Top coating composition

Abstract

The present invention relates to a top coating composition comprising polymer (A), surfactant (B) and solvent (S). The polymer (A) comprises a side chain comprising a fused aromatic ring. The surfactant (B) comprises an aliphatic hydrocarbon portion (B1) and an alkylene oxide portion (B2). the solvent (S) comprises water (S1). 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

[0001] Foreignfiling_text P24-255-SEC-WO01 20251002

[0002] TOP COATING COMPOSITION

[0003] Field of the invention

[0004] The present invention relates to a top coating composition, and using thereof.

[0005] Background Art

[0006] 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.

[0007] 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.

[0008] 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.

[0009] Patent document 2 describes a TARC composition comprising a solvent and an anthracene skeleton-containing polymer having a hydrophilic group.

[0010] Patent Literature

[0011] 1. US7544750

[0012] 2. US2010279235Foreignfiling_text P24-255-SEC-WO01 20251002

[0013] Summary of the invention

[0014] The present invention aims to provide a top coating composition that addresses above mentioned challenges, offering good properties fit to mass production processes.

[0015] Inventors have found that at least one of inventions described 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 reduce film loss of underneath photoresist layer; 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 provide a process composition friendly to human and environment; and possible to improve yield of device production.

[0016] Namely, it is found a top coating composition comprising polymer (A), surfactant (B) and solvent (S). The present invention also provides a method for manufacturing top coating, resist patterns, and a device.

[0017] Technical effects of the invention

[0018] The present Inventors have found that one or more of the above-described technical problems can be solved by the features as defined in the claims.

[0019] Definition of the terms

[0020] Unless otherwise specified in the present specification, the definitions and examples described in this paragraph are followed.

[0021] 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 %) isForeignfiling_text P24-255-SEC-WO01 20251002

[0022] described, it means sum of the plurality of species.

[0023] “And / or” includes a combination of all elements and also includes single use of the element.

[0024] When a numerical range is indicated using “to”

[0025]

[0026] 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.

[0027] 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.).

[0028] 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.

[0029] Celsius is used as the temperature unit. For example, 20 degrees means 20 degrees Celsius.

[0030] 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.

[0031] Detailed description of the invention

[0032] Herein later, detailed embodiments are explained as explanatory purposes. These should not be taken into consideration to limit the scope of the claims.

[0033] According to the present invention, said top coating composition comprises polymer (A), surfactant (B) and solvent (S); whereinForeignfiling_text P24-255-SEC-WO01 20251002

[0034] the polymer (A) comprises a side chain comprising a fused aromatic ring; surfactant (B) comprises a aliphatic hydrocarbon portion (B1) and an alkylene oxide portion (B2):

[0035] the solvent (S) comprises water (S1 );

[0036] the content of water (S1 ) relative to total of solvent (S) is 90 to 100 mass%.

[0037] As one embodiment of this invention, the top coating composition preferably essentially consists of polymer (A), surfactant (B), solvent (S), basic compound (C), polymer (D), and additive (E) (more preferably consists of polymer (A), surfactant (B), solvent (S), basic compound (C), polymer (D), and additive (E)).

[0038] - Composition

[0039] The top coating composition of this invention comprises any embodiments described in this specification. The top coating composition is applied on the photoresist layer, and is made into a top coating.

[0040] 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 detail later.

[0041] As one more preferable embodiment of this invention, the top anti-reflective coating composition is an ArF top anti-reflective coating composition. The ArF top anti-reflective coating composition is one concrete example of top anti-reflective coating composition, which is used in the photolithography process with using ArF light exposure.

[0042] As one further 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0043] 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. As one embodiment of this invention, the top composition can have a feature of its dynamic surface tension of 60 mN / m or lower. The dynamic surface tension is more preferably 30 to 60 mN / m (further preferably 40 to 60 mN / m). The dynamic surface tension can be measured using the bubble pressure method in accordance with ISO standards. 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).

[0044] It is one preferable embodiment of this invention that the top coating composition has less or none of fluorine (F) in it. Average mass amount of the fluorine 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%) relative 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”.

[0045] - Polymer (A)

[0046] The polymer (A) comprises a side chain comprising a fused aromatic ring. The side chain of the polymer is a branched structure that is bonded to the main chain.

[0047] As one embodiment of this invention, the fused aromatic ring in the polymer (A) can have a heteroatom or can have none of a heteroatom. Examples of such heteroatom are preferably N, S, or O (more preferably N or S; furtherForeignfiling_text P24-255-SEC-WO01 20251002

[0048] preferably N). Embodiments of fused aromatic rings having a heteroatom are, for example, quinoline, isoquinoline and indole.

[0049] As a more preferable embodiment of the invention, the fused aromatic ring in the polymer (A) does not have a heteroatom, which is composed of only C and H. Embodiments of fused aromatic rings not having a heteroatom are, for example, naphthalene, phenanthrene, anthracene, tryphenylene, pyrene, chrysene, and perylene.

[0050] The top coat topcoat composition of this invention can comprise multiple types of polymer (A) in it, as long as each of polymer (A) comprises a side chain comprising a fused aromatic ring.

[0051] End portion of polymer (A) can be modified with any type of modification group, which are publicly available. For example, one or more end portions of polymer (A) can be modified by -C(CH3)2(CN), -C(CH3)2-C=NH(NH3), or -(4-cyanovaleric acid).

[0052] It is one preferable embodiment of this invention that the polymer (A) has less or none of fluorine (F) in it. Average mass amount of the fluorine 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%) relative to the total of polymer (A). This number can be calculated from average of atomic mass.

[0053] It is one embodiment of this invention that the content of polymer (A) relative 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%).

[0054] The polymer (A) can take copolymerization status, as preferably random copolymer, graft copolymer, block copolymer, alternating copolymer, or anyForeignfiling_text P24-255-SEC-WO01 20251002

[0055] mixture of any of these (more preferably random copolymer, block copolymer, or alternating copolymer; further preferably random copolymer).

[0056] 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).

[0057] Molecular weight of polymer (A) can be determined Gel Permeation Chromatography. Preferably polystyrene can be used as a reference.

[0058] Unless described otherwise, the same applies to following descriptions as to molecular weight of any type of polymer.

[0059] - UnitAI

[0060] According to the present invention, said polymer (A) can comprise unit A1. The unit A1 is represented by formula A1.

[0061] LA12

[0062]

[0063] - Formula A1

[0064] RA11, RA12and RA13are each independently H or methyl. RA11is preferably methyl. RA12and RA13are preferably H.

[0065] R14is each independently C1-10alkyl, C1-10alkoxyl, -OH, -COOH, -COORA15, -SO3H, or cyano,Foreignfiling_text P24-255-SEC-WO01 20251002

[0066] where one or more of methylene in alkyl portion in RAU can be replaced by ether linker, one or more of methyl in alkyl portion in RAU can be replaced by hydroxyl, and one or more of alkyl of RAU can further include heteroatom.

[0067] RA15is each independently C1-6alkyl, -SO3H, cyano, C2-4alkenyl or C2-4alkynyl.

[0068] RA14is preferably C1-10alkyl, -OH, or -COOH; more preferably C1-10alkyl, or -OH; further preferably C1-10alkyl; further more preferably C1-5alkyl.

[0069] Said alkyl of RA14is linear, branched, cyclic or any combination of any of these; preferably linear, branched or combination of linear and branched; more preferably linear.

[0070] One or more of methylene in alkyl portion in RA14can be replaced by ether linker. In the case that multiple methylene in alkyl portion in R14are 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 RA14is replaced by ether linker.

[0071] One or more of methyl in alkyl portion in RA14can be replaced by hydroxyl. It is preferable that one methyl in alkyl portion in RA14is replaced by hydroxyl. It is preferable embodiment of the invention that none of methyl in alkyl portion in RA14is replaced by hydroxyl.

[0072] One or more of alkyl of RA14can further include heteroatom. It is one preferable embodiment of this invention that one of RA14further 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 RA14can further include heteroatom.

[0073] RA15is preferably C1-6linear alkyl, C3-6branched alkyl, -SO3H, cyano, C2-4alkenyl or C2-4alkynyl; 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0074] As one of embodiment, -CH(OH)-CH2-OH can be regarded as such RA14with replacements. In this embodiment, two methyls of original C4alkly (-CH(CH3)-CH2-CH3) are substituted by hydroxyls (-OH).

[0075] As another embodiment, -CH(OH)-CH2-OCH3can be regarded as such RA14with a substitution and a replacement. In this embodiment, original C5alkyl is (-CH(CH3)-CH2-CH2-CH3), in which one methyl is replaced by -OH and one methylene (-CH2) is replaced by -O-.

[0076] As further embodiment which this invention provides, -CH2-OH can be regarded as such RA14with a replacement. In this embodiment, original C2alkyl is (-CH2-CH3), in which a methyl is replaced by -OH.

[0077] LA11is single bond, or -COO-; preferably -COO-.

[0078] LA12is single bond, or C1-3alkylene; 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 LA12. It is also another preferable embodiment of this invention that anthracene bonds to main chain at 2ndposition, via LA12.

[0079] nA11is number of 0 to 9; preferably 0 to 5; more preferably 0 to 3; further preferably 0 or 1; further more preferably 0.

[0080] nA12is 0 or 1. In the case where 193 nm irradiation is used in aforementioned step (4), preferably nA12takes 0 and the fused aromatic ring takes a naphthalene structure. In the case where 248 nm irradiation is used in step (4), preferably nA12takes 1 and the fused aromatic ring takes an anthracene structure.

[0081] As one embodiment of this invention, below left unit can be read by original scope of formula A1. Where, RA11, RA12and RA13are H; nA11= nA12=0; and LA11is -COO-, and LA12is methylene. Anthracene bonds to main chain at 9thposition, via LA12.Foreignfiling_text P24-255-SEC-WO01 20251002

[0082] As another embodiment of this invention, below right unit can be read by original scope of formula A1. Where, RA11, RA12and RA13are methyl; RA14is -OH; nA11=1; nA12=0; and LA11and LA12are single bond. Anthracene bonds to main chain at 1stposition, via LA12.

[0083]

[0084] Examples of the unit A1 include the followings.

[0085]

[0086] Foreignfiling_text P24-255-SEC-WO01 20251002

[0087]

[0088] Number of unit A1 and in polymer (A) is denoted as nA1. The total number of all unit contained in the polymer (A) is denoted as nAtotal.

[0089] As one preferable embodiment of this invention, the following condition is satisfied,

[0090] 0% < (nA1 / nAtotal) < 90%.

[0091] (nA1 I nAtotal) is preferably 1 to 70%; more preferably 5 to 50%; further preferably 10 to 30%; further more preferably 15 to 20%.

[0092] Although not to be bound by theory, it is believed that the top coating made from the top coating composition comprising polymer A which has unit A1 can exhibit useful properties, for example, optical property like the n value and / or k value, when irradiated by 193 or 248 nm wavelength light.

[0093] Unit A2Foreignfiling_text P24-255-SEC-WO01 20251002

[0094] According to the present invention, said polymer (A) can comprise unit A2. The unit A2 is represented by formula A2.

[0095] RA22

[0096] A23

[0097]

[0098] - Formula A2

[0099] RA21, RA22 and RA23 are each independently H or methyl. RA21 is preferably methyl. RA22 and RA23 are preferably H..

[0100] RA24 is each independently H or methyl; preferably H.

[0101] RA25 is H, hydroxyl, C1-6 alkoxyl, -SO3H or -COOH; preferably H, hydroxyl, or methoxy; more preferably H or hydroxyl, further preferably hydroxyl.

[0102] LA21 is single bond, -CO- or C1-6 alkylene; preferably single bond, -CO- or -CH2-; more preferably single bond or -CO-; further preferably -CO-.

[0103] LA22 is single bond, or C1-10 alkylene; preferably single bond, or C1-4 alkylene; more preferably single bond.

[0104] nA21is number of 1 to 10; preferably number of 1 to 9; more preferably number of 2 to 8.

[0105] As one embodiment of this invention, below left unit can be read by original scope of formula A2. Where, RA21, RA22 and RA23 are H; RA24 is H; RA25 is hydroxyl; LA21is -CO-; LA22is single bond; and nA21is 3. As one embodiment of this invention, below right unit can be read by original scopeForeignfiling_text P24-255-SEC-WO01 20251002

[0106] of formula A2. Where, RA21 is methyl, RA22 and RA23 are H; RA24 is methyl; RA25 is methoxy; LA21is single bond; LA22is single bond; and nA21is 1.

[0107] o

[0108]

[0109] Although not to be bound by theory, the top coating made from the top coating composition comprising polymer A which has unit A2 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.

[0110] Number of unit A2 in polymer (A) is denoted as nA2.

[0111] nA2 and nAtotalcan satisfy following,

[0112] 0% < (nA2 / nAtotal) < 95%.

[0113] (nA2 I nAtotal) is preferably 5 to 90%; more preferably 10 to 80%; further preferably 20 to 70%; further more preferably 40 to 60%. It is also another aspect of this invention that (nA2 I nAtotal) is 0.0%.

[0114] - Unit A3

[0115] According to the present invention, said polymer (A) can further comprise unit A3. The unit A3 is represented by formula A3.Foreignfiling_text P24-255-SEC-WO01 20251002

[0116]

[0117] - Formula A3

[0118] RA31, RA32and RA33are each independently H or methyl. RA31is preferably methyl. RA32and RA33are preferably H.

[0119] LA31is single bond, or -COO-; preferably -COO-.

[0120] RA34 is H, or C1-10 alkyl.

[0121] In the alkyl of RA34, one or more of methylene portion can be replaced by -O-, or -CO- In the case that multiple methylene in alkyl portion in RA34 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 RA34 is replaced by -O-.

[0122] In the alkyl of RA34, one or more H can be replaced by hydroxyl. It is preferable embodiment of the invention that none of H of RA34 is replaced by hydroxyl.

[0123] RA34 is preferably H, or C1-4 alkyl; more preferably H, methyl, ethyl, or n-propyl; further preferably H.

[0124] The number of unit A3 in polymer (A) is denoted as nA3.

[0125] nA3 and nAtotalcan satisfy following,

[0126] 0% < (nA3 / nAtotal) < 70%.

[0127] (nA31 nAtotal) is preferably 0.1 to 70%; more preferably 10 to 60%; further preferably 20 to 60%; further more preferably 20 to 50%.

[0128] 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 coatingForeignfiling_text P24-255-SEC-WO01 20251002

[0129] composition can exhibit good property, e.g., good solubility and / or removability by developer (e.g., 2.38 mass% TMAH).

[0130] - Other unit

[0131] According to the present invention, said polymer (A) can further comprise unit other than unit A1, A2 or A3.

[0132] The number of unit other than unit A1, A2 or A3 in polymer (A) is denoted as nAother.

[0133] nAother and nAtotalsatisfies below,

[0134] 0% < (nAother I nAtotal) < 20%

[0135] (nAother I nAtotal) is preferably 0 to 10%; more preferably 0% or more and less than 10%; further preferably more than 0% and less than 5%.

[0136] It is one preferable embodiment of this invention that the “other unit” in polymer (A) has less or none of fluorine(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%) relative to the total of the “other unit”. This number can be calculated from average of atomic mass.

[0137] It is preferable that the polymer (A) essentially consists of repeating units A1, A2 and A3. It is more preferable that the polymer (A) consists of repeating units A1, A2 and A3 ((nAother I nAtotal)= 0%). It goes without saying, for the sake of clarity, it is included into said embodiment that the end portion of polymer (A) is modified.

[0138] - Surfactant (B)

[0139] The top coating composition of this invention comprises surfactant (B), which comprises an aliphatic hydrocarbon portion (B1) and an alkylene oxide portion (B2). As preferable one embodiment of this invention, surfactant (B) is a nonionic surfactant. As one embodiment of this invention,Foreignfiling_text P24-255-SEC-WO01 20251002

[0140] surfactant (B) preferably does not comprise an aromatic hydrocarbon structure (more preferably does not comprise cyclic ring structure).

[0141] Surfactant (B) can be represented by below formula (B’).

[0142]

[0143] Formula (B’) The left side of formula (B’) explains an aliphatic hydrocarbon portion (B1). The right side of formula (B’) explains an alkylene oxide portion (B2).

[0144] Ali is a C2-30 aliphatic hydrocarbon, which comprises one or multiple of -CH2- (methylene), -CH=CH- (vinylene), -C=C- (acetylene), or any combination of any of these. As one embodiment of this invention, Ali preferably does not comprise an aromatic hydrocarbon structure (more preferably does not comprise cyclic ring structure). Ali is preferably C2-30 alkane, C2-30 alkene, C2-30 alkyne, or any combination of any of these (more preferably C2-20 alkane, C2-4 alkyne, or any combination of any of these; further preferably C2-18 alkane, or a combination of C2-18 alkane and -C=C-). The alkane portion of Ali is preferably linear or branched alkane, or their combination (more preferably linear alkane, or branched alkane). It is one embodiment of this invention that Ali comprises preferably one or none of -C=C- (more preferably one -C=C-).

[0145] nB11is 0, 1 or 2; preferably 0 or 1, more preferably 0. When nB11is 0, Ali works as the aliphatic hydrocarbon portion (B1), and bonds to an alkylene oxide portion (B2).Foreignfiling_text P24-255-SEC-WO01 20251002

[0146] X is -0-, -C00-, -N=, or -C(=O)-N=. When one of X is -O-, or -COO- one linkage site starts from the X to bond one of alkylene oxide portion (B2). Rest of the alkylene oxide portion (B2) can bond to another X, or can bond to Ali directly. When one of X is -N=, or -C(=O)-N=, two linkage sites start from the X to bond two of alkylene oxide portions (B2). Rest of the alkylene oxide portion (B2) can bond to another X, or can bond to Ali directly.

[0147] As one embodiment of this invention, the below compound can be read by original scope of formula (B’). Where, Ali is an Ce alkyl, nsn=1, and the one of X is “-N=”. nB22= nB24=1. “Alki-O-" and “Alk2-O-" bond to the X. The two linkage sites start from the X to bond two of alkylene oxide portions (B2). “Alks-O-" bonds to the Ali. Another alkylene oxide portion (B2) bonds to Ali directly. nB11= nB21=20, nB25=30. Alk1, Alk2, and Alk3are ethylene. RB21, RB22and RB23are -OH.

[0148] 30

[0149]

[0150] Each of nB2i, nB23 and nB25 is independently a number of 1 to 50 (preferably 2 to 30; more preferably 3 to 20; further more preferably 3 to 10).

[0151] nB22 is 0 or 1. One preferable embodiment of nB22 is 0. Another preferable embodiment of nB22 is 1.

[0152] When nB22 is 0, the group denoted by nB22 does not exist in the surfactant (B). The same applies to nB24.Foreignfiling_text P24-255-SEC-WO01 20251002

[0153] As one embodiment of this invention, the below compound can be read by original scope of formula (B’). Where, Ali is C5alkyl, nB11=0, nB21=9, nB22=nB24=0, Alk1is ethylene, and RB21is -OH.

[0154]

[0155] A distribution of repetitions is acceptable for formula (B'). As one embodiment of this invention, the below compound can be read by original scope of formula (B’). Ali is a combination of two C6alkyls and one -C≡C-(acetylene). nB11=0, nB22=1, and nB24=0. Alk1and Alk2are ethylene. RB21and RB22are -OH. nB21is denoted as m, and nB22is denoted as n.

[0156] (nB21+nB22)=(m+n)= 5. Because distribution of repetitions is accepted for formula (B’), each of nB2i, nB23 and nB25 can take a number, which is not an integer.

[0157]

[0158] nB24 is 0, 1 or 2 (more preferably 0 or 1; further preferably 0).

[0159] Each of Alk1, Alk2, and Alk3is independently C1-4alkylene (preferably methylene, ethylene, or n-propylene; more preferably ethylene).

[0160] Each of RB21, RB22and RB23is independently preferably -OH, C1-4alkyl, or C1-4alkoxyl (more preferably -OH, methyl, t-butyl, or methoxy; further preferably -OH or methyl; further more preferably -OH).Foreignfiling_text P24-255-SEC-WO01 20251002

[0161] H portion of the surfactant (B) can be replaced or not-replaced by fluoro. It is one of preferable embodiment that none of H portion of the surfactant (B) is replaced by fluoro.

[0162] Surfactant (B) can be represented by below formula (B”). When nsn is 0, Formula (B’) takes formula (B”).

[0163] B21

[0164] B22

[0165] >nB22

[0166]

[0167] JnB24

[0168] Formula (B”) Explanations and detailed embodiments of each of symbols in formula (B”) are each independently same to the ones of formula (B’).

[0169] Examples of the surfactant (B) include the followings.

[0170]

[0171] Foreignfiling_text P24-255-SEC-WO01 20251002

[0172] n is 2-30. m is 6-30.

[0173] m+n is 3 to 20. x is 3 to 20. HO

[0174] 20

[0175]

[0176] Although not to be bound by theory, it is believed that combination of polymer (A) and surfactant (B) is good for solubilities of solutes in the top coating composition.

[0177] It is one embodiment of this invention that the content of surfactant (B) relative to total of polymer (A) is 0.0001 to 300 mass% (preferably 0.001 to 100 mass%; more preferably 0.01 to 50 mass%; further preferably 0.1 to 25 mass%; further more preferably 1 to 5 mass%).Foreignfiling_text P24-255-SEC-WO01 20251002

[0178] Average mass amount of the fluorine in the surfactant (B) 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%) relative to the total of the surfactant (B). This number can be calculated from average of atomic mass.

[0179] - Solvent (S)

[0180] The top coating composition comprises solvent (S). The solvent (S) comprises water (S1 ). The content of water (S1 ) relative to total of solvent (S) is 90 to 100 mass%.

[0181] One preferable embodiment of water (S1) is DIW. As one embodiment of this invention, the content of water (S1 ) relative to total of solvent (S) is preferably 92 to 100 mass% (more preferably 95 to 100 mass%; further preferably 98 to 100 mass%; further more preferably 100 mass%).

[0182] As one embodiment of this invention, the content of solvent (S) relative 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%).

[0183] It is another embodiment of this invention that solvent (S) comprises organic solvent (S2). The contents of organic solvent (S2) relative to total of solvent (S) can be 0 to 10 mass% (preferably 0.00001 to 8 mass%; more preferably 0.00001 to 5 mass%; further preferably 0.00001 to 2 mass%). It is one embodiment of this invention, the solvent (S) doesn’t comprise organic solvent (S2) (0.00000 mass%).

[0184] Although not to be bounded by theory, such amount or none of organic solvent (S2) can reduce film loss of underneath photoresist layer, and / or can inhibit intermixing of underneath photoresist layer.Foreignfiling_text P24-255-SEC-WO01 20251002

[0185] The solvent (S) can comprise both of water (S1) and organic solvent (S2). As one aspect of this invention, the mass weight ratio between water (S1 ) and organic solvent (S2) is preferably 100:0 to 90:10 (more preferably 100: 0.00001 to 95: 0.00001; further preferably 100: 0.00001 to 98: 0.00001).

[0186] Although not to be bounded by theory, because solubilities of the solutes are good in the top coating composition, it is possible to reduce the amount of organic solvent (S2).

[0187] Organic solvent (S2) can comprise, for example alcohol solvent (S2-1), ketone solvent (S2-2), ester solvent (S2-3), ether solvent (S2-4), and other types of organic solvent (S2-5). For example, alcohol solvent (S2-1) is methyl alcohol, ethyl alcohol, isopropyl alcohol (IPA), 2-mehyl pentanol, diacetone alcohol, and any mixture of any of these. For example, ketone solvent (S2-2) is acetone, methyl ethyl ketone, or mixture of these. For example, ester solvent (S2-3) is methyl acetate, ethyl acetate, ethyl lactate, propylene glycol methyl ether acetate (PGMEA), cellosolve acetate, alkylcellosolve acetate, carbitol acetate, or any mixture of any of these. For example, ether solvent (S2-4) 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 (S2-5) is dimethylformamide, dimethyl sulfoxide, or any mixture of any of these.

[0188] Organic solvent (S2) is preferably alcohol solvent (S2-1), or ether solvent (S2-4), or mixture of them; more preferably alcohol solvent (S2-1 ), or ether solvent (S2-4); further preferably alcohol solvent (S2-1). It is other embodiment of this invention that organic solvent (S2) is IPA. Although not to be bound by theory, it is good for the effect of this invention to select solvent (S) which doesn’t dissolved photoresist layer when the top coating composition applied onto it.Foreignfiling_text P24-255-SEC-WO01 20251002

[0189] - Basic compound (C)

[0190] The top coating composition of this invention can further comprise basic compound (C).

[0191] Examples of the basic compound (C) include the followings:

[0192] (i) ammonia,

[0193] (ii) C1-16primary aliphatic amines and derivatives thereof (for example, methylamine, ethylamine, isopropylamine, n-butylamine, tert-butylamine, cyclohexylamine, ethylenediamine, tetraethylenediamine, ethanol amine etc.),

[0194] (iii) C2-32secondary aliphatic amines and derivatives thereof (for example, dimethylamine, diethylamine, methylethylamine, dicyclohexylamine, N, N-dimethylmethylenediamine, etc.),

[0195] (iv) C3-48tertiary 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.),

[0196] (v) C6-30aromatic amines and derivatives thereof (for example, aniline, benzylamine, naphthylamine, N-methylaniline, 2-methylaniline, 4-aminobenzoic acid, phenylalanine, etc.), and

[0197] (vi) C5-30heterocyclic amines and derivatives thereof (for example, pyrrole, oxazole, thiazol, imidazole, 4-methylimidazole, pyridine, methylpyridine, butylpyridine, etc.).

[0198] It is one aspect of this invention that the content of basic compound (C) relative 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% relative to polymer (A)).Foreignfiling_text P24-255-SEC-WO01 20251002

[0199] - Polymer (D)

[0200] The top coating composition of this invention can further comprise polymer (D). Polymer (D) can be regarded as sub polymer in this composition. By including polymer (D), coatability of the composition and rigidness of the top coating made from the top coating composition can be controlled.

[0201] Polymer (D) is different from polymer (A) and surfactant (B).

[0202] In the case the polymer (D) comprises multiple types of unit, the polymer (D) 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).

[0203] As one embodiment of this invention, the content of polymer (D) relative 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 (D) (0 mass% relative to polymer (A)).

[0204] It is one aspect of this invention that the Mw of the polymer (D) is preferably 5 to 100 kDa (more preferably 10 to 70 kDa; further preferably 15 to 60 kDa).

[0205] It is one preferable embodiment of this invention that the polymer (D) has less or none of fluorine (F) in it. Average mass amount of the fluorine in the polymer (D) 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%) relative to the total of polymer (D). This number can be calculated from average of atomic mass.

[0206] - Additives (E)Foreignfiling_text P24-255-SEC-WO01 20251002

[0207] The top coating composition of this invention can further comprise additive (E). The additive is preferably an acid, a dye, an antiseptic, an antioxidant, a thickener, a surface smoothing agent, a substrate adhesion enhancer, an antifoaming agent, or any combination of any of these (more preferably an acid, a dye, an antiseptic, an antioxidant, a thickener, or any combination of any of these; further preferably an acid, a dye, or their combination; further more preferably a dye). Known compounds can be used for any one of these purposes.

[0208] As one embodiment of this invention, the content of additive (F) relative 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% relative to polymer (A)).

[0209] Method for manufacturing top coating composition

[0210] This invention provides a method for manufacturing top coating. The method comprises following below steps.

[0211] (1) applying a photoresist composition above a substrate to form a photoresist layer; and

[0212] (2) applying any embodiment of the top coating composition described in this specification on the photoresist layer to form a top coating.

[0213] In this specification, unless otherwise specified, the numbers in parentheses indicating the steps mean the order.

[0214] Step (1)

[0215] Any known substrate can be used in the methods of this invention. Substrate is, for example, a silicon / silicon dioxide-coated 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0216] 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.

[0217] 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.

[0218] 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 method 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.

[0219] 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).

[0220] 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.

[0221] 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 theForeignfiling_text P24-255-SEC-WO01 20251002

[0222] center of the substrate (having photoresist layer on it) and existed DIW is replaced by the top coating composition.

[0223] Step (2)

[0224] 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 by evaporation) and solid components including polymer (A) forms top coating.

[0225] The thickness of the top coating is preferably 3 to 50 nm (more preferably 10 to 45 nm; further preferably 10 to 40 nm).

[0226] 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.

[0227] The manufactured coating of this invention can give good optical properties as top coating.

[0228] 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).

[0229] The k value of the manufactured top coating irradiated by 193 wavelength (ArF excimer laser) gives preferably “0.1 < k < 0.3” (more preferably “0.1 < k < 0.2”; further preferably “0.1 < k < 0.15”).

[0230] The n value of the manufactured top coating irradiated by 193 nm wavelength gives preferably “1.20 < n < 1.40” (more preferably “1.25 < n < 1.39”; further preferably “1.30 < n < 1.38”).Foreignfiling_text P24-255-SEC-WO01 20251002

[0231] 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”).

[0232] The n value of the manufactured top coating irradiated by 248 nm wavelength gives preferably “1.3 < n < 1.5” (more preferably “1,3< n < 1.4”.

[0233] 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.

[0234] - Method for manufacturing resist patterns

[0235] This invention provides a method for manufacturing resist patterns. The method comprises following below steps.

[0236] Manufacturing top coating on photoresist layer. Details of this step is described above as step (1) and step (2).

[0237] (3) Optionally baking the photoresist layer.

[0238] (4) Exposing the photoresist layer by 193 or 248 nm irradiation, through the top coating.

[0239] (5) Optionally baking the exposed photoresist layer.

[0240] And (6) developing the exposed photoresist layer.

[0241] Optionally the method for manufacturing resist pattern can further comprises step of (7) cleaning resist pattern by cleaning liquid.

[0242] Optionally the method for manufacturing resist pattern can further comprises step (4-2) removing the top coating, or (5-2) removing the top coating.

[0243] 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 topForeignfiling_text P24-255-SEC-WO01 20251002

[0244] coating, the “photoresist layer” in step (5) means photoresist layer only, because the top coating on the photoresist layer is already removed.

[0245] Step (3)

[0246] 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.

[0247] The temperature of this baking is preferably 75 to 200°C (more preferably 90 to 150 C degree). The time of this baking is preferably 30 to 240 seconds (more preferably 45 to 120 seconds).

[0248] Step (4)

[0249] To make the resist pattern, a predetermined mask is used for this exposure. The method of this invention comprises exposing the photoresist layer by 193 or 248 nm irradiation, through the top coating. This wavelength accepts a range of ±1 %. The irradiation light goes through the top coating of this invention.

[0250] Step (4-2) and step (5-2)

[0251] 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).

[0252] 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).

[0253] 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.

[0254] 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0255] 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. For example, solvent (B) used in the top coating composition (or mixture with polar solvent) can be used for this purpose.

[0256] Step (5)

[0257] 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).

[0258] Step (6)

[0259] 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.

[0260] 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0261] In the case the photoresist composition is positive tone photoresist composition, the photoresist portion receiving irradiation light become soluble to the developer.

[0262] After development, the photoresist layer can be dried, by for example spin drying.

[0263] Step (7)

[0264] 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.

[0265] 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 % relative to the total of the cleaning liquid. It can reduce a surface tension of such cleaning liquid to avoid pattern collapse.

[0266] 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.

[0267] As one preferable embodiment, the top coating has a feature that it can be removed by a developer. This removability can be measured by the 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 room 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0268] - Method for manufacturing device

[0269] The 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;

[0270] Etching using the resist patterns manufactured by the method described above as a mask, and processing a substrate; or

[0271] Doping ion into the substrate or underlayer with using the resist patterns manufactured by the method described above.

[0272] The resist patterns manufacturing method is described step by step in preceding descriptions.

[0273] The subject of etching and ion doping through resist patterns as a mask can be a substrate or an underlayer. Underlayer means layer(s) fabricated between substrate and photoresist layer. Multiple types of underlayer fabrication are encompassed in such underlayer (for example, such constitution of “Substrate / SOC / BAR / Photoresist layer / Top coating”).

[0274] Preferably single layer is used as the underlayer. Examples of the underlayer are BARC or Spin on Carbon layer (SOC), which are preferably having properties of higher etching resistance than photoresist layer / patterns.

[0275] Etching using the resist pattens as a mask

[0276] For etching, any publicly known method such as dry etching and wet etching can be used, and dry etching is more preferable.

[0277] 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0278] The method of this invention can further comprise step of forming a wiring on the processed substate.

[0279] Doping ion into the substrate or underlayer

[0280] For 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.

[0281] Device

[0282] The 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 the present invention, this packaged product is called a device. Preferably, the device is a semiconductor device.

[0283] 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.

[0284] Examples

[0285] Synthesis example 1 - polymer 1

[0286] 9-anthracenylmethyl methacrylate, Polyethylene 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.Foreignfiling_text P24-255-SEC-WO01 20251002

[0287] Evaluation example 1 - Polymer 1

[0288] The polymer 1 and below surfactant 1 are dissolved in deionized water to obtain 2.5 mass% polymer 1 and 0.03 mass% surfactant 1. The solution is shaken for 30 min and left still for overnight at room temperature. This results in obtaining composition 1. The composition 1 is spin coated on silicon wafer at 1,500 rpm for 20 sec and baked at 110C for 60 seconds. Obtained film is analyzed using Woollam ellipsometer to give n=1.450, k=0.261 at 248nm and film thickness of 80 nm.

[0289]

[0290] HO m n OHSurfactant 1. (m+n) is 5. SF-2502 (Takemoto oil & fat co., ltd.)

[0291] Synthesis example 2 - polymer 2

[0292] 9-anthracenylmethyl methacrylate and methacrylic acid are mixed in 9.4:90.6 molar ratio and polymerized in PGME using 3 mol% 2,2'-Azobis(isobutyronitrlle). The resulting polymer 2 is purified by precipitation with heptane, and volatiles are removed under reduced pressure.

[0293] Evaluation example 2 - Polymer 2

[0294] The polymer 2 and above surfactant 1 are dissolved in deionized water to obtain 2.5 mass% polymer 2 and 0.03 mass% surfactant 1. The solution is shaken for 30 min and left still for overnight at room temperature. This results in obtaining composition 2. The composition 2 is spin coated on silicon wafer at 3,500 rpm for 20 sec and baked at 110C for 60 seconds. Obtained film is analyzed using Woollam ellipsometer to give n=1.508, k=0.307 at 248nm and film thickness of 93 nm.

[0295] Preparation examples of working example compositions 3Foreignfiling_text P24-255-SEC-WO01 20251002

[0296] Polymer and surfactant are added to solvent as the described mass parts as listed in Table 1. The solution is shaken for 30 min and left still for overnight at room temperature. This results in obtaining a working example composition 3.

[0297] Table 1

[0298] Comparative Working Examples Examples 3 4 5 6 7 8 1 2 3 Polymer 1 1.00 1.00 1.00 1.00 1.00 1.00

[0299] 1.0 Polymer 2 1.00 1.00 0 Surfactant 1,

[0300] SF-2502 0.03 0.01 0.50 0.03

[0301] Surfactant 2,

[0302] D-1006EH 0.03

[0303] Surfactant 3,

[0304] D-1109-S 0.03

[0305] Comparative

[0306] surfactant,

[0307] A-40-S 0.03

[0308] Deionized 84. Water (DIW) 98.97 99.00 98.50 98.97 98.97 98.97 98.97 99.00 00 Isopropanol 5.00

[0309] 15. Ethanol 00

[0310]

[0311] Solubility A A A A A B A C A

[0312] Surfactant 2, Polyoxyethylene alkyl ether (D-1006EH, Takemoto oil) Surfactant 3, Polyoxyethylene alkyl ether (D-1109-S, Takemoto oil)

[0313]

[0314] Comparative surfactant (A-40-S, Takemoto oil)Foreignfiling_text P24-255-SEC-WO01 20251002

[0315] Preparation example of working example compositions of 4 to 8, and comparative example compositions of 1 to 3

[0316] In the same manner as in the “Preparation examples of working example compositions 3” above, using polymer, surfactant, solvent and / or mass part of each of them as listed in Table 1, working example compositions of 4 to 8, and comparative example compositions of 1 to 3 are prepared.

[0317] Evaluation example - Solubility

[0318] A solubility of each composition listed in Table 1 is visually evaluated based on the following standard. Results are described in Table 1.

[0319] A: The composition is transparent without residue.

[0320] B: The composition is transparent, but residue observed.

[0321] C: The composition is cloudy.

[0322] Because comparative example composition 2 is cloudy, following evaluations are not taken on the comparative example composition 2.

[0323] Evaluation example - Wettability

[0324] Film thickness of each layer is evaluated using Woollam ellipsometer.

[0325] Same applies to example session herein later.

[0326] Photoresist AZ DX6270P (Merck Electronics ltd) is a chemically amplified positive photoresist composition. AZ DX6270P is spin coated on silicon wafer at 2,650 rpm and baked at 120C for 90 seconds to give DX6270P layer. Film thickness of DX6270P layer is approximately 400 nm. Each of top coating composition listed in Table 1 is spin coated on the DX6270P layer to give top coating layer. Each of top coating layer is approximately 28 nm.

[0327] Wettability is visually evaluated based on the following standard. Results are described in Table 2.

[0328] A: Top coating layer is spread on whole wafer.

[0329] B: Top coating layer is spread partially on whole wafer.Foreignfiling_text P24-255-SEC-WO01 20251002

[0330] C: The solution is not spread on wafer.

[0331] Table 2

[0332] Comparative Working Examp es Examples 3 4 5 6 7 8 1 3 Wettability A B A A A A C A FT of fleshly

[0333] made PR 399 400 400 398 400 401 398 402 FT of PR

[0334] after

[0335] developmen

[0336] t 352 354 345 350 350 347 335 330 Film loss

[0337] amount (nm) 47 46 55 48 50 54 63 72 Film loss

[0338]

[0339] evaluation A A B A A B C C (note: in the above Table 2, FT is an abbreviation of “film thickness, and PR is an abbreviation of “photoresist”.)

[0340] Evaluation example - Film loss

[0341] AZ DX6270P is spin coated on silicon wafer at 2,650 rpm and baked at 120C for 90 seconds to give DX6270P layer. The film thickness of DX6270P layer is approximately 400 nm, and described in Table 2. Each of top coating composition listed in Table 1 is spin coated on the DX6270P layer to give top coating layer. The film thickness of top coating layer is approximately 28 nm.

[0342] The wafer with each top coating layer on DX6270P layer is baked at 130C for 90 seconds. As development each wafer is immersed in 2.38wt% TMAH solution for 60 seconds, and then rinsed DIWfor 30 seconds. And each wafer is air dried. The film thickness of DX6270P layer is again measured and described in Table 2.

[0343] Film loss is defined as a difference between photoresist layer thicknesses of freshly made film and after immersion in 2.38wt% TMAH solution. Each of film loss is described in Table 2. The greater the film loss, the stronger the intermixing that occursForeignfiling_text P24-255-SEC-WO01 20251002

[0344] Film loss is evaluated based on the following standard.

[0345] A: Film loss is 50 nm or less.

[0346] B: Film loss is more than 50 nm, and less than 60 nm.

[0347] C: Film loss is 60 nm or more, and less than 80 nm.

[0348] D: Film loss is 80 nm, or more.

[0349] Evaluation example - Solubility in developer

[0350] The composition 2 described in Table 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 600MIR Developer (Merck Electronics ltd) 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 a top coating made from the composition 2.

Claims

Foreignfiling_text P24-255-SEC-WO01 20251002Patent Claims1. A top coating composition comprising polymer (A), surfactant (B) and solvent (S);whereinthe polymer (A) comprises a side chain comprising a fused aromatic ring;surfactant (B) comprises an aliphatic hydrocarbon portion (B1) and an alkylene oxide portion (B2):the solvent (S) comprises water (S1 );the content of water (S1 ) relative to total of solvent (S) is 90 to 100 mass%.

2. The top coating composition according to claim 1, where the surfactant (B) is a nonionic surfactant;optionally the surfactant (B) is represented by below formula (B’)O——Alk1nB21O——Alk2nB22O——Alk3JnB24 Formula (B’) where Ali is a C2-30aliphatic hydrocarbon, which comprises one or multiple of -CH2-, -CH=CH- -C≡C-, or any combination of any of these; nB11is 0, 1 or 2;X is -O-, -COO-, -N=, or -C(=O)-N=;each of nB21, nB23and nB25is independently a number of 1 to 50; nB22is 0 or 1; nB24is 0, 1 or 2;each of Alk1, Alk2, and Alk3is independently C1-4alkylene;each of RB21, RB22and RB23is independently -OH, C1-4alkyl, or C1-4Foreignfiling_text P24-255-SEC-WO01 20251002alkoxyl; andH portion of the surfactant (B) can be replaced or not-replaced by fluoro.

3. The top coating composition according to claim 1 or 2, where the fused aromatic ring in the polymer (A) has a heteroatom or have none of a heteroatom.

4. The top coating composition according to any of claim 1 to 3, wherein the polymer (A) comprises unit A1;unit A1 is represented by formula A1;LA12 / formula (A1)RA11, RA12and RA13are each independently H or methyl;RA14is each independently C1-10alkyl, C1-10alkoxyl, -OH, -COOH, -COORA15, -SO3H, or cyano;where one or more of methylene in alkyl portion in RA14can be replaced by ether linker, one or more of methyl in alkyl portion in R14A1can be replaced by hydroxyl, and one or more of alkyl of RA14can further include heteroatom;RA15is each independently C1-6alkyl, -SO3H, cyano, C2-4alkenyl or C2-4alkynyl;LA11is single bond, or -COO-;Foreignfiling_text P24-255-SEC-WO01 20251002LA12 is single bond, or C1-3 alkylene;nA11 is number of 0 to 9; andnA12 is 0 or 1.

5. The top coating composition according to any of claim 1 to 4, wherein the polymer (A) comprises unit A2;unit A2 is represented by formula A2;Formula A2RA21, RA22 and RA23 are each independently H or methyl,RA24 is each independently H or methyl,RA25 is H, hydroxyl, C1-6 alkoxyl, -SO3H or -COOH,LA21 is single bond, -CO- or C1-6 alkylene,LA22 is single bond, or C1-10 alkylene, andnA21 is number of 1 to 10.

6. The top coating composition according to any of claim 1 to 5, wherein the polymer (A) comprises unit A3;unit A3 is represented by formula A3;Foreignfiling_text P24-255-SEC-WO01 20251002Formula A3RA31, RA32 and RA33 are each independently H or methyl,LA31 is single bond, or -COO- RA34 is H, or C1-10 alkyl,in the alkyl of RA34, one or more of methylene portion can be replaced by -O-, or -CO-, andin the alkyl of RA34, one or more H can be replaced by hydroxyl.

7. The top coating composition according to any of claim 4 to 6, where each number of unit A1, unit A2 and A3 in polymer (A) are denoted as nA1, nA2 and nA3 respectively, and the total number of all unit contained in the polymer (A) is denoted as nAtotal, these satisfy following,0% < (nA1 / nAtotal) < 90%;0% < (nA2 I nAtotal) < 95%; or0% < (nA3 / nAtotal) < 70%.

8. The top coating composition according to any of claim 1 to 7, where the solvent (S) further comprises organic solvent (S2), and the content of organic solvent (S2) relative to total of solvent (S) is 0 to 10 mass%.

9. The top coating composition according to any of claim 1 to 8, further comprising basic compound (C), polymer (D), or additive (E).Foreignfiling_text P24-255-SEC-WO01 2025100210. The top coating composition according to any of claim 1 to 9, wherein the Mw of polymer (A) is 5 to 100 kDa;optionally the Mw of polymer (D) is 5 to 100 kDa.

11. The top coating composition according to any of claim 1 to 10, where the content of polymer (A) relative to total of the top coating composition is 0.10 to 15 mass%;optionally the content of surfactant (B) relative to total of polymer (A) is 0.0001 to 300 mass%;optionally the content of solvent (S) relative to total of the top coating composition is 40 to 99.99 mass%;optionally the content of basic compound (C) relative to total of polymer (A) is 0 to 10 mass%;optionally the content of polymer (D) relative to total of polymer (A) is 0 to 25.0 mass%;optionally the content of additive (E) relative to total of polymer (A) is 0 to 25.0 mass%; oroptionally the dynamic surface tension of the top coating composition is 60 mN / m or lower.

12. The top coating composition according to any of claim 1 to 11, where it is a top anti-reflective coating composition;optionally the top anti-reflective coating composition is ArF top anti- reflective coating composition; oroptionally the top anti-reflective coating composition is KrF top anti- reflective coating composition.

13. A method for manufacturing top coating comprising following steps;(1) applying a photoresist composition above a substrate to form a photoresist layer; and(2) applying the top coating composition according to any of claim 1 toForeignfiling_text P24-255-SEC-WO01 2025100212 on the photoresist layer to form a top coating.

14. The method for manufacturing top coating according to claim 13;whereinthe n value of the manufactured top coating irradiated by 248 nm wavelength gives “1.3 < n < 1.5”; and / orthe k value of the manufactured top coating irradiated by 248 nm wavelength gives “0.1 < k < 0.3”.

15. The method for manufacturing top coating according to claim 13;whereinthe n value of the manufactured top coating irradiated by 193 nm wavelength gives “1.20 < n < 1.40”; and / orthe k value of the manufactured top coating irradiated by 193 nm wavelength gives “0.1 < k < 0.3”.

16. A method for manufacturing resist patterns comprising following steps;manufacturing top coating on photoresist layer according to claim 13 or 15;(3) optionally baking the photoresist layer;(4) exposing the photoresist layer by 193 or 248 nm irradiation, through the top coating;(5) optionally baking the exposed photoresist layer; and(6) developing the exposed photoresist layer;whereinoptionally 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.

17. The method for manufacturing resist patterns according to claim 16; wherein the top coating has a feature that it can be removed by aForeignfiling_text P24-255-SEC-WO01 20251002developer.

18. A method for manufacturing a device, comprisingetching using the resist patterns manufactured by the method according to claim 16 or 17 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 16 or 17.

19. The method for manufacturing a device according to claim 18, further comprising forming a wiring on the processed substrate; optionally, the device is a semiconductor device.

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