Top coating composition

Abstract

The present invention relates to a top coating composition comprising polymer (A), which comprises repeating unit A1 and A2. The composition can be used for a top coat composition, which can exhibit at least one of properties of advanced material or high performance material. The composition can be used in the nanotechnology process to make semiconductor device / display device application, for example liquid crystal, quantum dot or OLED display fabricated on a substrate, and controlled by semiconductors.

Description

Foreignfilingjext P24-242-SEC-WO01 20250925Top Coating CompositionField of the Invention

[0001] The present invention relates to a top coating composition, and using thereof.Background Art

[0002] In recent years, the miniaturization and high integration of semiconductor devices have progressed rapidly, increasing the importance of photolithography technology. In photolithography, the precision of resist pattern formation is directly linked to the performance and reliability of the devices, necessitating improvements in resist materials and process technologies.

[0003] A top coating is a film formed on or above the resist film exhibiting, for example gas protection. In the formation of resist patterns, the interference of exposure light due to reflection can become an issue. A top anti-reflective coating (TARC) can suppress the reflection of the exposure light. By using TARC, it is possible to reduce pattern distortion and dimensional variation caused by the interference of exposure light, enabling high- precision pattern formation.

[0004] Patent document 1 describes a Top anti-reflective coating (TARC) composition for 193 nm lithography, which has an aqueous base-soluble polymer having aromatic moieties for example naphthyl unit.

[0005] Patent document 2 describes a TARC composition comprising a solvent and an anthracene skeleton-containing polymer having a hydrophilic group.

[0006] Patent Literature1. US7544750Foreignfilingjext P24-242-SEC-WO01 202509252. US2010279235Summary of the invention

[0007] The present invention aims to provide a top coating composition that addresses above mentioned challenges, offering good properties fit to mass production processes.

[0008] Inventors have found that at least one of inventions describes hereinafter can solve one or more of following problems: possible to improve solubilities of components of top coating compositions to their solvent; possible to make (e.g., lower) a reflective index of the resultant top coating appropriate figure; possible to make the resultant top coating soluble to developer; possible to inhibit defect caused by residue from development; possible to inhibit an intermixing of top coating composition with underneath photoresist layer; possible to make a top coating composition having good wettability on photoresist layer; possible to lower an amplitude of a swing curve; possible to lower swing ratio; possible to provide a process composition friendly to human and environment; and possible to improve yield of device production.

[0009] Namely, it is found a top coating composition comprising polymer (A). The present invention also provides a method for manufacturing top coating, resist patterns, and a device. Also, the present invention provides a polymer (A). Details follow.Technical effects of the invention

[0010] Inventors have found that at least one of inventions which can exhibit their technical effects, and can solve one or more of above mentioned problems.Definition of the terms

[0011] Unless otherwise specified in the present specification, the definitions and examples described in this paragraph areForeignfilingjext P24-242-SEC-WO01 20250925 followed.

[0012] The singular form includes the plural form and “one” or “that” means “at least one”. An element of a concept can be expressed by a plurality of species, and when the amount (for example, mass % or mol %) is described, it means sum of the plurality of species.

[0013] “And / or” includes a combination of all elements and also includes single use of the element.

[0014] When a numerical range is indicated using “to” or it includes both endpoints and units thereof are common. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.

[0015] The descriptions such as “Cx-y”, “Cx-Cy” and “Cx” mean the number of carbons in a molecule or substituent. For example, C1-6 alkyl means an alkyl chain having 1 or more and 6 or less carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl etc.).

[0016] When a polymer has multiple types of repeating units, these repeating units undergo copolymerization. This copolymerization may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, n, m or the like that is attached next to parentheses indicate the number of repetitions.

[0017] Celsius is used as the temperature unit. For example, 20 degrees means 20 degrees Celsius.Foreignfilingjext P24-242-SEC-WO01 20250925

[0018] The additive refers to a compound itself having a function thereof (for example, in the case of a base generator, a compound itself that generates a base). An embodiment in which the compound is dissolved or dispersed in a solvent and added to a composition is also possible. As one embodiment of the present invention, it is preferable that such a solvent is contained in the composition according to the present invention as the solvent (B) or another component.Detailed description of the invention

[0019] Herein later, detailed embodiments are explained as explanatory purposes. These should not be taken into consideration to limit the scope of the claims.

[0020] According to the present invention, said top coating composition comprises polymer (A). The polymer (A) comprises repeating unit A1 and A2.

[0021] Each number of unit A1 and unit A2 in polymer (A) are denoted as nA1 and nA2 respectively. The total number of all unit contained in the polymer (A) is denoted as nAtotai.

[0022] These satisfy following,0% < (nA1 I nAtotai) < 90%, and 0% < (nA2 / nAtotai) < 95%.

[0023] (nA1 I nAtotai) is preferably 1 to 70%; more preferably 5 to 50%; further preferably 10 to 30%; further more preferably 15 to 20%.

[0024] (nA2 I nAtotai) is preferably 5 to 90%; more preferably 10 to 80%; further preferably 20 to 70%; further more preferably 40 to 60%.Foreignfilingjext P24-242-SEC-WO01 20250925

[0025] End portion of polymer (A) can be modified with any type of modification group, which are available by the prior art. For example, modifying one or more of end portion of polymer (A) can be modified by -C(CH3)2(CN), -C(CH3)2-C=NH(NH3), or - (4-cyanovaleric acid).

[0026] It is one preferable embodiment of this invention that the polymer (A) has less or none of fluoro (-F) in it. Average mass amount of the fluoro in the polymer is preferably 0.00 to 5.0 mass% (more preferably 0.00 to 1 .0 mass%; further preferably 0.00 to 0.1 mass%; further more preferably 0.00 mass%) comparing to the total of polymer (A). This number can be calculated from average of atomic mass.

[0027] Repeating unit A1According to the present invention, said polymer (A) comprises repeating unit A1 . The repeating unit A1 is represented by formula A1.- Formula A1

[0028] Ri 1 , R12 and RI3are each independently H or methyl. Ri 1 is preferably methyl. R12 and RI3are preferably H.

[0029] R14 is each independently C1-10 alkyl, C1-10 alkoxyl, -OH,-COOH, -COOR15, -SO3H, or cyano, where one or more of methylene in alkyl portion in R14 can beForeignfilingjext P24-242-SEC-WO01 20250925 replaced by ether linker, one or more of methyl in alkyl portion in R14 can be replaced by hydroxyl, and one or more of alkyl of R14 can further include heteroatom.

[0030] R15 is each independently C1-6 alkyl, -SO3H, cyano, C2-4 alkenyl or C2-4 alkynyl.

[0031] R14 is preferably C1-10 alkyl, -OH, or -COOH; more preferably C1-10 alkyl, or -OH; further preferably C1-10 alkyl; further more preferably C1-5 alkyl.

[0032] Said alkyl of R14 is linear, branched cyclic or any combination of any of these; preferably linear, branched or combination of linear and branched; more preferably linear.

[0033] One or more of methylene in alkyl portion in R14 can be replaced by ether linker. In the case that plural methylene in alkyl portion in R14 are replaced by ether linker (-O-), it is preferable that such ether linkers are not adjacent each other. It is preferable embodiment of the invention that none of methylene in alkyl portion in R14 is replaced by ether linker.

[0034] One or more of methyl in alkyl portion in R14 can be replaced by hydroxyl. It is preferable that one methyl in alkyl portion in R14 is replaced by hydroxyl. It is preferable embodiment of the invention that none of methyl in alkyl portion in R14 is replaced by hydroxyl.

[0035] One or more of alkyl of R14 can further include heteroatom. It is one preferable embodiment of this invention that one of R14 further include heteroatom. More preferably that heteroatom is S or N; further preferably N. It is also another preferable embodiment of the invention that none of alkyl of R14 can further include heteroatom.Foreignfilingjext P24-242-SEC-WO01 20250925

[0036] R15 is preferably C1-6 linear alkyl, C3-6 branched alkyl, -SO3H, cyano, C2-4 alkenyl or C2-4 alkynyl; more preferably methyl, ethyl ,n-propyl, i-propyl, n-butyl, t-butyl, cyano, vinyl or ethynyl; further preferably methyl, ethyl ,n-propyl, vinyl or ethynyl.

[0037] As one of embodiment, -CH(OH)-CH2-OH can be regarded as such Ru with replacements. In this embodiment, two methyls of original C4 alkly (-CH(CH3)-CH2-CH3) are substituted by hydroxyls (-OH).

[0038] As another embodiment, -CH(OH)-CH2-OCH3 can be regarded as such Ru with a substitution and a replacement. In this embodiment, original Cs alkyl is (-CH(CH3)-CH2-CH2-CH3), in which one methyl is replaced by -OH and one methylene (- CH2) is replaced by -O-.

[0039] As further embodiment which this invention provides, - CH2-OH can be regarded as such R14 with a replacement. In this embodiment, original C2 alkyl is (-CH2-CH3), in which a methyl is replaced by -OH.

[0040] L11 is single bond, or -COO-; preferably -COO-.L12 is single bond, or C1-3 alkylene; preferably single bond, or methylene; more preferably methylene. It is one preferable embodiment of this invention that anthracene bonds to main chain at 9thposition, via L12.

[0041] nn is number of 0 to 9; preferably 0 to 5; more preferably 0 to 3; further preferably 0 or 1 ; further more preferably 0.Foreignfilingjext P24-242-SEC-WO01 20250925

[0042] As one embodiment of this invention, below left unit can be read by original scope of formula A1. Where, Ru , R12 and R13 are H; nn=0; and L11 is -COO-, and L12 is methylene. Anthracene bonds to main chain at 9thposition, via L12.

[0043] As another embodiment of this invention, below right unit can be read by original scope of formula A1. Where, R11 , R12 and R13 are methyl; R14 is -OH; m 1 =1 ; and L11 and L12 are single bond. Anthracene bonds to main chain at 1stposition, via L12.

[0044] Repeating unit A2According to the present invention, said polymer (A) comprises repeating unit A2. The repeating unit A2 is represented by formula A2.Foreignfilingjext P24-242-SEC-WO01 20250925- Formula A2

[0045] R21 , R22 and R23 are each independently H or methyl.R21 is preferably methyl. R22 and R23 are preferably H.

[0046] R24 is each independently H or methyl; preferably H.

[0047] R25 is H, hydroxyl, C1-6 alkoxyl, or -COOH; preferably H, hydroxyl, or methoxy ; more preferably H or hydroxyl, further preferably hydroxyl.

[0048] L21 is single bond, -CO- or C1-6 alkylene; preferably single bond, -CO- or -CH2-; more preferably single bond or - CO-; further preferably -CO-.

[0049] L22 is single bond, or C1-10 alkylene; preferably single bond, or C1-4 alkylene; more preferably single bond.

[0050] n2i is number of 1 to 10; preferably number of 1 to 9; more preferably number of 2 to 8.

[0051] As one embodiment of this invention, below left unit can be read by original scope of formula A2. Where, R21 , R22 and R23 are H; R24 is H; R25 is hydroxyl; L21 is -CO-; L22 is single bond; and n2i is 3. As one embodiment of this invention, below right unit can be read by original scope of formula A2. Where,Foreignfilingjext P24-242-SEC-WO01 20250925R21 is methyl, R22 and R23 are H; R24 is methyl; R25 is methoxy;L21 is single bond; L22 is single bond; and n2i is 1.

[0052] Although not to be bound by theory, it is believed that the top coating made from the top coating composition comprising polymer A which have both of unit A1 and unit A2 can exhibit useful properties. For example, said useful property is optical property like the n value and / or k value, when irradiated by 248 nm wavelength light. Although not to be bound by theory, it is believed that unit A2 in polymer (A) can exhibit good solubility to the solvent (B) (e.g., DIW), which the skilled person can choose not to substantially dissolve underneath photoresist layer, but capable to dissolve solid components (e.g., polymer (A)) of the top coating composition.

[0053] Repeating unit A3According to the present invention, said polymer (A) can further comprise repeating unit A3. The repeating unit A3 is represented by formula A3.Foreignfilingjext P24-242-SEC-WO01 20250925- Formula A3

[0054] R31, R32 and R33 are each independently H or methyl.R31 is preferably methyl. R32 and R33 are preferably H.

[0055] l_3i is single bond, or -COO-; preferably -COO-. R34 is H, or C1-10 alkyl.

[0056] In the alkyl of R34, one or more of methylene portion can be replaced by -O-, or -CO-. In the case that plural methylene in alkyl portion in R34 are replaced by -O-, it is preferable that such ether linkers are not adjacent each other. It is preferable embodiment of the invention that none of methylene in alkyl portion in R34 is replaced by -O-.

[0057] In the alkyl of R34, one or more H can be replaced by hydroxyl. It is preferable embodiment of the invention that none of H of R34 is replaced by hydroxyl.

[0058] R34 is preferably H, or C1-4 alkyl; more preferably H, methyl, ethyl, or n-propyl; further preferably H.

[0059] The number of unit A3 in polymer (A) is denoted as nA3. nA3 and nAtotai satisfies following, 0% < (nA3 / nAtotai) < 70%.

[0060] (nA31 nAtotai) is preferably 0.1 to 70%; more preferably 10 to 60%; further preferably 20 to 60%; further more preferably 20 to 50%.Foreignfilingjext P24-242-SEC-WO01 20250925

[0061] Although not to be bound by theory, it is believed that in the case polymer (A) comprising unit A3, the top coating made from the top coating composition can exhibit good property, e.g., good solubility and / or removability by developer (e.g., 2.38 mass% TMAH).

[0062] Other unitAccording to the present invention, said polymer (A) can further comprise unit other than unit A1 , A2 or A3.

[0063] The number of unit other than unit A1 , A2 or A3 in polymer (A) is denoted as nAother. nAother and nAtotai satisfies below, 0% < (nAother I nAtotai) < 20%

[0064] (nAother I nAtotai) is preferably 0 to 10%; more preferably 0% or more and less than 10%; further preferably more than 0% and less than 5%.

[0065] It is one preferable embodiment of this invention that the “other unit” in polymer (A) has less or none of fluoro (-F) in it. Average mass amount of the fluoro in the “other unit” is preferably 0.00 to 20.0 mass% (more preferably 0.00 to 10.0 mass%; further preferably 0.00 to 1 .0 mass%; further more preferably 0.00 mass%) comparing to the total of the “other unit”. This number can be calculated from average of atomic mass.

[0066] It is preferable that the polymer (A) essentially consists of repeating unit A1 , A2 and A3. It is more preferable that the polymer (A) consists of repeating unit A1 , A2 and A3 ((nAother I nAtotai)= 0%). It goes without saying, for the sake of clarity, it isForeignfilingjext P24-242-SEC-WO01 20250925 included into said embodiment that end portion of polymer (A) is modified.

[0067] It is one embodiment of this invention that the content of polymer (A) comparing to total of the top coating composition is preferably 0.10 to 15 mass% (more preferably 0.5 to 10 mass%; further preferably 0.5 to 5 mass %; further more preferably 0.8 to 4 mass%).

[0068] The top coat composition of this invention can comprise multiple types of polymer (A) in it, as far as each of polymer (A) comprises unit A1 and unit A2.

[0069] The polymer (A) can take the copolymerization status, as preferably random copolymer, graft copolymer, block copolymer, alternating copolymer, or any mixture of any of these (more preferably random copolymer, block copolymer, or alternating copolymer; further preferably random copolymer).

[0070] It is one aspect of this invention that the molecular weight (Mw) of the polymer (A) is preferably 5 to 100 kDa (more preferably 10 to 70 kDa; further preferably 15 to 60 kDa).

[0071] Molecular weight of polymer (A) can be determined Gel Permeation Chromatography. Preferably polystyrene can be used as a reference. Unless described otherwise, same apply to following descriptions as to molecular weight of any type of polymer.

[0072] As another aspect, this invention provide polymer (A), which comprises unit A1 and unit A2, where nA1 , nA2 and nAtotai satisfy “0% < (nA1 / nAtotai) < 90%” and “0% < (nA2 / nAtotai) 95%”. Definitions, explanations, descriptions andForeignfilingjext P24-242-SEC-WO01 20250925 embodiments of each elements of the polymer (A) are independently same to described above.

[0073] CompositionThe top coating composition of this invention comprise any embodiments described in this specification. The top coating composition is applied on the photoresist layer, and is made to a top coating.

[0074] As one preferable embodiment of this invention, the top coating composition is a top anti-reflective coating composition. The top anti-reflective coating composition is used to make a coating on photoresist layer, and exhibits anti-reflective properties. These properties are described in detailed in later.

[0075] As one more preferable embodiment of this invention, the top anti-reflective coating composition is a KrF top anti- reflective coating composition. The KrF top anti-reflective coating composition is one concrete example of top anti- reflective coating composition, which is used in the photolithography process with using KrF light exposure.

[0076] As one embodiment of this invention, but not to be bound by theory, it is believed that it is advantageous that the top coating composition exhibits good wettability on the underneath photoresist layer. When the top coating composition is dropped on a photoresist layer, it is one preferable embodiment of this invention that the contact angle of such droplet is 40 or less degree (more preferably 35 or less degree; further preferably 1-35 degree; further more preferably 1-30 degree).

[0077] It is one preferable embodiment of this invention that the top coating composition has less or none of fluoro (-F) in it.Foreignfilingjext P24-242-SEC-WO01 20250925Average mass amount of the fluoro in the solid components is preferably 0.00 to 5.0 mass% (more preferably 0.00 to 1 .0 mass%; further preferably 0.00 to 0.1 mass%; further more preferably 0.00 mass%) comparing to the total of the solid components. This number can be calculated from average of atomic mass. In here, solid components mean “components other than solvent (B)”, and / or “components which will remain as a top coating formed from the top coating composition”.

[0078] SolventThe top coating composition can further comprise solvent (B). Solvent known in public can be applied to the solvent (B) of this invention.

[0079] As one embodiment of this invention, the content of solvent (B) comparing to total of the top coating composition is preferably 40 to 99.99% (more preferably 60 to 99.9%; further preferably 80 to 99.5%; further more preferably 90 to 99.50%).

[0080] It is one preferable embodiment of this invention that solvent (B) comprises water (B1 ). One preferable embodiment of water (B1 ) is DIW. As one embodiment of this invention, the content of water (B1 ) comparing to total of solvent (B) is preferably 0 to 100 mass% (more preferably 50 to 100 mass%; further preferably 90 to 100 mass%; further more preferably 95 to 100 mass%). It is one embodiment of this invention, the solvent (B) doesn’t comprise water (B1 ) (0 mass%).

[0081] It is one preferable embodiment of this invention that solvent (B) comprises organic solvent (B2). The contents of organic solvent (B2) comparing to total of solvent (B) is preferably 0 to 100 mass% (more preferably 50 to 100 mass%; further preferably 90 to 100 mass%; further more preferably 95Foreignfilingjext P24-242-SEC-WO01 20250925 to 100 mass%). It is one embodiment of this invention, the solvent (B) doesn’t comprise organic solvent (B2) (0 mass%).

[0082] The solvent (B) can comprise both of water (B1 ) and organic solvent (B2). As one aspect of this invention, the mass weight ratio between water (B1 ) and organic solvent (B2) is preferably 100:1 to 1 :20 (more preferably 50:1 to 1 :4 ; further preferably 30:1 to 1 :3 ; further more preferably 20:1 to 1 :2).

[0083] Although not to be bounded by theory, because of good solubilities, it is possible to reduce the amount of organic solvent (B2). It is one embodiment of this invention that organic solvent (B2) comparing to total of solvent (B) is preferably 0 to 20 mass% (more preferably 0 to 15 mass%; further preferably 0.01 to 10 mass%; further more preferably 0.01 to 8 mass%). It is one embodiment of this invention, the solvent (B) doesn’t comprise organic solvent (B2) (0 mass%).

[0084] It is another embodiment of this invention that organic solvent (B2) comparing to total of top coating composition is preferably 0 to 20 mass% (more preferably 0 to 15 mass%; further preferably 0.01 to 10 mass%; further more preferably 0.01 to 8 mass%). It is one embodiment of this invention, the solvent (B) doesn’t comprise organic solvent (B2) (0 mass%).

[0085] Organic solvent (B2) can comprise, for example alcohol solvent (B2-1 ), ketone solvent (B2-2), ester solvent (B2-3), ether solvent (B2-4), and other types of organic solvent (B2-5). For example, alcohol solvent (B2-1 ) is methyl alcohol, ethyl alcohol, isopropyl alcohol (IPA), 2-mehyl pentanol, diacetone alcohol, and any mixture of any of these. For example, ketone solvent (B2-2) is acetone, methyl ethyl ketone, or mixture of these. For example, ester solvent (B2-3) is methyl acetate, ethyl acetate, ethyl lactate, propylene glycol methyl etherForeignfilingjext P24-242-SEC-WO01 20250925 acetate (PGMEA), cellosolve acetate, alkylcellosolve acetate, carbitol acetate, or any mixture of any of these. For example, ether solvent (B2-4) is diethyl ether, dibutyl ether, propylene glycol monomethyl ether (PGME), methyl cellosolve, ethyl cellosolve, butyl cellosolve, butylcarbitol, or any mixture of any of these. For example other types of organic solvent (B2-5) is dimethylformamide, dimethyl sulfoxide, or any mixture of any of these.

[0086] Organic solvent (B2) is preferably alcohol solvent (B2-1 ), or ether solvent (B2-4), or mixture of them; more preferably alcohol solvent (B2-1 ), or ether solvent (B2-4); further preferably ether solvent (B2-4). It is also one preferable embodiment of this invention that the organic solvent (B2) is alcohol solvent (B2-1 ). It is other embodiment of this invention that organic solvent (B2) is selected at least one from IPA or PGME. Although not to be bound by theory, it is good for the effect of this invention to select solvent (B) which doesn’t dissolved photoresist layer when the top coating composition applied onto it.

[0087] The contents of alcohol solvent (B2-1 ) comparing to total of solvent (B) is preferably 0 to 100 mass% (more preferably 0 to 50 mass%; further preferably 1 to 50 mass%; further more preferably 5 to 25 mass%). It is one embodiment of this invention, the solvent (B) doesn’t comprise alcohol solvent (B2- 1) (0 mass%).

[0088] Basic compoundThe top coating composition of this invention can further comprise basic compound (C).Foreignfilingjext P24-242-SEC-WO01 20250925

[0089] Examples of the basic compound (C) include the followings:(i) ammonia,(ii) C1-16 primary aliphatic amines and derivatives thereof (for example, methylamine, ethylamine, isopropylamine, n-butylamine, tert-butylamine, cyclohexylamine, ethylenediamine, tetraethylenediamine, ethanol amine etc.),(iii) C2-32 secondary aliphatic amines and derivatives thereof (for example, dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, N,N-dimethylmethylenediamine, etc.),(iv) C3-48 tertiary aliphatic amines and derivatives thereof (for example, trimethylamine, triethylamine, tripropylamine, dimethylethylamine, tricyclohexylamine, N,N,N’,N’- tetramethylethylenediamine, N,N,N’,N’-tetraethyl- ethylenediamine, N,N,N’,N”,N”-pentamethyl- diethylenetriamine, tris[2- (dimethylamino)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, etc.),(v) C6-30 aromatic amines and derivatives thereof (for example, aniline, benzylamine, naphthylamine, N-methylaniline, 2- methylaniline, 4-aminobenzoic acid, phenylalanine, etc.), and(vi) C5-30 heterocyclic amines and derivatives thereof (for example, pyrrole, oxazole, thiazol, imidazole, 4-methylimidazole, pyridine, methylpyridine, butylpyridine, etc.).

[0090] It is one aspect of this invention that the content of basic compound (C) comparing to total of polymer (A) is preferably 0 to 10 mass% (more preferably 0.1 to 9 mass%; further preferably 3 to 8 mass%). It is one embodiment of this invention that the top coating composition doesn’t comprise basic compound (C) (0 mass% comparing to polymer (A)).

[0091] SurfactantThe top coating composition of this invention can further comprise surfactant (D).Foreignfilingjext P24-242-SEC-WO01 20250925

[0092] The surfactant (D) includes, for example;(a) anionic surfactants, such as alkyl-diphenyletherdisulfonic acid, alkyldiphenylethersulfonic acid, alkylbenzenesulfonic acid, polyoxyethylenealkylethersulfuric acid, alkylsulfuric acid, and ammonium salts or organic amine salts thereof;(b) cationic surfactants, such as hexadecyltrimethylammonium hydroxide;(c) nonionic surfactants, such as polyoxyethylenealkylether (e.g., polyoxyethylenelaurylether, polyoxyethyleneoleylether, polyoxyethylenecetylether), polyoxyethylene-fatty acid diester, polyoxyethylene-fatty acid monoester, polyoxyethylenepolyoxypropylene block polymer; and acetylene glycol derivatives;(d) amphoteric surfactants, such as 2-alkyl-N-carboxymethyl- N-hydroxyethyl-imidazoliniumbetaine, and amidopropylhydroxysulfonebetaine laurylate; and(e) polymeric surfactants, such as polyvinylsulfonic acid, polyoxyethylenealkylether, polyoxyethylenelaurylether, polyoxyethyleneoleylether, polyoxyethylenecetylether, polyoxyethylene-fatty acid diester, polyoxyethylene-fatty acid monoester, polyoxyethylenepolyoxypropylene block polymer, acetylene glycol derivatives, and polyalkylene sulfuric acid, polysiloxanes.

[0093] It is one preferable embodiment of this invention that the (e) polymeric surfactant has less or none of fluoro (-F) in it. Average mass amount of the fluoro in the (e) polymeric surfactant is preferably 0.00 to 20.0 mass% (more preferably 0.00 to 10.0 mass%; further preferably 0.00 to 1 .0 mass%; further more preferably 0.00 mass%) comparing to the total of the (e) polymeric surfactant. This number can be calculated from average of atomic mass. As preferable one embodiment of this invention, surfactant (D) is (c) nonionic surfactant.Foreignfilingjext P24-242-SEC-WO01 20250925

[0094] It is one embodiment of this invention that the content of surfactant (D) comparing to total of polymer (A) is preferably 0 to 25 mass% (more preferably 0.1 to 20 mass%; further preferably 1 to 15 mass%; further more preferably 1 to 5 mass%). It is one embodiment of this invention that the top coating composition doesn’t comprise surfactant (D) (0 mass% comparing to polymer (A)).

[0095] PolymerThe top coating composition of this invention can further comprise polymer (E). Polymer (E) can be regarded as sub polymer in this composition. By including polymer (E), coatability of the composition and rigidness of the top coating made from the top coating composition can be controlled. Polymer (E) is different from polymer (A). Polymer (E) is different from (e) polymeric surfactant of surfactant (D).

[0096] In the case the polymer (E) comprises multiple types of repeating unit, the polymer (E) can take the copolymerization status, as preferably random copolymer, graft copolymer, block copolymer, alternating copolymer, or any mixture of any of these (more preferably random copolymer, block copolymer, or alternating copolymer; further preferably random copolymer).

[0097] As one embodiment of this invention, the content of polymer (E) comparing to total of polymer (A) is preferably 0 to 25.0 mass% (more preferably 0 to 20.0 mass%; further preferably 0.1 to 20.0 mass%; further more preferably 5 to 20.0 mass%). It is one embodiment of this invention that the top coating composition doesn’t comprise polymer (E) (0 mass% comparing to polymer (A)).Foreignfilingjext P24-242-SEC-WO01 20250925

[0098] It is one aspect of this invention that the Mw of the polymer (E) is preferably 5 to 100 kDa (more preferably 10 to 70 kDa; further preferably 15 to 60 kDa).

[0099] It is one preferable embodiment of this invention that the polymer (E) has less or none of fluoro (-F) in it. Average mass amount of the fluoro in the polymer (E) is preferably 0.00 to 5.0 mass% (more preferably 0.00 to 1 .0 mass%; further preferably 0.00 to 0.1 mass%; further more preferably 0.00 mass%) comparing to the total of polymer (E). This number can be calculated from average of atomic mass.

[0100] AdditivesThe top coating composition of this invention can further comprise additive (F). The additive is preferably a dye, a surface smoothing agent, an acid, a substrate adhesion enhancer, an antifoaming agent, an antiseptic, or any combination of any of these (more preferably an acid, or an antiseptic). Known compounds can be used for any one of these purposes.

[0101] As one embodiment of this invention, the content of additive (F) comparing to total of polymer (A) is preferably 0 to 25.0 mass% (more preferably 0 to 20.0 mass%; further preferably 0.1 to 20.0 mass%; further more preferably 5 to 20.0 mass%). It is one embodiment of this invention that the top coating composition doesn’t comprise additive (F) (0 mass% comparing to polymer (A)).

[0102] Method for manufacturing top coating compositionThis invention provides a method for manufacturing top coating.The method comprises following below steps.Foreignfilingjext P24-242-SEC-WO01 20250925(1 ) applying a photoresist composition above a substrate to form a photoresist layer; and(2) applying any embodiment of the top coating composition described in this specification on the photoresist layer to form a top coating.In this specification, unless otherwise specified, the numbers in parentheses indicating the steps mean the order.

[0103] Step (1 )Any known substrate can be used in the methods of this invention. Substrate is for example, a silicon / silicon dioxidecoated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, an ITO substrate, etc. A fabrication of multiple types of chemical layers is one embodiment of the substrate used in methods of this invention.

[0104] In the present invention, "above" includes the case of applying directly on a substrate and the case of applying on underlayer. One example of such underlayer is a bottom anti- reflective coating (BARC). BARC may be formed directly on a substrate, and a photoresist composition may be applied directly on BARC. The application method is not particularly limited, but examples thereof include a method of coating with a spinner or coater.

[0105] The photoresist composition used in methods of this invention is preferably positive tone photoresist composition or negative tone photoresist composition (more preferably positive tone photoresist composition). The photoresist composition used in methods of this invention is preferably chemically amplified photoresist composition.

[0106] The photoresist composition applied above a substrate becomes a photoresist layer. Heating is one preferable measure to cause this change. Thus, step (1 ) of this methodForeignfilingjext P24-242-SEC-WO01 20250925 can be “applying a photoresist composition above a substrate, and heating it to form a photoresist layer”. The heating in step (1 ) can be called as pre bake. The temperature of pre bake is preferably 75 to 140°C (more preferably 80 to 100 C degree). The time of pre bake is preferably 30 to 240 seconds (more preferably 45 to 120 seconds). The pre bake is preferably carried out in air or nitrogen gas atmosphere.

[0107] The thickness of the photoresist layer is preferably 50 to 1 ,500 nm (more preferably 100 to 900 nm; further preferably 200 to 500 nm).

[0108] Before proceeding to step (2), it is possible for this method to comprise pre wetting step, which wet the surface of the photoresist layer. For example, pre wetting liquid is DIW.

[0109] In the case this method comprises pre wetting step, it is a preferable embodiment of this invention that the pre wetting liquid on the surface of the photoresist layer is gradually replaced by the top coating composition, when the top coating composition applied in the step (2). For example, with slowly rotating the substrate, the top coating composition is gradually poured at the center of the substrate (having photoresist layer on it) and existed DIW is replaced by the top coating composition.

[0110] Step (2)The top coating composition applied on the photoresist layer becomes a top coating. The application method is not particularly limited, but examples thereof include a method of coating with a spinner or coater. Spin coating is one of preferable embodiment of this invention as the applying measure of step (2). During such applying measure, solvent (B) in the top coating composition is removed (preferably byForeignfilingjext P24-242-SEC-WO01 20250925 evaporation) and solid components including polymer (A) forms top coating.

[0111] The thickness of the top coating is preferably 3 to 50 nm (more preferably 10 to 45 nm; further preferably 10 to 40 nm).

[0112] It is also one of preferable embodiment of this invention that the top coating composition is applied on the photoresist layer, before the photoresist layer is completely dried (for example by pre bake). In such case, the solvent (B) of the top coating composition can be removed by pre bake.

[0113] The manufactured coating of this invention can give good optical properties as top coating.

[0114] Absorption parameter k (k value) and Index of reflection n (n value) can be measured and calculated using an ellipsometer, such as a J. A. Woollam M-2000 Ellipsometer (software Complete EASE).

[0115] The k value of the manufactured top coating irradiated by 248 nm wavelength (KrF excimer laser) gives preferably “0.1 < k < 0.3” (more preferably “0.15 < k < 0.28”; further preferably “0.20 < k < 0.28”) .

[0116] The n value of the manufactured top coating irradiated by 248 nm wavelength gives preferably “1 .3 < n < 1 .5” (more preferably “1 .4 < n < 1 .5”).

[0117] Not to be bound by theory, it is believed that by controlling the contents of the top composition, it is possible to obtain a top coating with desirable optical properties fit to the underneath layer and substrate, to control reflective light, and / or to avoid undesired phenomenon (e.g., swing ratio).Foreignfilingjext P24-242-SEC-WO01 20250925

[0118] Method for manufacturing resist patternsThis invention provides a method for manufacturing resist patterns. The method comprises following below steps. Manufacturing top coating on photoresist layer. Details of this step is described above as step (1 ) and step (2).(3) Optionally baking the photoresist layer.(4) Exposing the photoresist layer by 248 nm irradiation, through the top coating.(5) Optionally baking the exposed photoresist layer. And (6) developing the exposed photoresist layer.Optionally the method for manufacturing resist pattern can further comprises step of (7) cleaning resist pattern by cleaning liquid.Optionally the method for manufacturing resist pattern can further comprises step (4-2) removing the top coating, or (5-2) removing the top coating.

[0119] In the step (3) and following steps, the term of “photoresist layer” means the fabricated photoresist layer and top coating, unless specifically described. In the case top coating is removed, the step subject to photoresist layer only. For example, if this method comprises step (4-2) removing the top coating, the “photoresist layer” in step (5) means photoresist layer only, because the top coating on the photoresist layer is already removed.

[0120] Step (3)The method of this invention can comprise baking the photoresist layer. This step can come between step (2) forming top coating and step (4) exposure.The temperature of this baking is preferably 75 to 200°C (more preferably 90 to 150 C degree). The time of this baking isForeignfilingjext P24-242-SEC-WO01 20250925 preferably 30 to 240 seconds (more preferably 45 to 120 seconds).

[0121] Step (4)To make the resist pattern, a predetermined mask is used for this exposure.The method of this invention comprises exposing the photoresist layer by 248 nm irradiation, through the top coating. The irradiation light goes through the top coating of this invention. Exposure is done by 248 nm irradiation. This wavelength accepts a range of ±1%.

[0122] Step (4-2) and step (5-2)The method of this invention can further comprise a step (4-2) removing the top coating after step (4), and before step (5) or step (6).

[0123] Also, it is possible of this invention that the method can further comprise a step (5-2) removing the top coating between step (5) and step (6).

[0124] In the case the step (4-2) is used in this method, the step (5-2) is not used in the method. In the case the step (5-2) is used in this method, the step (4-2) is not used in the method.

[0125] Each of step (4-2) and (5-2) doesn’t remove photoresist layer. Dissolution of upper portion of photoresist layer is accepted in each of step (4-2) and step (5-2), for example 0 to 10 % of photoresist layer thickness reduction allowed.

[0126] For such remover in step (4-2) and step (5-2), known liquid can be used as far as the liquid only removes only the top coating, but not substantially remove photoresist layer. ForForeignfilingjext P24-242-SEC-WO01 20250925 example, solvent (B) used in the top coating composition (or mixture with polar solvent) can be used for this purpose.

[0127] Step (5)The method of this invention can further comprise baking the exposed photoresist layer. Such bake can be called as Post Exposure Bake (PEB).The PEB temperature is preferably 100 to 220 C degree (more preferably 110 to 150 C degree), and the heating time is preferably 30 to 240 seconds (more preferably 45 to 120 seconds).

[0128] Step (6)The method of this invention comprises developing the exposed photoresist layer. In case that top coating remains on the photoresist layer before this developing, both of top coating and photoresist layer are removed by developer. Development of the exposed resist film is performed using a developer to form a resist pattern.

[0129] Examples of the developer include an alkali developer and an organic solvent development or the like, and the alkali developer is preferred. The more preferred embodiment as the developer in this method is a 2.38 mass % (±1 % is accepted) tetramethylammonium hydroxide (TMAH) aqueous solution. Further, a surfactant or the like can also be added to the developer. The temperature of the developer is preferably 5 to 50°C (more preferably 25 to 40°C) and the developing time is preferably 10 to 300 seconds (more preferably 20 to 60 seconds). As the developing method, any publicly known method such as immersive development and paddle development can be used.Foreignfilingjext P24-242-SEC-WO01 20250925

[0130] In the case the photoresist composition is positive tone photoresist composition, the photoresist portion receiving irradiation light become soluble to the developer.

[0131] After development, the photoresist layer can be dried, by for example spin drying.

[0132] Step (7)The method of this invention can further comprise cleaning resist pattern by cleaning liquid. Step (7) can be used to clean the resist pattern in order to remove localized residues came from preceding steps.

[0133] As the cleaning liquid, water (for example DIW), organic solvents (for example, IPA, PGME, PGMEA, PGEE, nBA are included) or mixture of them are included. It is one preferred embodiment of this invention that cleaning liquid comprises a surfactant as 0.001 to 10 mass % comparing to the total of the cleaning liquid. It can reduce a surface tension of such cleaning liquid to avoid pattern collapse.

[0134] As a preferred embodiment of this invention, the cleaning is performed by replacing the developer with the cleaning liquid. Examples of the cleaning liquid include those described in JP 2019-519804 A and WO 2021 / 204651 A1. Sequential cleaning by multiple types of cleaning liquid is included in this step (7), for example 1stcleaning is done by DIW, and 2ndcleaning follows by DIW including a surfactant.

[0135] As one preferable embodiment, the top coating has a feature that it can be removed by a developer. This removability can be measured following method. Preparing a top coating of 20 nm thickness on silicon wafer on silicon wafer; developing it by 2.38 mass % TMAH for 1 min at roomForeignfilingjext P24-242-SEC-WO01 20250925 temperature; spin drying the substrate. The reduced amount of the top coating thickness can give preferably 80 to 100% (more preferably 90 to 100%; further preferably 95 to 100%). Here 100% means that there is no remained top coating on the wafer.

[0136] As another preferred embodiment, the photoresist patterns have a feature that swing ratios is less than 20%, more preferable less than 10%, even more preferable less than 5%. The swing ratio is defined as the difference between maxima and minima of the key lithography parameter, e.g. critical dimension or dose to print, divided by the average value (max+min) / 2.

[0137] Method for manufacturing deviceThe manufactured resist patterns can be used both for etching mask and ion dope mask. Thus, this invention further provides a method for manufacturing a device, which comprises;Etching using the resist patterns manufactured by the method described above as a mask, and processing a substrate; or Doping ion into the substrate or underlayer with using the resist patterns manufactured by the method described above. The resist patterns manufacturing method is described step by step in preceding descriptions.

[0138] The subject of etching and ion doping though resist patterns as a mask can be both of substrate or underlayer. Underlayer means layer(s) fabricated between substrate and photoresist layer. Multiple types of underlayer fabrication is encompassed in such underlayer (for example, such constitution of “Substrate / SOC / BAR / Photoresist layer / Top coating”). Preferably single layer is used as the underlayer. Examples of the underlayer are BARC or Spin on Carbon layerForeignfilingjext P24-242-SEC-WO01 20250925(SOC), which are preferably having properties of higher etching resistance than photoresist layer / patterns.

[0139] Etching using the resist pattens as a maskFor etching, any publicly known method such as dry etching and wet etching can be used, and dry etching is more preferable.For example, underlayer can be etched using the resist patterns as an etching mask, and the substrate can be etched using the obtained underlayer patterns as an etching mask to process the substrate. Further, while etching the underlayer using the resist pattern as an etching mask, the substrate can also be uninterruptedly etched. The processed substrate becomes, for example, a patterned substrate. After processing, the remained resist pattens or their residues can be removed, if necessary.

[0140] The method of this invention can further comprise step of forming a wiring on the processed substate.

[0141] Doping ion into the substrate or underlayerFor ion doping, any publicly know method can be used.Preferably the subject of ion doping though resist patterns as a mask is around surface of the substrate. For example, conductive impurity ion is doped into surface and slight depth of the surface of the substrate. With this method, controlled conductivity patterns can be designed on the substrate.

[0142] DeviceThe substrate is further processed to form a device, with applying known methods. Preferably, the method further comprises a step of forming a wiring on the processed substrate. If necessary, the substrate is cut into chips, connected to lead frames, and packaged with resin. In theForeignfilingjext P24-242-SEC-WO01 20250925 present invention, this packaged product is called a device. Preferably, the device is a semiconductor device.

[0143] The present invention is further illustrated by the examples following hereinafter which shall in no way be construed as limiting. The skilled person will acknowledge that various modifications, additions and alternations may be made to the invention without departing from the spirit and scope of the invention as defined in the appended claims.Examples

[0144] Working Example 1 - polymer synthesis and analysis 9-anthracenylmethyl methacrylate, Poly(ethylene glycol) methacrylate (average Mn 360), and methacrylic acid are mixed in 18:41 :41 molar ratio and polymerized in Tetrahydrofuran (THF) using 3 mol% 2,2'- Azobis(isobutyronitrlle). The resulting polymer 1 is purified by precipitation with heptane, and volatiles are removed under reduced pressure.The polymer 1 is dissolved in PGME to obtain 3wt% solution. The resulting composition 1 is spin coated on silicon wafer at 3,500 rpm for 20 sec and baked at 110°C for 60 seconds. Films are analyzed using Woollam ellipsometer to give n=1 .450, k=0.261 at 248nm and film thickness of 86 nm.

[0145] Working Example 2 - Solubility in developer The composition described in Working Example 1 (Composition 1 ) is spin coated on silicon wafer at 3,500 rpm for 20 sec and baked at 110°C for 60 seconds. Film thickness is evaluated using Woollam ellipsometer to give 88.8±8.5 nm. The wafer is immersed in AZ 726 developer (Metalchem) for 60 seconds and then rinsed with DIW. Film thickness is evaluated using Woollam ellipsometer to give 4.9±0.6 nm, confirming solubility of the polymer 1 in AZ 726.Foreignfilingjext P24-242-SEC-WO01 20250925

[0146] Working Example 3 - Evaluation of intermixing with photoresist layerDX6270P (Merck Electronics ltd) is a chemically amplified positive photoresist composition. DX6270P is spin coated on silicon wafer at 2,650 rpm and baked at 120°C for 90 seconds to give DX6270P layer. Film thickness of it is evaluated using Woollam ellipsometer to give 397 nm. The polymer 1 is dissolved in DIWto obtain 1wt% solution, resulting in Composition 2. The DX6270P layer is pre-wetted with DIW and the Composition 2 is spin coated on silicon wafer at 1 ,500 rpm for 20 sec. The total thickness is evaluated using Woollam ellipsometer to give 417 nm. The silicon wafer is baked at 130°C for 90 seconds, immersed in 2.38wt% TMAH solution, and air dried. Film thickness is evaluated using Woollam ellipsometer to give 360 nm. Detected film loss is 37 nm. Film loss is defined as a difference between photoresist thicknesses of freshly made film and after immersion in 2.38wt% TMAH solution.The same procedure except for changing top coating composition from Composition 2 to Aquatar8A (Merck Electronics ltd) to give 30 nm photoresist film loss.

[0147] Working Example 4 - Preparation of top coating compositionThe polymer 1 is mixed with 94wt% DIW and 5wt% isopropanol to obtain 1wt% polymer solution, composition 3.

[0148] Working Example 5 - Preparation of sample wafers To make one set of wafers, twelve silicon substrates are individually coated using a spin-coater with a photoresist DX6270P at various rotation speeds to form photoresist layers with thicknesses of 330 to 440 nm at intervals of 10 nm. Thereafter, the substrates are subjected to soft-baking at 120°C for 90 seconds, to obtain twelve substrates coated withForeignfilingjext P24-242-SEC-WO01 20250925 the resist layers. To obtain samples, the twelve obtained substrates coated with the photoresist layers of different thicknesses are individually coated by using a spin-coater with the top coating composition described in the Working Example 4 at various rotation speeds to form the resultant films with thickness of 25 nm.The procedure is repeated eleven times to obtain eleven sets of wafers.

[0149] Comparative Example 1 - Preparation of Comparative Example 1Same procedures are applied to Working Example 5, except for changing top coating composition from Working Example 4 to AZ Aquatar8A (Merck Electronics ltd) and changing its thickness into 43 nm.

[0150] Reference Example 5 - Preparation of ReferenceExample 5Same procedures are applied to Working Example 5, except for no top coating is applied on top of DX6270P resist layers.

[0151] Working Example 6 Measurement of Swing Curve andSwing RatioEvery set of samples of the Working Example 5, Comparative Example 1 and Reference Example 5 is individually subjected to whole image exposure, using a photomask 500 nm L / S 1 :1. Doses from 160 to 260 J / m2at intervals of 10 J / m2are used.After exposure every sample is subjected to baking treatment at 135°C for 90 seconds, and subsequently subjected to development treatment. Thereafter, Critical Dimension (CD) is detected using SEM imaging. CD and dose-to-print (DTP) values are obtained from exposure latitude (EL) curves and plotted against photoresist film thickness. CD curve is obtained Fig 1.Foreignfilingjext P24-242-SEC-WO01 20250925

[0152] "Swing ratio" is obtained by dividing the difference between the maximum value and the minimum value of the curve by the average between the two, and presented in the Table 1.

[0153] "Reduction ratio" is defined as “1 -(Swing ratio with TARC / Swing ratio without TARC)”. Swing ratio without TARC use “Reference Example 5”.Table 1 :

[0154] Comparative Example 1 - Comparative polymer 1 synthesis 9-anthracenylmethyl methacrylate and methacrylic acid are mixed in 8:92 molar ratio and polymerized in Tetrahydrofuran (THF) using 3 mol% 2,2'-Azobis(isobutyronitrlle). The resulting Comparative polymer 1 is purified by precipitation with heptane, and volatiles are removed under reduced pressure.

[0155] Working Example 7 - Polymer 2 synthesis 9-anthracenylmethyl methacrylate, Poly(ethylene glycol) methacrylate (average Mn 360), and methacrylic acid are mixed in 10:7:83 molar ratio and polymerized in Tetrahydrofuran (THF) using 3 mol% 2,2'- Azobis(isobutyronitrlle). The resulting polymer 2 is purified byForeignfilingjext P24-242-SEC-WO01 20250925 precipitation with heptane, and volatiles are removed under reduced pressure.

[0156] Working Example 8 - Solubility in DIWPolymer 1 is mixed with DIW to prepare 1 wt% solution. The resulting mixture is left for mixing at ambient temperature for overnight. The resulting composition 4 appears as clear solution.

[0157] Polymer 1 is mixed with DIW to prepare 10 wt% solution. The resulting mixture is left for mixing at ambient temperature for overnight. The resulting composition 5 appears as clear solution.

[0158] Comparative polymer 1 is mixed with DIW to prepare 1 wt% solution. The resulting mixture is left for mixing at ambient temperature for overnight. The resulting Comparative composition 2 appears as turbid solution, solids clearly observed.

[0159] Polymer 2 is mixed with DIW to prepare 1 wt% solution. The resulting mixture is left for mixing at ambient temperature for overnight. The resulting composition 6 appears as turbid solution, solids clearly observed.

Claims

Foreignfilingjext P24-242-SEC-WO01 20250925Patent Claims1 . A top coating composition comprising polymer (A), wherein the polymer (A) comprises repeating unit A1 and unit A2;formula A1 , formula A2 where unit A1 is represented by formula A1 ,R11 , R12 and R13 are each independently H or methyl,R14 is each independently C1-10 alkyl, C1-10 alkoxyl, -OH, -COOH, - COOR15, -SO3H, or cyano, where one or more of methylene in alkyl portion in R14 can be replaced by ether linker, one or more of methyl in alkyl portion in R14 can be replaced by hydroxyl, and one or more of alkyl of R14 can further include heteroatom,R15 is each independently C1-6 alkyl, -SO3H, cyano, C2-4 alkenyl or C2-4 alkynyl,L11 is single bond, or -COO-L12 is single bond, or C1-3 alkylene, and m 1 is number of 0 to 9; where unit A2 is represented by formula A2,R21 , R22 and R23 are each independently H or methyl,R24 is each independently H or methyl,R25 is H, hydroxyl, C1-6 alkoxyl, or -COOH, L21 is single bond, -CO- or C1-6 alkylene, L22 is single bond, or C1-10 alkylene, andForeignfilingjext P24-242-SEC-WO01 20250925 ri2i is number of 1 to 10; where each number of unit A1 and unit A2 in polymer (A) are denoted as nA1 and nA2 respectively, and the total number of all unit contained in the polymer (A) is denoted as nAtotai, these satisfy following,0% < (nA1 I nAtotai) < 90%, and0% < (nA2 / nAtotai) < 95%.

2. The top coating composition according to claim 1 , wherein the polymer (A) further comprises unit A3,formula A3 where unit A3 is represented by formula A3,R31 , R32 and R33 are each independently H or methyl, l_3i is single bond, or -COO-,R34 is H, or C1-10 alkyl, in the alkyl of R34, one or more of methylene portion can be replaced by -O-, or -CO-, and in the alkyl of R34, one or more H can be replaced by hydroxyl; where the number of unit A3 in polymer (A) is denoted as nA3, these satisfy following,0% < (nA3 / nAtotai) < 70%.

3. The top coating composition according to claim 1 or 2, further comprising solvent (B); optionally the solvent (B) comprises water (B1 ); optionally the content of water (B1 ) comparing to total of solvent(B) is 50 to 100 mass%; optionally the solvent (B) comprises organic solvent (B2), and theForeignfilingjext P24-242-SEC-WO01 20250925 content of organic solvent (B2) comparing to total of solvent (B) is 0 to 100 mass%; or optionally the organic solvent (B2) comprises alcohol solvent (B2- 1 ), and the content of alcohol solvent (B2-1 ) comparing to total of solvent (B) is 0 to 100 mass%.

4. The top coating composition according to any of claim 1 to 3, further comprising basic compound (C), surfactant (D), or polymer (E).

5. The top coating composition according to any of claim 1 to 4, wherein the Mw of polymer (A) is 5 to 100 kDa; optionally the Mw of polymer (E) is 5 to 100 kDa.

6. The top coating composition according to any of claim 1 to 5, where the content of polymer (A) comparing to total of the top coating composition is 0.10 to 15 mass%; optionally the content of solvent (B) comparing to total of the top coating composition is 40 to 99.99 mass%; optionally the content of basic compound (C) comparing to total of polymer (A) is 0 to 10 mass%; or optionally the content of surfactant (D) comparing to total of polymer (A) is 0 to 25 mass%; or optionally the content of polymer (E) comparing to total of polymer (A) is 0 to 25.0 mass%.

7. The top coating composition according to any of claim 1 to 6, where it is a top anti-reflective coating composition; wherein optionally the top anti-reflective coating composition is KrF top anti-reflective coating composition.

8. A method for manufacturing top coating comprising following steps;(1 ) applying a photoresist composition above a substrate to form aForeignfilingjext P24-242-SEC-WO01 20250925 photoresist layer; and(2) applying the top coating composition according to any of claim 1 to 7 on the photoresist layer to form a top coating.

9. The method for manufacturing according to claim 8; wherein the n value of the manufactured top coating irradiated by 248 nm wavelength gives “1 .3 < n < 1 .5”; and / or the k value of the manufactured top coating irradiated by 248 nm wavelength gives “0.1 < k < 0.3”.

10. A method for manufacturing resist patterns comprising following steps; manufacturing top coating on photoresist layer according to claim 8 or 9;(3) optionally baking the photoresist layer;(4) exposing the photoresist layer by 248 nm irradiation, through the top coating;(5) optionally baking the exposed photoresist layer; and(6) developing the exposed photoresist layer; wherein optionally the method for manufacturing resist pattern further comprises step of (7) cleaning resist pattern by cleaning liquid; optionally the method for manufacturing resist pattern further comprises step (4-2) removing the top coating, or (5-2) removing the top coating.11 . The method for manufacturing resist patterns according to claim 10; wherein the top coating has a feature that it can be removed by a developer; or the photoresist patterns have a feature that swing ratio is less thanForeignfilingjext P24-242-SEC-WO01 2025092520%.

12. A method for manufacturing a device, comprising etching using the resist patterns manufactured by the method according to claim 10 or 11 as a mask, and processing a substrate; or doping ion into the substrate or underlayer with using the resist patterns manufactured by the method according claim 10 or 11 .

13. The method for manufacturing a device according to claim 12, further comprising forming a wiring on the processed substrate; optionally, the device is a semiconductor device.

14. A polymer (A) comprising repeating unit A1 and unit A2;formula A1 , formula A2 where unit A1 is represented by formula A1 ,Ri 1 , R12 and R13 are each independently H or methyl,R14 is each independently C1-10 alkyl, C1-10 alkoxyl, -OH, -COOH, - COOR15, -SO3H, or cyano, where one or more of methylene in alkyl portion in R14 can be replaced by ether linker, one or more of methyl in alkyl portion in R14 can be replaced by hydroxyl, and one or more of alkyl of R14 can further include heteroatom,R15 is each independently C1-6 alkyl, -SO3H, cyano, C2-4 alkenyl orForeignfilingjext P24-242-SEC-WO01 20250925C2-4 alkynyl,Li 1 is single bond, or -COO-L12 is single bond, or C1-3 alkylene, and m 1 is number of 0 to 9; where unit A2 is represented by formula A2,R21 , R22 and R23 are each independently H or methyl,R24 is each independently H or methyl,R25 is H, hydroxyl, C1-6 alkoxyl, or -COOH,L21 is single bond, -CO- or C1-6 alkylene,L22 is single bond, or C1-10 alkylene, and n2i is number of 1 to 10; where each number of unit A1 and unit A2 in polymer (A) are denoted as nA1 and nA2 respectively, and the total number of all unit contained in the polymer (A) is denoted as nAtotai, these satisfy following,0% < (nA1 I nAtotai) < 90%, and0% < (nA2 / nAtotai) < 95%.

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