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 same 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. Details about the chemical formula are described in the specification.

Description

[0001] Citations of Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0075624 filed in the Korean Intellectual Property Office on June 13, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a resist topcoat composition and a method for forming (or providing) a pattern using the resist topcoat composition. Background Art

[0004] Recently, the semiconductor industry has developed ultra-micro technology to produce patterns of several nanometers to tens of nanometers (eg, nanoscale patterns). Such ultra-micro technology relies on (essentially requires) an effective photolithography process.

[0005] The photolithography process of the related art involves forming (or providing) a material layer on a semiconductor substrate, coating a photoresist (photoresist) film thereon, exposing and developing the photoresist film to form (or provide) 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 materials and techniques for solving various problems arising in the process are desired or required.

[0007] For example, if extreme ultraviolet light (EUV) is irradiated onto the photoresist (on) (for example, when extreme ultraviolet light (EUV) is irradiated onto the photoresist (on)), due to the high energy of each photon, there may be a region in which a large amount of light or a small amount of light is randomly or undesirably irradiated, which is photo shot noise, or there may be a difference in EUV absorption between the top and bottom of the photoresist, which may cause pattern distribution degradation, such as an increase in roughness (LER: line edge roughness, LWR: line width roughness) and / or uniformity (IPU (in-point uniformity)) of the pattern. In order to improve or reduce such pattern distribution degradation, technical development is desired or required. Summary of the invention

[0008] One aspect according to one or more embodiments is directed to a resist top coating composition capable of reducing pattern distribution (eg, variation) by preventing or reducing pattern degradation.

[0009] One aspect according to one or more embodiments relates to a method of forming (or providing) a pattern using a resist top coating composition.

[0010] According to some embodiments, the resist top coating 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.

[0011]

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

[0013] R 1 and R 2 may each independently be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0014] L 1 and L 2 may each independently be a single bond, a substituted or unsubstituted C1 to C10 alkylene group and / or (eg, any suitable) combination thereof,

[0015] X 1 Can be a single bond; -O-; -S-; -S(O)-; -S(O)2-; -C(O)-; -C(=O)O-; -OC(=O)-; -OC(=O)O-; -NR a -, where R a may be hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group; and / or (e.g., any suitable) combination thereof,

[0016] R 5 may be hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl and / or (e.g., any suitable) combination thereof,

[0017] R 6 It can be hydrogen or C(=O)R b ,

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

[0019] R 5 , L 1 or L 2 at least one of which may include fluorine and hydroxyl groups,

[0020] R 7 may be hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, and / or (e.g., any suitable) combination thereof, and

[0021] m1 may be an integer selected from 1 to 4,

[0022]

[0023]

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

[0025] R 3 may be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0026] L 3 and L 4 may each independently be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, and / or (eg, any suitable) combination thereof,

[0027] R 8 To R 11 may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof,

[0028] n1 may be an integer selected from 1 to 6, and

[0029] *Can be a connection point.

[0030] In some embodiments, the first structural unit may be represented by Chemical Formula 1.

[0031] Chemical formula 1

[0032]

[0033] In Chemical Formula 1,

[0034] R 1 may be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0035] R k , R l , R m , R n and R 5 may each independently be hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl and / or (eg, any suitable) combination thereof,

[0036] m2 and m3 may each independently be an integer selected from 1 to 10,

[0037] X 1 Can be a single bond; -O-; -S-; -S(O)-; -S(O)2-; -C(O)-; -C(=O)O-; -OC(=O)-; -OC(=O)O-; -NR a -, where R a may be hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group; and / or (e.g., any suitable) combination thereof, and

[0038] R k , R l , R m , R n or R 5 At least one of may contain fluorine and hydroxyl groups.

[0039] In some embodiments, R in Chemical Formula 1 m , R n or R 5 At least one of may contain a fluorine group and a hydroxyl group.

[0040] In some embodiments, R in Chemical Formula 1 m or R n 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.

[0041] In some embodiments, R in Chemical Formula 1 m or R n 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.

[0042] In some embodiments, R in Chemical Formula 1 m It may 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 5 It may be hydroxy, fluorine, or a C1 to C10 alkyl group substituted with one or more fluorine groups or one or more hydroxyl groups.

[0043] In some embodiments, R in Chemical Formula 1 m or R n 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 hydroxyl group or a C1 to C5 alkyl group substituted with at least one of one or more hydroxyl groups or one or more C1 to C5 fluoroalkyl groups. 5It may be a C1 to C5 alkyl group substituted by one or more hydroxyl groups and / or substituted by one or more C1 to C5 fluoroalkyl groups.

[0044] In some embodiments, the first structural unit may be any one (eg, one) of the structures selected from Group I.

[0045] Group I

[0046]

[0047] In Group I, R 1 may each independently be hydrogen or methyl, and * may be a point of attachment.

[0048] In some embodiments, the second structural unit may be represented by any one (eg, one) selected from Chemical Formula 2-1 to Chemical Formula 2-4.

[0049]

[0050] In Chemical Formula 2-1 to Chemical Formula 2-4,

[0051] R 2 can be hydrogen or methyl,

[0052] R 6 , R 6a and R 6b may each independently be hydrogen or C(=O)R b ,

[0053] R b may be a substituted or unsubstituted C1 to C5 alkyl group,

[0054] R 7 may each independently be hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C10 alkyl and / or (e.g., any suitable) combination thereof, and

[0055] *Can be a connection point.

[0056] In some embodiments, R 7 At least one of may be a halogen.

[0057] In some embodiments, R 7 At least one of the may be an iodine group.

[0058] The second structural unit may be any one (eg, one) selected from the structures of Group II.

[0059] Group II

[0060]

[0061] In Group II, R 2 may each independently be hydrogen or methyl, and * may be a point of attachment.

[0062] In some embodiments, L 3 and L 4 may each independently be a single bond, a substituted or unsubstituted C1 to C5 alkylene group, or a substituted or unsubstituted C6 to C12 arylene group, and

[0063] R 8 To R 15 Each may independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0064] In some embodiments, the third structural unit may be any one (eg, one) selected from the structures of Group III.

[0065] Group III

[0066]

[0067] In Group III,

[0068] R 3 can be hydrogen or methyl, and * can be the point of attachment.

[0069] In some embodiments, the copolymer according to some embodiments 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 5 mol % to about 50 mol % of the third structural unit, based on a total of 100 mol % of the copolymer.

[0070] In some embodiments, the copolymer may have a weight average molecular weight of about 1,000 g / mol to about 50,000 g / mol.

[0071] In some embodiments, the copolymer according to some embodiments may be included in an amount of 0.1 wt % to 10 wt % based on the total weight of the resist top coating composition.

[0072] In some embodiments, the copolymer may be any one (eg, one) selected from those listed in Group IV or may include at least one (eg, one or more) selected from those listed in Group IV.

[0073] Group IV

[0074]

[0075] In Group IV, x:y:z can be 60:10:30, 60:20:20, 66:10:24, 69:12:19, 70:10:20, 70:20:10, or 80:10:10.

[0076] In some embodiments, the solvent may be an ether solvent represented by Chemical Formula 4.

[0077] Chemical formula 4

[0078]

[0079] In chemical formula 4,

[0080] R 12 and R 13 Each may independently be a substituted or unsubstituted C3 to C20 alkyl group.

[0081] In some embodiments, the ether solvent may be any one (e.g., one) selected from the following or may include at least one (e.g., one or more) selected from the following: diisopropyl ether, dipropyl ether, diisoamyl ether, diamyl ether, dibutyl ether, diisobutyl ether, di-sec-butyl ether, dihexyl ether, bis(2-ethylhexyl) ether, didecyl ether, diundecyl ether, didodecyl ether, ditetradecyl ether, hexadecyl ether, butyl methyl ether, butyl The invention may be any one of the following: the invention may be any one of the following: cyclopentyl 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 / or (e.g., any suitable) combinations thereof.

[0082] According to some embodiments, the method of forming (or providing) a pattern includes: coating and heating a photoresist composition on a substrate to form (or provide) a photoresist film; coating and heating the above-mentioned resist top coating composition on the photoresist film to form (or provide) a top coating layer; and exposing and developing the top coating layer and the photoresist film to form (or provide) a resist pattern.

[0083] The resist top coating composition according to some embodiments can remove excess activated acid from the top of the photoresist if exposed to EUV (for example, when exposed to EUV) to prevent or reduce pattern distribution degradation, such as roughness (LER, LWR) or IPU of the pattern due to EUV absorption difference between the top and bottom of the photoresist layer, and thereby improve pattern distribution and also significantly improve the IPU of the columnar pattern, desirably contributing to forming (or providing) a fine pattern of the photoresist. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] The above and other aspects, features and enhancements of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0085] Figure 1 is a schematic diagram for explaining a method of forming (or providing) a pattern using a resist top coating composition according to some embodiments.

[0086] Description of Reference Numerals

[0087] 1: Forming (or providing) a photoresist film

[0088] 2: Form (or provide) a photoresist top coating

[0089] 3: Expose and develop the photoresist film and photoresist topcoat to form (or provide) a resist pattern

[0090] 30: Photoresist top coating

[0091] 100: Substrate

[0092] 101: Photoresist film

[0093] 102b: Photoresist pattern DETAILED DESCRIPTION

[0094] Exemplary embodiments of the present disclosure will be described in more detail below, and those skilled in the art can easily perform the exemplary embodiments of the present disclosure. However, the present disclosure can be embodied in many different forms and should not be construed as being limited to the exemplary embodiments described herein.

[0095] In the accompanying drawings, for clarity, the thickness of layers, films, panels, regions and / or the like may be magnified, and throughout the text, the same reference numerals represent the same elements, and their repeated descriptions may not be provided in this 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 (for example, when 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 an intermediate element. Conversely, if an element is referred to as being "directly on another element" (for example, when an element is referred to as being "directly on another element"), there is no intermediate element.

[0096] As used herein, if no definition is otherwise provided (e.g., when no definition is otherwise provided), the term "substituted" refers to a substituent or at least one hydrogen atom of a compound being replaced by 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, a carbamimido group, a hydrazine group, a hydrazone 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 aralkyl group, a C6 to C30 allyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaralkyl 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 / or (e.g., any suitable) combination thereof.

[0097] As used herein, if no definition is otherwise provided (eg, when no definition is otherwise provided), the term "hetero" refers to one including 1 to 10 heteroatoms selected from N, O, S and P.

[0098] Unless otherwise specified in this specification, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using a 1200 series gel permeation chromatograph (GPC) of Agilent Technologies (column: LF-804 of Shodex Company, standard sample: polystyrene of Shodex Company).

[0099] In addition, unless otherwise defined in the specification, "*" represents a connection point of a structural unit of a compound or a compound moiety.

[0100] Hereinafter, a resist top coating composition according to some embodiments is described.

[0101] The present disclosure relates to a photoresist topcoat composition capable of improving the intra-dot uniformity (IPU) of a contact hole (C / H) pattern, the line edge roughness (LER) / line width roughness (LWR) of a line and space (L / S) pattern, and / or the IPU of a columnar pattern by improving the sensitivity of the photoresist during a fine pattern forming (or providing) 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 in parallel (e.g., simultaneously) selectively reducing the acid concentration in an upper portion of the photoresist layer; and a method for forming (or providing) a photoresist pattern by using the topcoat layer.

[0102] In some embodiments, the 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.

[0103]

[0104] In Chemical Formula M-1 and Chemical Formula M-2,

[0105] R 1 and R 2 may each independently be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0106] L 1 and L 2 may each independently be a single bond, a substituted or unsubstituted C1 to C10 alkylene group and / or (eg, any suitable) combination thereof,

[0107] X 1 It may be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -NR a -(where R a may be hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl) and / or (e.g., any suitable) combination thereof,

[0108] R 5 may be hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl and / or (e.g., any suitable) combination thereof,

[0109] R 6 It can be hydrogen or C(=O)R b ,

[0110] Rb may be a substituted or unsubstituted C1 to C10 alkyl group,

[0111] R 5 , L 1 or L 2 At least one of may contain fluorine and hydroxyl, for example, R 5 , L 1 or L 2 At least one of may contain fluorine and R 5 , L 1 or L 2 At least one of may contain a hydroxyl group,

[0112] R 7 may be hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C10 alkyl, and / or (e.g., any suitable) combination thereof, and

[0113] m1 may be an integer selected from 1 to 4,

[0114]

[0115]

[0116] In the chemical formula M-3A and the chemical formula M-3B,

[0117] R 3 may be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0118] L 3 and L 4 may each independently be a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C20 arylene group, and / or (eg, any suitable) combination thereof,

[0119] R 8 To R 11 may each independently be hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C20 aryl, and / or (e.g., any suitable) combination thereof,

[0120] n1 may be an integer selected from 1 to 6, and

[0121] *Can be a connection point.

[0122] The photoresist top coating composition according to some embodiments may be coated on top of a photoresist film to significantly improve LER / LWR of an L / S pattern, IPU of a C / H pattern, and / or IPU of a pillar pattern, and improve sensitivity of the photoresist.

[0123] The first structural unit included in the copolymer of the composition has the property of being almost non-reactive with the photoresist but having suitable solubility (e.g., good solubility) in the solvent, and thus can protect the photoresist while minimizing or reducing the impact on the photoresist, the second structural unit can increase EUV absorption to improve sensitivity, and the third structural unit modifies the photoresist surface on the top of the photoresist layer to be easily soluble in an alkaline developer, thereby removing or reducing the circular contour area of ​​the upper layer of the photoresist generated during the exposure process during the development process, and / or controlling the upper etching during development by reacting with the acid generated from the photoresist to improve the IPU or LWR of the pattern to have, for example, a rectangular shape.

[0124] On the other hand, if the photoresist top coating composition remains after development (for example, when the photoresist top coating composition remains after development), it may cause a scum defect in the L / S pattern or a not-open defect in the C / H pattern, resulting in a decrease in product yield.

[0125] However, the photoresist top coating composition according to some embodiments may be removed during a development process and thus may not cause defects in various suitable patterns.

[0126] In the chemical formula M-2, if m1 is 2 or more (for example, when m1 is 2 or more), each OR 6 May be the same as or different from each other.

[0127] In the chemical formula M-2, if 5-m1 is 2 or more (for example, when 5-m1 is 2 or more), each R 7 May be the same as or different from each other.

[0128] R 5 , L 1 or L 2 The expression that at least one of the fluorine and hydroxyl groups is contained in the following may include the following cases, R 5 may be a C1 to C20 alkyl group substituted with at least one fluorine group and at least one hydroxyl group, or

[0129] L 1 or 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

[0130] L 1 or L 2 At least one of may be a C1 to C10 alkylene group substituted with one or more fluorine groups, and L 1 or L 2At least one of the other may be a C1 to C10 alkylene group substituted with one or more hydroxyl groups, or

[0131] R 5 can be fluorine, and L 1 or L 2 At least one of may be a C1 to C10 alkylene group substituted with one or more hydroxyl groups, or

[0132] R 5 can be a hydroxyl group, and L 1 or L 2 At least one of may be a C1 to C10 alkylene group substituted with one or more fluorines, or

[0133] R 5 may be a C1 to C10 alkyl group substituted with one or more fluorine groups and one or more hydroxy groups, or

[0134] 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.

[0135] In some embodiments, the first structural unit may be represented by Chemical Formula 1.

[0136] Chemical formula 1

[0137]

[0138] In Chemical Formula 1,

[0139] R 1 may be hydrogen or a substituted or unsubstituted C1 to C10 alkyl group,

[0140] R k , R l , R m , R n and R 5 may each independently be hydrogen, fluorine, hydroxyl, substituted or unsubstituted C1 to C20 alkyl and / or (eg, any suitable) combination thereof,

[0141] m2 and m3 may each independently be an integer selected from 1 to 10,

[0142] X 1 It may be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -NR a -(where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl) and / or (e.g., any suitable) combination thereof, and

[0143] R k , R l , R m , R n and R 5 At least one of may contain fluorine and hydroxyl, for example, R k , R l , R m , R n or R 5 At least one of may contain fluorine and R k , R l , R m , R n or R 5 At least one of the may contain a hydroxyl group.

[0144] In Chemical Formula 1, if m2 is 2 or more (for example, when m2 is 2 or more), each R k May be the same as or different from each other.

[0145] In Chemical Formula 1, if m2 is 2 or more (for example, when m2 is 2 or more), each R l May be the same as or different from each other.

[0146] In Chemical Formula 1, if m3 is 2 or more (for example, when m3 is 2 or more), each R m May be the same as or different from each other.

[0147] In Chemical Formula 1, if m3 is 2 or more (for example, when m3 is 2 or more), each R n May be the same as or different from each other.

[0148] R k , R l , R m , R n or R 5 The expression that at least one of contains fluorine and hydroxyl may include the following:

[0149] R k , R l , R m , R n or R 5 At least one of may each independently contain both fluorine and hydroxyl groups, or

[0150] R k , R l , R m , R n or R 5At least one of may each independently comprise 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

[0151] R k , R l , R m , R n or R 5 At least one of may each independently comprise a C1 to C10 alkyl group substituted with one or more hydroxyl groups and one or more fluorine groups, or

[0152] R k , R l , R m , R n or R 5 At least one of may each independently comprise a C1 to C5 alkyl group substituted with one or more hydroxyl groups and one or more C1 to C5 fluoroalkyl groups, or

[0153] R k , R l , R m , R n or R 5 At least one of them may be fluorine, and the remaining R k , R l , R m , R n or R 5 At least one of may be a hydroxyl group, or

[0154] R k , R l , R m , R n or R 5 At least one of them is fluorine, and the remaining R k , R l , R m , R n or R 5 At least one of may contain a C1 to C10 alkyl group substituted with one or more hydroxyl groups, or

[0155] R k , R l , R m , R n or R 5 At least one of R k , R l , R m , R n or R 5 At least one of may contain a C1 to C10 alkyl group substituted with one or more fluorines, or

[0156] R k , R l , R m , R n or R 5 At least one of R k , R l , R m , R n or R 5 At least one of the groups may be a C1 to C20 alkyl group substituted with one or more hydroxyl groups.

[0157] For example, R 1 can be hydrogen or methyl,

[0158] X 1 Can be a single bond, -O- or -NR a -(where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl), and

[0159] R 5 It may be fluorine, hydroxy, a C1 to C10 alkyl group substituted by at least one fluorine, or a C1 to C10 alkyl group substituted by at least one hydroxy.

[0160] In some embodiments, in Chemical Formula 1, R m , R n or R 5 At least one of may contain fluorine and hydroxyl groups.

[0161] In some embodiments, in Chemical Formula 1, R m or R n 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.

[0162] In some embodiments, in Chemical Formula 1, R m or R n 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.

[0163] In some embodiments, in Chemical Formula 1, R m It may 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 5It may be hydroxy, fluorine, or a C1 to C10 alkyl group substituted with at least one of fluorine and hydroxy.

[0164] In some embodiments, in Chemical Formula 1, R m or R n 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 of a hydroxy group and a C1 to C5 fluoroalkyl group.

[0165] For example, the first structural unit may be any one (eg, one) of the structures selected from Group I.

[0166] Group I

[0167]

[0168] In Group I,

[0169] R 1 may each independently be hydrogen or methyl, and * may be a point of attachment.

[0170] In some embodiments, the second structural unit may be represented by any one selected from Chemical Formula 2-1 to Chemical Formula 2-4.

[0171]

[0172] In Chemical Formula 2-1 to Chemical Formula 2-4,

[0173] R 2 can be hydrogen or methyl,

[0174] R 6 , R 6a and R 6b may each independently be hydrogen or C(=O)R b ,

[0175] R b may be a substituted or unsubstituted C1 to C5 alkyl group,

[0176] R 7 may each independently be hydrogen, halogen, hydroxyl, substituted or unsubstituted C1 to C10 alkyl and / or (e.g., any suitable) combination thereof, and

[0177] *Can be a connection point.

[0178] In Chemical Formulae 2-1 to 2-4, each R 7 Can be different from or the same as each other.

[0179] As an example, R 7At least one of may be a halogen.

[0180] In some embodiments, R 7 At least one of the may be an iodine group.

[0181] If the second structural unit includes an iodine group (eg, when the second structural unit includes an iodine group), the sensitivity may be further improved.

[0182] For example, the second structural unit may be any one (eg, one) selected from the structures of Group II.

[0183] Group II

[0184]

[0185]

[0186] In Group II,

[0187] R 2 may each independently be hydrogen or methyl, and * may be a point of attachment.

[0188] For example, L 3 and L 4 may each independently be a single bond, a substituted or unsubstituted C1 to C5 alkylene group, or a substituted or unsubstituted C6 to C12 arylene group, and

[0189] R 8 To R 11 Each may independently be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

[0190] The third structural unit may be any one (eg, one) selected from the structures of Group III.

[0191] Group III

[0192]

[0193] In Group III,

[0194] R 3 can be hydrogen or methyl, and * can be the point of attachment.

[0195] The copolymer may include about 30 mol % to about 95 mol % of the first structural unit, about 1 mol % to about 30 mol % of the second structural unit, and about 1 mol % to about 40 mol % of the third structural unit.

[0196] In some embodiments, the copolymer may include about 55mol% to about 90mol% of the first structural unit, about 5mol% to about 30mol% of the second structural unit, and about 5mol% 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 20mol% of the second structural unit, and about 5mol% to about 25mol% of the third structural unit.

[0197] If the molar ratio of each structural unit included in the copolymer is within the above range (eg, when 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 can be uniformly (substantially uniformly) coated.

[0198] Copolymer can have the weight average molecular weight (Mw) of about 1,000g / mol to about 50,000g / mol. For example, it can have the weight average molecular weight of about 2,000g / mol to about 30,000g / mol or about 3,000g / mol to about 20,000g / mol, but the disclosure is not limited thereto. If the weight average molecular weight of copolymer is within the above range (for example, when the weight average molecular weight of copolymer is within the above range), the carbon content (for example, amount) of the resist top coating composition comprising copolymer and the solubility in the solvent can be improved or optimized.

[0199] 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.

[0200] The solvent may be an ether solvent represented by Chemical Formula 4.

[0201] Chemical formula 4

[0202]

[0203] In chemical formula 4,

[0204] R 12 and R 13 Each may independently be a substituted or unsubstituted C3 to C20 alkyl group.

[0205] For example, the ether solvent can be any one selected from the following or can include at least one selected from the following: 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, didodecyl 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 / or their (e.g., any suitable) combination.

[0206] For the aforementioned composition (eg, copolymer), the ether solvent may have sufficient solubility or dispersibility.

[0207] In one or more 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 the present disclosure is not limited thereto.

[0208] The resist topcoat composition may further include additives including a surfactant, a thermal acid generator, a plasticizer, and / or (eg, any suitable) combinations thereof.

[0209] The surfactant may be, for example, alkylbenzene sulfonate, alkyl pyridinium salt, polyethylene glycol, quaternary ammonium salt, and / or the like, but the present disclosure is not limited thereto.

[0210] The thermal acid generator may include (e.g., may be) an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid and / or naphthoic acid, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic alkyl sulfonates, but the present disclosure is not limited thereto.

[0211] The amounts of these additives used can be readily adjusted depending on the desired or suitable physical properties and may not be provided.

[0212] In one or more embodiments, a method of forming (or providing) a pattern using the aforementioned photoresist topcoat composition may be provided. In some embodiments, the fabricated pattern may be a photoresist pattern.

[0213] According to some exemplary embodiments, the method of forming (or providing) a pattern includes: coating and heating a photoresist composition on a substrate to form (or provide) a photoresist film; coating and heating the aforementioned photoresist top coating composition on the photoresist film to form (or provide) a top coating layer; and exposing and developing the top coating layer and the photoresist film to form (or provide) an etchant pattern.

[0214] Hereinafter, the method for forming (or providing) a pattern using the aforementioned photoresist top coating composition will be described with reference to the accompanying drawings. The accompanying drawings are schematic diagrams for illustrating the method for forming (or providing) a pattern using a photoresist top coating composition according to the present disclosure. In this article, listing a process in a particular order should not necessarily mean that the present invention or the claims require the particular order. That is, the general rule is that unless the steps, tasks or actions of a process (e.g., a method claim) actually list the order, the steps, tasks or actions should not be interpreted as requiring the order.

[0215] 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 formed 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, or a silicon oxide film.

[0216] A photoresist composition is coated on the thin film and heated to form (or provide) a photoresist film 101 (stage 1). Subsequently, a photoresist topcoat composition is coated on the photoresist film and heated to form (or provide) a photoresist topcoat layer 30 (stage 2).

[0217] The heating may be performed at a temperature of about 80°C to about 500°C.

[0218] Then, the photoresist topcoat layer 30 and the photoresist film 101 are exposed to high energy radiation.

[0219] For example, the high-energy radiation 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).

[0220] 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 film (i.e., the region not covered by the patterned mask) becomes soluble in the developer (e.g., has a soluble property), so that the exposed region has a different solubility from the unexposed region of the photoresist film.

[0221] The photoresist pattern 102b may be formed by dissolving and removing the photoresist film 101 and the photoresist topcoat layer 30 corresponding to the exposed area using a developer (stage 3).

[0222] For example, the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter referred to as an organic developer).

[0223] 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.

[0224] 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 mass %, and a pH of, for example, about 10 to about 15.

[0225] 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.

[0226] 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, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and / or the like.

[0227] Examples of ester solvents may include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate and 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 / or the like.

[0228] Any suitable alcohol solvent, amide solvent, ether solvent, and hydrocarbon solvent may be used.

[0229] In some embodiments, a plurality of the solvents may be mixed, or may be mixed with a solvent other than the above solvents or water. As the developer as a whole, the water content (e.g., amount) may desirably be less than about 50 wt %, less than about 20 wt %, or less than about 10 wt %, and in one embodiment, the developer may be substantially free of water.

[0230] The content (eg, amount) of the organic solvent may desirably be about 50 wt % to about 100 wt %, about 80 wt % to about 100 wt %, or about 90 wt % to about 100 wt %, and in one embodiment, about 95 wt % to about 100 wt % based on the total amount of the organic developer.

[0231] The organic developer may contain a suitable surfactant in an appropriate amount or a suitable amount as desired or required.

[0232] The content (eg, amount) of the surfactant may generally be about 0.001 wt % to about 5 wt %, desirably 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.

[0233] In some embodiments, the organic developer may include an inhibitor.

[0234] Subsequently, the exposed thin film is etched by applying the photoresist pattern 102b as an etching mask. Thus, the thin film is formed into a thin film pattern.

[0235] For example, the thin film may be etched 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.

[0236] In the exposure process performed above, the thin film pattern formed by the photoresist pattern 102b formed by the exposure process performed by using the EUV light source can have a width corresponding to the photoresist pattern 102b. In some embodiments, the photoresist pattern 102b can have a width of about 5 nanometers (nm) to about 100nm. In some embodiments, the thin film pattern formed by the exposure process performed by using 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 or about 5nm to about 20nm, which is similar to the width of the photoresist pattern 102b, and in one embodiment, the thin film pattern can be formed to have a width less than or equal to about 20nm.

[0237] Hereinafter, the present disclosure will be described in more detail through examples involving the synthesis of the aforementioned polymer and the preparation of a photoresist top coating composition containing the same. However, the present disclosure is not technically limited to the following examples.

[0238] Synthesis example

[0239] Synthesis Example 1: Synthesis of Compound 1a

[0240] 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 in 110mL of ether and then stirred. After stirring for 30 minutes, the 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-acrylate represented by Chemical Formula 1a.

[0241] * 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)

[0242] * 19 F-NMR (acetone-d6): δ-70.12 (6F, m), -65.38 (6F, m)

[0243] Chemical formula 1a

[0244]

[0245] Synthesis Example 2: Preparation of Copolymer (R1)

[0246] In a 250 mL 2-necked round-bottom flask, a compound represented by Chemical Formula 1a (29.45 g, 66 mmol), a compound represented by Chemical Formula 1b (DIHS (di-iodine hydroxylstyrene), Daejeong Chemical Co., Ltd.) (3.72 g, 10 mmol), a compound represented by Chemical Formula 1c (ethoxyethoxystyrene, Tokyo Chemical Industry (TCI)) (4.61 g, 24 mmol) and 158 g of diisoamyl ether (DIAE) were added under a nitrogen atmosphere, and then heated to 100° C. When the internal temperature reached 100° C., 18.42 g of a 25 wt% V-601 / DIAE solution (V-601, 4.61 g, 30 mmol) was slowly added thereto, and after 6 hours, the reaction solution was cooled to room temperature, and then concentrated to have a solid content (e.g., amount) of 50%. 270 g of heptane was added to the concentrated solution, and the polymer produced therefrom was filtered. The filtered polymer was completely dissolved in 34 g of DIAE, and 270 g of heptane was added thereto for precipitation, which was repeated twice to obtain a precipitate, and the precipitate was completely dried to prepare a final copolymer R1 (Mw=5,000).

[0247]

[0248] Synthesis Example 3: Preparation of Copolymer (R2)

[0249] Copolymer R2 (Mw=4,500) was prepared in substantially the same manner as Synthesis Example 2, except that the compound represented by Chemical Formula 2c (2-(4-vinylphenoxy)tetrahydro-2H-pyran, Sigma-Aldrich Corporation) (6.77 g, 16 mmol) was used instead of the compound represented by Chemical Formula 1c.

[0250] Chemical formula 2c

[0251]

[0252] Synthesis Example 4: Preparation of Copolymer R3

[0253] Copolymer R3 (Mw = 5,500) was prepared in substantially the same manner as in Synthesis Example 2, except that the compound represented by Chemical Formula 2a (5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)-2-pentyl methacrylate, Sigma-Aldrich Corporation) (20.59 g, 70 mmol) was used instead of the compound represented by Chemical Formula 1a, and the compound represented by Chemical Formula 1b (diiodohydroxystyrene (DIHS), Daejung Chemicals & Metals) (7.44 g, 20 mmol) and the compound represented by Chemical Formula 1c (ethoxyethoxystyrene, TCI (Tokyo Chemical Industry)) (1.92 g, 10 mmol) and 124 g of diisoamyl ether (DIAE) were used.

[0254] Chemical formula 2a

[0255]

[0256]

[0257] Synthesis Example 5: Preparation of Copolymer R4

[0258] Copolymer R4 (Mw = 4,700) was prepared in substantially the same manner as in Synthesis Example 4, except that a compound represented by Chemical Formula 2a (5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)-2-pentyl methacrylate, Sigma-Aldrich Corporation) (20.59 g, 70 mmol), a compound represented by Chemical Formula 1b (DIHS (diiodohydroxystyrene), Daejung Chemicals & Metals) (3.72 g, 10 mmol) and a compound represented by Chemical Formula 2c (2-(4-vinylphenoxy)tetrahydro-2H-pyran, Sigma-Aldrich Corporation) (5.65 g, 20 mmol) were used.

[0259]

[0260] Synthesis Example 6: Preparation of Copolymer R5

[0261] Copolymer R5 (Mw = 5,900) was prepared in substantially the same manner as in Synthesis Example 2, except that the compound represented by Chemical Formula 3a (4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butyl methacrylate, Sigma-Aldrich Corporation) (19.33 g, 69 mmol) was used instead of the compound represented by Chemical Formula 1a, and the compound represented by Chemical Formula 1b (DIHS (diiodohydroxystyrene, Daejung Chemicals & Metals) (4.46 g, 12 mmol), the compound represented by Chemical Formula 1c (ethoxyethoxystyrene, TCI (Tokyo Chemical Industry)) (3.65 g, 19 mmol) and 114 g of diisoamyl ether (DIAE) were used.

[0262] Chemical formula 3a

[0263]

[0264]

[0265] Synthesis Example 7: Preparation of Copolymer R6

[0266] Copolymer R6 (Mw = 4,700) was prepared in substantially the same manner as in Synthesis Example 3, except that the compound represented by Chemical Formula 3a (4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butyl methacrylate, Sigma-Aldrich Corporation) (19.33 g, 69 mmol) was used instead of the compound represented by Chemical Formula 1a, and the compound represented by Chemical Formula 1b (DIHS (diiodohydroxystyrene, Daejung Chemicals & Metals) (4.46 g, 12 mmol) and the compound represented by Chemical Formula 2c (2-(4-vinylphenoxy)tetrahydro-2H-pyran, Sigma-Aldrich Corporation) (5.36 g, 19 mmol) and 121 g of diisoamyl ether (DIAE) were used.

[0267]

[0268] Comparative Synthesis Example 1: Preparation of Copolymer R7

[0269] Copolymer R7 (Mw=4,000) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 2b (29.38 g, 79 mmol) and the compound represented by Chemical Formula 1c (4.04 g, 21 mmol) were used, but the compound represented by Chemical Formula 1a was not used.

[0270] Chemical formula 2b

[0271]

[0272]

[0273] Comparative Synthesis Example 2: Preparation of Copolymer R8

[0274] Copolymer R8 (Mw=4,000) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 2b (23.51 g, 79 mmol) and the compound represented by Chemical Formula 2c (4.74 g, 21 mmol) were used, but the compound represented by Chemical Formula 1a was not used.

[0275]

[0276] Comparative Synthesis Example 3: Preparation of Copolymer R9

[0277] Copolymer R9 (Mw=4,500) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 1b (21.94 g, 59 mmol) and the compound represented by Chemical Formula 1c (7.88 g, 41 mmol) were used, but the compound represented by Chemical Formula 1a was not used.

[0278]

[0279] Comparative Synthesis Example 4: Preparation of Copolymer R10

[0280] Copolymer R10 (Mw=4,500) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 1b (17.56 g, 59 mmol) and the compound represented by Chemical Formula 2c (9.26 g, 41 mmol) were used, but the compound represented by Chemical Formula 1a was not used.

[0281]

[0282] Comparative Synthesis Example 5: Preparation of Copolymer R11

[0283] Copolymer R11 (Mw=5,500) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 1a (28.2 g, 79 mmol) and the compound represented by Chemical Formula 1c (3.23 g, 21 mmol) were used, but the compound represented by Chemical Formula 1b was not used.

[0284]

[0285] Comparative Synthesis Example 6: Preparation of Copolymer R12

[0286] Copolymer R12 (Mw=5,000) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 1a (28.2 g, 79 mmol) and the compound represented by Chemical Formula 2c (4.74 g, 21 mmol) were used, but the compound represented by Chemical Formula 1b was not used.

[0287]

[0288] Comparative Synthesis Example 7: Preparation of Copolymer R13

[0289] Copolymer R13 (Mw=5,500) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 2a (17.36 g, 59 mmol) and the compound represented by Chemical Formula 1c (7.88 g, 49 mmol) were used, but the compound represented by Chemical Formula 1b was not used.

[0290]

[0291] Comparative Synthesis Example 8: Preparation of Copolymer R14

[0292] Copolymer R14 (Mw=5,000) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 2a (17.36 g, 59 mmol) and the compound represented by Chemical Formula 2c (11.57 g, 41 mmol) were used, but the compound represented by Chemical Formula 1b was not used.

[0293]

[0294] Comparative Synthesis Example 9: Preparation of Copolymer R15

[0295] Copolymer R15 (Mw=5,000) was prepared in substantially the same manner as Synthesis Example 2 except that the compound represented by Chemical Formula 1a (21.06 g, 59 mmol) and the compound represented by Chemical Formula 1b (12.20 g, 41 mmol) were used, but the compound represented by Chemical Formula 1c was not used.

[0296]

[0297] Preparation of resist topcoat composition

[0298] Example 1

[0299] 0.5 wt % of the copolymer R1 according to Synthesis Example 2 was dissolved in 100 g of DIAE, then stirred at room temperature (23° C.) for 24 hours and filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.45 μm to prepare a resist top coating composition according to Example 1.

[0300] Examples 2 to 6 and Comparative Examples 1 to 9

[0301] Each resist top coating composition was prepared in substantially the same manner as in Example 1, except that the copolymers according to Synthesis Examples 3 to 7 and Comparative Synthesis Examples 1 to 9 were used instead of Copolymer R1, respectively.

[0302] Evaluation 1: Solubility evaluation

[0303] 1 g of each copolymer of Synthesis Examples 2 to 7 and Comparative Synthesis Examples 1 to 9 was added to 50 g of DIAE (2 wt %) and then stirred for 24 hours, and the obtained solution was checked with naked eyes whether precipitates were generated, and the results are shown in Table 1.

[0304] Evaluation Criteria

[0305] Solubility ○: No foreign matter, transparent liquid state

[0306] Solubility Δ: No precipitation, slightly opaque

[0307] Solubility X: produces precipitate or the solution becomes completely turbid

[0308] Evaluation 2: Development evaluation

[0309] Each of the photoresist top coating compositions according to Examples 1 to 6 and Comparative Examples 1 to 9 was spin-coated on a silicon substrate and heat-treated on a hot plate at 110° C. for 1 minute to form (or provide) a photoresist top coating layer of about 5 nm thick. The substrate having the top coating layer formed thereon was rinsed with a 2.38% tetramethylammonium hydroxide aqueous solution and heat-treated again on a hot plate at 110° C. for 1 minute, and then, a change in the thickness of the top coating layer was measured, and the results are shown in Table 1.

[0310] *Residual film after development (%) = [Top coating thickness before development (nm) - Top coating thickness after development (nm)] x 100 / Top coating thickness before development (nm)

[0311] Evaluation Criteria

[0312] ○: If the residual film after development (%) calculated by the above calculation formula is 98% or more.

[0313] Δ: If the residual film after development (%) calculated using the above calculation formula is 90% or more but less than 98%.

[0314] X: If the residual film after development (%) calculated using the above formula is less than 90%

[0315] Evaluation 3: Evaluation of sensitivity and LWR

[0316] 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 thereon, and then heat-treated on a hot plate at 110° C. for 1 minute to form (or provide) a photoresist top coating layer of about 5 nm in thickness.

[0317] 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 (or providing) a critical dimension (CD) of 50 nm was examined in an interpolation method, and the results are shown in Table 1.

[0318] After checking the optimal sensitivity, the line width roughness (LWR) distribution 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 distribution, and its final average value is shown in Table 1.

[0319] Table 1

[0320]

[0321] Referring to Table 1, if the resist top coating composition according to one embodiment of the present disclosure is applied (for example, when the resist top coating composition according to one embodiment of the present disclosure is applied), not only excellent or appropriate solubility, developability, and sensitivity are achieved, but also an excellent or appropriate LWR improvement effect is obtained because pattern degradation is suppressed or reduced.

[0322] In contrast, the resist top coating composition of the comparative example exhibited relatively deteriorated developability and sensitivity and had no LWR improving effect.

[0323] When describing embodiments of the present invention, the use of "may" refers to "one or more embodiments of the present invention". As used herein, the terms "substantially", "about" and the like are used as approximate terms rather than terms of degree, and are intended to explain the inherent deviations in the measured or calculated values ​​that will be recognized by those of ordinary skill in the art. In addition, any numerical range described herein is intended to include all sub-ranges of the same numerical precision contained in the range. For example, the range of "1.0 to 10.0" is intended to include (and include) all sub-ranges between the minimum value 1.0 and the maximum value 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all numerical lower limits contained therein, and any minimum numerical limit described in this specification is intended to include all numerical upper limits contained therein. Therefore, the applicant reserves the right to modify this specification (including claims) to explicitly state any sub-ranges contained in the range explicitly described herein. All these ranges are intended to be inherently described in this specification.

[0324] It should be understood that the embodiments described herein should be considered to be merely descriptive and not for limiting purposes. The description of features or aspects within each embodiment should generally be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it should be understood by those of ordinary skill in the art that various changes may be made to them in form and detail without departing from the spirit and scope defined by the appended claims 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 or a substituted or unsubstituted C1 to C10 alkylene group, X 1 The single key is -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O- or -NR a -, where R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl, R 5 is hydrogen, fluorine, hydroxyl or substituted or unsubstituted C1 to C20 alkyl, R 6 is hydrogen or C(=O)R b , R b is a substituted or unsubstituted C1 to C10 alkyl group, R 5 , L 1 or L 2 At least one of them contains fluorine and R 5 , L 1 or L 2 at least one of which contains a hydroxyl group, R 7 is hydrogen, halogen, hydroxyl or substituted or unsubstituted C1 to C10 alkyl, and m1 is an integer selected from 1 to 4, Chemical formula M-3A Chemical formula M-3B 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, L 3 and L 4 are each independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group, R 8 To R 11 are each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, or substituted or unsubstituted C6 to C20 aryl, n1 is an integer selected from 1 to 6, 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 k , R l , R m , R n and R 5 are each independently hydrogen, fluorine, hydroxyl or substituted or unsubstituted C1 to C20 alkyl, m2 and m3 are each independently an integer selected from 1 to 10, X 1 The single key is -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O- or -NR a -, R a is hydrogen, deuterium or substituted or unsubstituted C1 to C10 alkyl, and R k , R l , R m , R n or R 5 At least one of them contains fluorine and R k , R l , R m , R n or R 5 At least one of the two comprises a hydroxyl group.

3. The resist top coating composition according to claim 2, wherein In Chemical Formula 1, R m , R n or R 5 At least one of them contains fluorine and R m , R n or R 5 At least one of the two comprises a hydroxyl group.

4. The resist top coating composition according to claim 2, wherein In Chemical Formula 1, R m or R n At least one of is fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 5 It is a hydroxy group or a C1 to C10 alkyl group substituted with at least one hydroxy group.

5. The resist top coating composition according to claim 2, wherein In Chemical Formula 1, R m or R n At least one of is a hydroxyl group or a C1 to C10 alkyl group substituted with at least one hydroxyl group, and R 5 is fluorine or a C1 to C10 alkyl group substituted by at least one fluorine.

6. The resist top coating composition according to claim 2, wherein In Chemical Formula 1, R m is hydroxy or C1 to C10 alkyl substituted with at least one hydroxy, R n is fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 5 It is hydroxy, fluorine, or a C1 to C10 alkyl group substituted with at least one of fluorine and hydroxy.

7. The resist top coating composition according to claim 2, wherein In Chemical Formula 1, R m or R n At least one of is fluorine or a C1 to C10 alkyl group substituted with at least one fluorine, and R 5 It is a hydroxy group or a C1 to C5 alkyl group substituted with at least one of a hydroxy group and a C1 to C5 fluoroalkyl group.

8. The resist top coating composition according to claim 1, wherein The first structural unit is represented by any one of the structural units selected from Group I: Group I In Group I, R 1 are each independently hydrogen or methyl, and * is the connection point.

9. 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: 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 7 are each independently hydrogen, halogen, hydroxyl or substituted or unsubstituted C1 to C10 alkyl, and * is the connection point.

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

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

12. The resist top coating composition according to claim 1, wherein The second structural unit is represented by any one of the structural units selected from Group II: Group II In Group II, R 2 are each independently hydrogen or methyl, and * is the connection point.

13. The resist top coating composition according to claim 1, wherein L 3 and L 4 are each independently a single bond, a substituted or unsubstituted C1 to C5 alkylene group, or a substituted or unsubstituted C6 to C12 arylene group, and R 8 To R 11 Each is independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C12 aryl.

14. The resist top coating composition according to claim 1, wherein The third structural unit is represented by any one of the structural units selected from Group III: Group III In Group III, R 3 is hydrogen or methyl, and * is the connection point.

15. 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 30 mol % of the second structural unit, and 1 mol % to 40 mol % of the third structural unit.

16. The resist top coating composition according to claim 1, wherein The copolymer has a weight average molecular weight of about 1,000 to about 50,000 g / mol.

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

18. The resist top coating composition according to claim 1, wherein The solvent is an ether solvent represented by Chemical Formula 4: In chemical formula 4, R 12 and R 13 Each is independently a substituted or unsubstituted C3 to C20 alkyl group.

19. A method for forming a pattern, the method comprising: coating and heating a photoresist composition on a substrate to form a photoresist film, coating and heating the resist top coating composition according to any one of claims 1 to 18 on the photoresist film to form a top coating layer, and The top coating layer and the photoresist film are exposed and developed to form a resist pattern.

Images