) is used instead of the compound represented by Chemical Formula 1a, and the compound represented by Chemical Formula 2b (1.5 g, 4 mmol) is used instead of the compound represented by Chemical Formula 1b.

[0264]

[0265] Synthesis Example 6: Preparation of Copolymer R5

[0266] Copolymer R5 (Mw=5,000) was prepared in substantially the same manner as in Synthesis Example 2, except that the compound represented by Chemical Formula 3a (10.1 g, 36 mmol) (MA-TTBD, HALOCARBON) was used instead of the compound represented by Chemical Formula 1a.

[0267] Chemical formula 3a

[0268]

[0269] Synthesis Example 7: Preparation of Copolymer R6

[0270] The preparation method of copolymer R6 (Mw=5,000) is basically the same as that of Synthesis Example 2, except that the compound represented by Chemical Formula 3a (10.1 g, 36 mmol) is used instead of the compound represented by Chemical Formula 1a, and the compound represented by Chemical Formula 2b (1.5 g, 4 mmol) is used instead of the compound represented by Chemical Formula 1b.

[0271]

[0272] Synthesis Example 8: Preparation of Copolymer R7

[0273] The preparation method of copolymer R7 (Mw=5,000) was substantially the same as that of Synthesis Example 2, except that the compound represented by Formula 1b was not used.

[0274]

[0275] Preparation of photoresist topcoat composition

[0276] Example 1

[0277] 0.98 g (0.5 wt %) of the copolymer R1 in Synthesis Example 2 and 1.47 mg (0.15 wt %) of the photoacid generator represented by P1 were dissolved in 199 g of a DIAE / PGME mixed solvent (w / w=97 / 3), and then stirred at room temperature (23° C.) for 24 hours and filtered through a polytetrafluoroethylene (TEFLON) filter having a pore size of 0.45 μm to prepare a resist top coating composition.

[0278]

[0279] Examples 2 to 34

[0280] Each resist topcoat composition was prepared in substantially the same manner as in Example 1, except that the type of copolymer and the type of photoacid generator were changed as shown in Table 1.

[0281] P2:

[0282] P3:

[0283] P4:

[0284] P5:

[0285] P6:

[0286] P7:

[0287] P8:

[0288] Comparative Example 1

[0289] A resist topcoat composition was prepared in substantially the same manner as in Example 1, except that no photoacid generator was used.

[0290] Comparative Example 2

[0291] A resist topcoat composition was prepared in substantially the same manner as in Example 1, except that the copolymer R7 of Synthesis Example 8 was used instead of the copolymer R1.

[0292] Evaluation 1: Solubility evaluation

[0293] Each of the compositions according to Examples 1 to 34 and Comparative Examples 1 and 2 was stirred for 24 hours and inspected for the presence or absence of precipitates with the naked eye (without magnification). The results are shown in Table 1.

[0294] (No precipitation - solubility ○, Precipitation - solubility ×)

[0295] Evaluation 2: Development evaluation

[0296] Each of the photoresist topcoat compositions prepared in the Examples and Comparative Examples was spin-coated onto a silicon substrate and heat-treated on a hot plate at 110°C for 1 minute to form a photoresist topcoat layer approximately 5 nm thick. The substrate with the topcoat layer formed was rinsed with a 2.38% aqueous solution of tetramethylammonium hydroxide and heat-treated again on a hot plate at 110°C for 1 minute. The change in topcoat layer thickness was then measured, and the results are shown in Table 1.

[0297] *Residual film after development (%) = [Top coating thickness before development (nm) - Top coating thickness after development (nm)] × 100 / Top coating thickness before development (nm)

[0298] (Residual film after development ≤ 20% - developability ○, top coating thickness after development > 20% - developability ×)

[0299] Evaluation 3: Sensitivity evaluation

[0300] A resist bottom layer (thickness: ) and photoresist films for EUV (thickness: ), each of the photoresist top coating compositions of Examples and Comparative Examples was spin-coated and then heat-treated on a hot plate at 110° C. for 1 minute to form a top coating layer for photoresist having a thickness of about 5 nm.

[0301] Using the NXE3400B EUV system, line and space patterns were formed in a focus-energy matrix (FEM) format on a wafer forming a topcoat layer for photoresist. Using interpolation, the sensitivity capable of forming a critical dimension (CD) of 26.0 nm was confirmed. The results are shown in Table 1.

[0302] Table 1

[0303]

[0304] Referring to Table 1, if the resist top coating composition according to the example embodiment is applied, it is confirmed that not only the solubility and developability are excellent, but also the sensitivity is excellent since the generation of acid is promoted in the exposed area.

[0305] In contrast, the resist top coating composition according to the comparative example did not show improved sensitivity or showed deteriorated sensitivity.

[0306] While certain embodiments have been described and illustrated herein, it should be apparent to those skilled in the art that the present disclosure is not limited to the described embodiments and that various modifications and conversions may be made without departing from the spirit and scope of the present disclosure. Therefore, such modified or converted embodiments should not be understood separately from the technical ideas and aspects of the present disclosure, and such modified embodiments are within the scope of the appended claims and their equivalents.

Claims

1. A resist top coating composition comprising: A copolymer comprising a first structural unit represented by Chemical Formula M-1 and a second structural unit represented by Chemical Formula M-2; Photoacid generators; as well as solvents, wherein the photoacid generator is a nonionic compound or an ionic compound, The nonionic compound includes an organic sulfonate group, and The ionic compound includes at least one selected from the group consisting of a conjugate base of an inorganic acid and a conjugate base of an organic sulfonic acid as an anion: In Chemical Formula M-1 and Chemical Formula M-2, R 1 and R 2 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, 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 For single bonds, -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 a substituted or unsubstituted C1 to C10 alkyl group, R 3 is hydrogen, fluorine, hydroxy, substituted or unsubstituted C1 to C20 alkyl, or a combination thereof, R 4 is hydrogen, or C(=O)R b , R b is a substituted or unsubstituted C1 to C10 alkyl group, Selected from R 3 , L 1 and L 2 at least one of which includes fluorine and hydroxyl groups, R 5 is hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, m1 is an integer from 1 to 4, and * indicates the connection point.

2. The resist topcoat composition according to claim 1, wherein: The first structural unit is represented by Chemical Formula 1: Chemical formula 1 Wherein, in Chemical Formula 1, R 1 is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group, R k 、R l 、R m 、R n and R 3 are each independently hydrogen, fluorine, hydroxy, 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 For single bonds, -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 a substituted or unsubstituted C1 to C10 alkyl group, and Selected from R k 、R l 、R m 、R n and R 3 At least one of includes fluorine and hydroxyl.

3. The resist topcoat composition according to claim 1, wherein: The first structural unit is at least 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 resist topcoat 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: Among them, in Chemical Formula 2-1 to Chemical Formula 2-4, R 2 is hydrogen or methyl, R 4 、R 4a and R 4b are each independently hydrogen, or C(=O)R b , R b is a substituted or unsubstituted C1 to C5 alkyl group, R 5a 、R 5b 、R 5c and R 5d are each independently hydrogen, halogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl, or a combination thereof, and * indicates the connection point.

5. The resist topcoat composition according to claim 4, wherein: Selected from R 5a 、R 5b 、R 5c and R 5d At least one of them is an iodine group.

6. The resist topcoat composition according to claim 1, wherein: The second structural unit is at least one selected from Group II: Group II Among them, in Group II, R 2 Each is independently hydrogen or methyl, and * is the point of attachment.

7. The resist topcoat composition according to claim 1, wherein: The copolymer includes 50 mol % to 99 mol % of the first structural unit and 1 mol % to 50 mol % of the second structural unit.

8. The resist topcoat composition according to claim 1, wherein: The copolymer has a weight average molecular weight of 1,000 to 50,000 g / mol.

9. The resist topcoat composition according to claim 1, wherein: The nonionic compound is represented by any one selected from Chemical Formula 3 to Chemical Formula 6: Among them, in Chemical Formula 3 to Chemical Formula 6, R 6 to R 15 each independently represents halogen, hydroxyl, ester, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heterocyclyl, or a combination thereof, L 3 To L 8 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, or a combination thereof, Q is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C2 to C10 alkenylene group, A is a cyclic organic group, and n1 is an integer of 0 or 1.

10. The resist topcoat composition according to claim 9, wherein: A is substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted norbornene, substituted or unsubstituted norbornene, substituted or unsubstituted tricyclodecane, substituted or unsubstituted tetracyclodecane, substituted or unsubstituted tetracyclododecane, substituted or unsubstituted adamantane, substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted phenanthrene, substituted or unsubstituted anthracene, substituted or unsubstituted furan, substituted or unsubstituted thiophene, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted pyridine.

11. The resist topcoat composition according to claim 9, wherein: R 6 、R 7 、R 9 and R 10 are each independently halogen, hydroxyl, ester, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, or substituted or unsubstituted hexyl, and R 8 、R 11 to R 15 and each is independently halogen, hydroxy, an ester group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted hexyl group, a substituted or unsubstituted substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted cycloheptyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, or a substituted or unsubstituted pyridyl group.

12. The resist topcoat composition according to claim 1, wherein: The nonionic compound is at least one compound selected from group IV: Group IV 13. The resist topcoat composition according to claim 1, wherein: The ionic compound is represented by Chemical Formula 7 or Chemical Formula 8: In Chemical Formula 7 and Chemical Formula 8, M 1 is F, Cl, Br or I, M 2 is O, S, Se or Te, R 16 to R 20 are each independently halogen, hydroxyl, ester, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 aliphatic unsaturated organic groups including one or more double or triple bonds, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and Z - It is an anion derived from the conjugate base of an inorganic acid or the conjugate base of an organic sulfonic acid.

14. The resist topcoat composition according to claim 13, wherein: The ionic compound is represented by Chemical Formula 7-1 or Chemical Formula 8-1: Chemical Formula 7-1 Chemical formula 8-1 In Chemical Formula 7-1 and Chemical Formula 8-1, R 26 to R 50 are each independently hydrogen, halogen, hydroxyl, ester, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and Z - It is an anion derived from the conjugate base of an inorganic acid or the conjugate base of an organic sulfonic acid.

15. The resist topcoat composition according to claim 13, wherein: Z - Select from PF6 - 、BF4 - 、SbF6 - and organic sulfonic acid anions.

16. The resist topcoat composition according to claim 15, wherein: The organic sulfonic acid anion is represented by Chemical Formula 9: Chemical formula 9 In Chemical Formula 9, R 21 is hydrogen, fluorine, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a cyclic organic group, or a combination thereof, L 9 is a single bond, O, S, OC(═O), a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a combination thereof, R 22 to R 23 are each independently hydrogen, fluorine, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 aliphatic unsaturated organic group including one or more double or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and n2 is an integer from 0 to 10.

17. The resist topcoat composition according to claim 1, wherein: The ionic compound is at least one compound selected from group V: Group V 18. The resist topcoat composition according to claim 1, wherein: The photoacid generator is present in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer.

19. The resist topcoat composition according to claim 1, wherein: The solvent is an ether solvent.

20. 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 claim 1 on the photoresist layer to form a top coating layer, and The topcoat layer and the photoresist layer are exposed and developed to form a resist pattern.

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