TW200903172A - Resin for formation of upper antireflective film, composition for formation of upper antireflective film, and resist pattern formation method - Google Patents

Abstract

Disclosed are: a resin for forming an upper antireflective film which can reduce a standing wave effect satisfactorily and has excellent solubility in an alkaline developer in lithography; a composition for forming the upper antireflective film; and a method for forming a resist pattern. Specifically, the resin for forming an upper antireflective film has at least one unit selected from a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), has a weight average molecular weight of 1000 to 100000 as measured by GPC method, and is soluble in an alkaline developer. (1) (2) wherein R<1> to R<14> independently represent a hydrogen atom, -OH, -COOH or -SO3H, provided that all of R<1> to R<7> or R<8> to R<14> do not represent a hydrogen atom in a molecule.

Description

[Technical Field] The present invention relates to a resin for forming an upper antireflection film, a composition for forming an upper antireflection film, and a method for forming a photoresist pattern. Further, the present invention relates to the formation of an upper antireflection film which is excellent in the standing wave effect and is excellent in solubility in an alkali developer in lithography (especially 193 nm lithography). A resin and an upper anti-reflection film forming composition and a photoresist pattern forming method. Further, the present invention relates to an upper anti-reflection film which is excellent in the standing wave effect and the probe defect in the lithography (especially 193 nm lithography) and which is excellent in solubility with respect to an alkali developer. A forming composition and a photoresist pattern forming method. [Prior Art] Conventionally, in the field of microfabrication represented by the manufacture of integrated circuit components, in order to obtain a higher degree of integration, the miniaturization of the processing size in lithography is progressing, and ArF is currently used. Excimer laser (wavelength 193 nm) 'F-excimer laser (wavelength I57nm) and other micro-machining lithography technologies of the order of about 200 nm or less are considered necessary. A component which has an acid dissociable functional group and a component which causes an acid to be irradiated by radiation (hereinafter referred to as "exposure") (hereinafter referred to as "acid generation" in terms of a photoresist having such an excimer laser irradiation. There are a number of proposals for the use of chemically enhanced photoresists (hereinafter referred to as "chemically enhanced photoresists"). In the chemically enhanced photoresist, for example, a resin having a tertiary butyl ester group of a carboxylic acid or a tertiary butyl carbonate group of a phenol and a photoresist of an acid generator are proposed. The photoresist is obtained by the acid action of the exposure to 'dissociate the tertiary butyl ester group or the tertiary butyl carbonate group present in the resin' to make the resin an acidic group having a carboxyl group or a phenolic hydroxyl group. As a result, the exposure region of the photoresist film is used to become easily soluble in the alkali developer. In such lithography, finer pattern formation is required in the future, and in particular, ArF excimer laser (wavelength 193 nm) is used. The review of microfabrication was extremely enthusiastic. However, the radiation used in the lithography process is usually a single wavelength, so that the incident radiation and the reflected radiation above and below the photoresist film interfere with each other in the photoresist film. The result is called a standing wave. The effect of "effect" or "multiple interference effect", that is, even if the exposure amount is constant, the thickness of the photoresist film fluctuates due to the effective exposure amount of the radiation relative to the photoresist film in the film. When a phenomenon occurs, there is a problem that the formation of the photoresist pattern is adversely affected. For example, due to the composition or viscosity of the photoresist, the coating conditions of the photoresist, etc., may cause a change in the thickness of the coating film, or a difference in the thickness of the substrate or a difference in the thickness of the coating film (in the case of a concave portion) The thickness of the portion is thicker, and the difference in the film thickness due to the change in the effective exposure amount with respect to the photoresist film causes the pattern size to vary or the dimensional accuracy of the photoresist pattern to decrease. The problem of such a standing wave effect is an important issue particularly in the ion implantation step in which the substrate reflectance is large, and thus these problems are overcome. In order to solve the problem of the standing wave effect, a method of forming an upper anti-reflection film on the photoresist film to suppress reflection on the surface of the photoresist film, and reducing the multiple interference in the film 200903172 has been proposed. For example, in the non-patent document 1, it is described in the photoresist film, and the upper antireflection film is laminated with polyoxyalkylene oxide, polyethyl vinyl ether, polyvinyl alcohol or the like to reduce the standing wave effect. In this case, the reflection suppressing effect in the surface of the photoresist film mainly depends on the refractive index and the film thickness of the antireflection film, and the refractive index of the ideal upper antireflection film is /&quot; n (n is the refractive index of the resist The film thickness of the ideal upper anti-reflection film is λ / 4 m (λ indicates the wavelength of the radiation, and m indicates the refractive index of the upper anti-reflection film) an odd multiple. Non-Patent Document 1: J. Eectrochem. Soc., Vol.l37, No. 12, P.3 900 (1 990) The refractive index of a general photoresist is 1. 6 to 1. 8, and therefore, in order to sufficiently suppress the standing wave effect, it is refracted. An upper anti-reflection film having a rate of 1.4 or less is necessary. However, the refractive index of the upper anti-reflection film formed of polyoxyalkylene oxide, polyethyl vinyl ether or polyvinyl alcohol is generally 1.5 or more, and the standing wave effect cannot be sufficiently suppressed, and in the future, the processing size is followed in the lithography. In the micronization, the management of the pattern line width is becoming stricter, and the upper layer anti-reflection film having a smaller refractive index is necessary. Further, it is also necessary that the upper anti-reflection film has a small refractive index and a high transmittance. When the upper anti-reflection film is strongly absorbed, the light reaching the photoresist film becomes weak, so that the sensitivity is lowered and the manufacturing efficiency is lowered. Therefore, the absorption coefficient (k値) of the upper anti-reflection film is preferably small, and 0.25 or less is quite practical. Moreover, in the manufacture of integrated circuit components in recent years, in the lithography process, defects occurring during development of the photoresist film cause problems, bridged defects or dross defects in the line and gap patterns, and contact holes. In the pattern, there are -8 - 200903172 poor opening defects or dross defects. One of the causes of such defects is the case where the developer is a poorly soluble substance which is reattached on the photoresist or on the substrate during the rinsing after development. This defect is called a probe defect. In the improvement of the probe defect, the production of the integrated circuit component has been associated with an increase in productivity. Therefore, there have been many beggings so far, and there is still no solution that can sufficiently satisfy the demand. SUMMARY OF THE INVENTION Problems to be Solved by the Invention The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a lithography technique (especially 193 nm lithography) which can sufficiently reduce the standing wave effect and is developed relative to alkali The liquid solubility is an excellent antireflection film forming resin, an upper antireflection film forming composition, and a resist pattern forming method. In addition, in the lithography (especially 193 nm lithography), the composition for forming an upper antireflection film and the light which are excellent in solubility in an alkali developer can be sufficiently reduced in the standing wave effect and the probe defect. Resistance pattern forming method. Means for Solving the Problem The means for achieving the above object is as follows. [1] A resin for forming an upper antireflection film is characterized by containing a repeating unit represented by the following formula (1), and the following formula (2) At least one of the indicated repeating units has a weight average molecular weight of from 1,000 to 100,000 as measured by gel permeation chromatography and is soluble in an alkali developer '200903172

[In the formula (1), R1 to R7 each represent a hydrogen atom, -〇H, -COOH or -S03H' and R1 to R7 are not all hydrogen atoms], [Chemical 2]

[In the formula (2), R8 to R14 each represent a hydrogen atom, -OH, -COOH or -so3h, and r8 to r "will not all be a hydrogen atom." [2] As the upper layer of the item [1] The resin for forming an antireflection film, which comprises a repeating unit of the formula (1) and the formula (2), and contains at least one of -OH, -COOH and -S03H, and repeats the unit. The resin for forming an antireflection film of the above-mentioned item [1] further contains at least one of the repeating units represented by the following formulas (3) to (6). -10-200903172 [Chem. 3]

D /

S03H [In the formula (3), R15 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, A represents a single bond, a carbonyl group or a carbonyloxy group, B represents a single bond or an imino group, and D represents a single bond or carbon. Number 2 to 12 of 2 organic groups], [Chemical 4]

COOH [In the formula (4), R16 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group [Chemical 5]

[In the formula (5), R17 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a fluorinated alkyl group having a carbon number of 1 to 12], -11 - (6) (6) 200903172 [Chemical 6]

19V20

OH [In the formula (6), R18 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, P represents a single bond, a carbonyl group or a carbonyloxy group. Q represents a single bond or a carbon number of 1 to 21; The radicals 'R19 and R2() each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms. [4] A composition for forming an antireflection film according to any one of the above [1] to [3], wherein the resin for forming an antireflection film and the solvent are contained. [5] A photoresist pattern forming method comprising: (1) a step of forming a photoresist film on a substrate; and (2) using a composition for forming an antireflection film of the above [4], a step of forming an upper anti-reflection film on the photoresist film, and (3) irradiating radiation on a region of the photoresist film formed by the upper anti-reflection film, performing exposure, and (4) developing and removing the The step of the upper anti-reflection film. [6] A composition for forming an upper antireflection film, characterized by comprising a polymer (A) having an aromatic group and an aromatic polymer, and a sulphuric acid generator (B) At least one of the acid residues (C). [7] The composition for forming an antireflection film according to the above [6], wherein the compound (c) having the sulfonic acid residue is a compound represented by the following formula (1). 7]

(I) [In the formula (1), R21 represents a linear or branched alkyl group having 1 to 1 carbon atom, an alicyclic alkyl group having 3 to 20 carbon atoms or a derivative thereof, a hydroxyl group, a carboxyl group or an alkane Alkyl group, alkoxycarbonyl group, or alkylcarbonyloxy group, Z represents a linear, branched, alicyclic hydrocarbon group or a substituted aromatic hydrocarbon group having a carbon number of 4 to 12, and m is 0~ An integer of 4, n is an integer from 1 to 4, and R1 is a plural or plural, and may be the same or different from each other. [8] The composition for forming an antireflection film of the above [6] or [7], wherein the polymer (Α) contains a repeating unit represented by the following formula (II) and At least one of the repeating units represented by the formula (in) has a weight average molecular weight of from 1,000 to 100,000 as measured by gel permeation chromatography, [Chem. 8]

(Π) 13- 200903172, -OH, -COOH, or [in the formula (II), R22 to R28 each represent a hydrogen atom -S03H], [Chemical 9]

(ΙΠ), -OH, -COOH, or a composition for forming a composition, wherein in the repeating unit shown by (VII), in the formula (ΠΙ, R29 to R35 each represents a hydrogen atom -S Ο 3 Η). [9] The above-mentioned eighth layer antireflective alcohol, the polymer (Α), further comprising the following formula (IV) to at least one species [Chemical 10]

[In the formula (IV), R36 represents a hydrogen atom 'methyl group, which is a single bond, a carbonyl group or a carbonyloxy group, a single bond, a linear chain having a carbon number of 1 to 2 fluorene, and a branched aromatic group having a substituent. Hydrocarbyl], hydroxymethyl or trifluoromethyl single bond or imino group, D is shown, alicyclic hydrocarbon group or-14- (V) 200903172 [Chemical 11] R37

COOH [In the formula (V), R3 7 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group], [Chemical 12]

(VI) [In the formula (VI), R3 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a fluorinated alkyl group having a carbon number of 1 to 1 2]

(VI) [In the formula (VII), R3 9 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, P represents a single bond, a carbonyl group or a carbonyloxy group, and Q represents a single bond, and the carbon number is 1 to 20 Linear, branched, alicyclic hydrocarbon group or aromatic group which may have a substituent -15-200903172 Group hydrocarbon group 'R4G and R41 each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a carbon number of 1 to 4 Alkyl fluoride]. [10] The composition for forming an overlayer antireflection film according to any one of [6] to [9] wherein the polymer (A) comprises a repeating unit represented by the following formula (VIII), and The repeating unit shown in the formula (IX). [Chem. 14]

Cf3

rM

c/^OH

[11] A photoresist pattern forming method, comprising: (1) a step of forming a photoresist film on a substrate, and (2) using a layer barrier according to any one of claims 6 to 10; a step of forming a composition for forming a reflective film, forming an upper anti-reflection film on the photoresist film, and (3) irradiating radiation on a region of the photoresist film formed by the upper anti-reflection film to perform exposure, and (4) A step of developing and removing the upper anti-reflection film. EFFECTS OF THE INVENTION -16- 200903172 According to the present invention, in the lithography (especially 193 nm lithography), the standing wave effect can be sufficiently reduced, and the upper anti-reflection film excellent in solubility with respect to the alkali developing solution can be formed. Further, in the lithography (especially 193 nm lithography), the standing wave effect and the probe defect can be sufficiently reduced, and the upper anti-reflection film excellent in solubility with respect to the alkali developer can be formed. Therefore, the present invention can be used extremely satisfactorily in the production of L S I which is expected to be further miniaturized in the future. Further, the present invention, particularly in the ion implantation step in 193 nm lithography, is particularly suitably used. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. In addition, in the present specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. [1] Resin for forming an antireflection film of the present invention The resin for forming an antireflection film of the present invention is a repeating unit represented by the following formula (1) (hereinafter referred to as "repetitive unit (1)"), and the following The repeating unit (hereinafter referred to as "repetitive unit (2)") represented by the formula (2) contains at least one of them, and is soluble in an alkali developing solution. [Chemistry 16]

-17- 200903172 [In the formula (1), R1 to R7 each represent a hydrogen atom, -OH, -COOH or -S〇3H, and all of R1 to R7 are not hydrogen atoms). [Chem. 17]

In the formula (2), R8 to R14 each represent a hydrogen atom, -OH, -COOH or -S03H, and all of R8 to R14 are not a hydrogen atom. In the present invention, the repeating units (1) and (2) contained in the resin for forming the upper antireflection film may be used alone or in combination of two or more. Further, in the resin for forming an antireflection film of the present invention, in order to promote the solubility of the alkali developer, at least one of -OH, -COOH and -S03H may be contained in addition to the repeating units (1) and (2). Repeat the unit. In the case of specific repeating units, there are repeating units as shown in the following formula (3) '(4), (5) and (6) (the following are each referred to as "repetitive units (3)", "repeated units" (4)", repeat unit (5)" and "repeated unit (6)"). In the present invention, it is preferred to contain at least one of the above-mentioned repeating units (3) to (6). [Chem. 18]

-18- 200903172 [In the formula (3), R15 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, A represents a single bond, a carbonyl group or a carbonyloxy group, and B represents a single bond or an imino group, and D shows a single a bond or a two-valent organic group having a carbon number of 1 to 12] [Chem. 19]

COOH [In the formula (4), R16 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group] [Chemical 20]

(5) [In the formula (5), R17 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a fluorinated alkyl group having a carbon number of 1 to 12] [Chem. 21]

(6) In the formula (6), R18 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and -19-200903172 p represents a single bond, and a carbonyl group or a carbonyloxy group Q represents a single bond or a carbon number of 1 ～2 of the valence organic group, R19 and R2&lt;) each exhibiting a hydrogen atom, a carbon number of 1 to 4, or a carbon number of 1 to 4 (chemical group). Here, in the formula (3) D In terms of a divalent organic group having 1 to 12 carbon atoms, there are, for example, methylene ' 1,2-vinyl' anthracene, 2 -propylidene, 1,1 -dimethyl-1,2-vinyl, 1, 3-propenyl-p-methyl-1,3-propenyl, 2-methyl-1,3-propenyl, 1,4-butenyl '1-methyl-1,4·butenyl' 2_A Base — 1,4-butenyl, 1,5-pentenyl ' 1,1-dimethyl-I,4-butenyl ' 2,2-dimethyl-1,4-butenyl, 1,2-dimethyl-1,4-butenyl, 1,6-hexenyl, 1,3-cyclopentenyl, 1,4-cyclohexenyl, etc. Further, the formula can be imparted thereto. (3) The appropriate monomer aspect of the repeating unit (3) is, for example, ethylene sulfonic acid, allyl sulfonic acid, 1-methyl sulfonate (sul foxy) ethyl ester, 4-ethylene 1-benzenesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid, etc. The appropriate monomer which can be imparted to the repeating unit (4) represented by the formula (4) is, for example, (meth)acrylic acid, α-trifluoromethacrylic acid, etc. Further, in the R17 of the formula (5) As the alkyl group having 1 to 12 carbon atoms, there are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, positive a linear or branched alkyl group such as pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, etc., cyclobutyl, cyclopentyl a cycloalkyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bicyclo[2.2.1]heptane-2-yl group, a bicyclo[2.2.2]octane-2-yl group, an adamantane-1 group And an alicyclic hydrocarbon group such as adamantane-2-yl group, etc. -20- 200903172 Further, in the case of the fluorinated alkyl group having 1 to 12 carbon atoms in the R17, there is, for example, a hydrogen of the alkyl group having 1 to 12 carbon atoms. An atom-partial moiety or a group in which all r is replaced by a fluorine atom. The Q-valent organic group having a carbon number of 1 to 12 in the formula (6) has, for example, a methylene group, a 1,2-vinyl group, and 1 , 2-propenyl, 1,1-dimethyl-i,2-vinyl, 1,3-propenyl, 1-methyl- 1,3-propenyl, 2-methyl-1,3-propenyl, 1,4-butenyl, 1-methyl·1,4-butenyl '2-methyl-1,4-butyl Alkenyl, 1,5-pentenyl, 1,1-dimethyl-1,4·butenyl, 2,2-dimethyl-1,4-butenyl 1, 1,2-dimethyl -1,4-butenyl, 1,6-hexenyl' ι, 3-cyclopentenyl, 1,4-cyclohexenyl and the like. Further, in the alkyl group having 1 to 4 carbon atoms in R19 and R2() of the formula (6), there are, for example, a methyl group, an ethyl group, a n-propyl 'isopropyl 'n-butyl ' 2 -methylpropyl group. , 1-methylpropyl, tertiary butyl and the like. Further, in the case of the fluorinated alkyl group having 1 to 4 carbon atoms in the R19 and R2Q, for example, a part of the hydrogen atom of the alkyl group having 1 to 4 carbon atoms or a group substituted by a fluorine atom may be used. In addition, R19 and R2() may be the same or different. Further, in terms of the appropriate monomer which can be imparted to the repeating unit (6) represented by the formula (6), there is, for example, (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2- Hydroxy-3-propyl)ester, (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) (meth)acrylate, (meth)acrylic acid (1, 1,1-trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl)ester (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxyl) -4-pentyl)ester 2-([5-(Γ,1',1·-trifluoro-2·-trifluoromethyl-21-hydroxy)propyl]bicyclo[2-. 1] heptyl} ester, (meth)acrylic acid 3_-21 - 200903172 {[8-(Γ,1',Γ_trifluoro-2,-trifluoromethyl-2,-hydroxy)propyl]tetracyclic [6-2_1'13'6. () 2'7] Tetyl} ester and the like. Further, the resin for forming an antireflection film of the present invention may contain a repeating unit represented by the following formula (7_υ or (7_2) in addition to the repeating units (1) to (6) [hereinafter referred to as "heavy weight" Overwrite unit (7)"] [Chem. 22]

The resin for forming an upper antireflection film contains a repeating unit (7), and the effect of standing wave as an antireflection film can be sufficiently reduced. Further, the resin for forming the upper anti-reflection film preferably contains both a repeating unit represented by the formula (7-i) and a repeating unit represented by the formula (7-2). In the resin for forming an antireflection film of the present invention, the total content of the repeating units (1) and (2) is not particularly limited, and in the resin, the total repeating unit is made 1% by mole. In the case, it is preferably 2 0 to 8 0 mol%, more preferably 3 0 to 7 0 mol ° /. 'Specially good for 4 0~6 0 mol%. When the content ratio is 20 to 80 mol%, the standing wave effect as the antireflection film can be sufficiently reduced and the transmittance can be sufficiently obtained at a wavelength of 193 nm, and a good pattern can be obtained while suppressing an increase in sensitivity. Further, the repeating unit (3) to (6)-22-200903172 which promotes the solubility of the alkali developing solution is not particularly limited, and the total repeating unit is 1% by mole in the resin. In the case of 20 to 80 mol%, more preferably 30 to mol%, and particularly preferably 40 to 60 mol%. When the content ratio is from 20 to 80% by volume, sufficient solubility with respect to the developer can be obtained, and the occurrence of the residue or the residue can be suppressed. Further, the content of the repeating unit (7) is not particularly limited, and in the case where the total repeating unit is 100 mol% in the resin, it is preferably 10 to 60 vol%, more preferably 20 to 50 mol. Ear%, especially good 30~50%. When the content ratio is in the range of 1 60 to 60 mol%, the standing wave effect of the antireflection film can be sufficiently reduced. Further, in the present invention, the weight average molecular weight (hereinafter referred to as "Mwj") measured by gel permeation chromatography (GPC method) of the resin for forming an upper antireflection film is from 1,000 to 100,000, preferably from 1,500 to 10,000. More than 2000 to 7000. In the case where the Mw is less than 1000, the film formation energy is insufficient. On the other hand, in the case of more than 100,000, no sufficient dissolution rate with respect to the developer is obtained, and there is a dissolving matter or Further, in the resin for forming an upper anti-reflection film of the present invention, for example, a hydroperoxide type, a di-n-based peroxide type, and a polymerizable unsaturated monomer for each of the repeated units are used. A radical polymerization initiator such as a thiol peroxide type azo-nitride may be produced by polymerization in a suitable solvent in the presence of a chain transfer agent as needed. For example, a solvent for the polymerization may be used. The hospital, the main hospital, the Zheng Gengyuan 'Zhengxinyuan' is the 壬 壬 ' ' 癸 癸 等 等 等 ' ' ' ' 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 此 此 此 此 此 此 此 此 此 此 此200903172 alkane, cycloheptane 'cyclooctane Cycloalkanes such as 'decahydronaphthalene' to Aberdeen; aromatic hydrocarbons such as benzene'toluene, xylene 'ethylbenzene' cumene; chlorobutanes, bromohexanes, 'dichloroethanes , halogenated hydrocarbons such as hexamethylene dibromide or chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetonate, methyl propionate, etc.; acetone, 2-butanone, 4 - a ketone such as methyl-2-pentanone or 2-heptanone; an ether such as tetrahydrofuran 'dimethoxyethane or diethoxyethane; and the like, which may be used alone or in combination. Further, the reaction temperature in the polymerization is usually 4 Torr to 120 ° C, preferably 50 to 100 ° C, and the reaction time is usually 1 to 2 4 hours, preferably 3 〜1 2小时。 [2] The composition for forming an upper anti-reflection film (1) The composition for forming an anti-reflection film of the upper layer of the present invention (1), which is characterized by a resin for forming an upper anti-reflection film and a solvent. The above description of the "resin for forming an upper anti-reflection film" can be applied as it is. In addition, the resin for forming the upper anti-reflection film may be used singly or in combination of two or more. In the case of applying the upper anti-reflection film-forming composition (1) to the photoresist film, the "solvent" can be used for intermixing with the photoresist film. Performance deterioration. Examples of such a solvent include monovalent alcohols, polyvalent alcohols, alkyl ethers of polyvalent alcohols, alkyl ether acetates of polyvalent alcohols, ethers, cyclic ethers, higher hydrocarbons, and aromatics. Hydrocarbons, ketones, esters, water, etc. -24- 200903172 @法. Specifically, in the case of the monovalent alcohol, the monovalent alcohol having a carbon number of 4 to 8 is one of the main words, and there are, for example, 2-methyl-1-propanol, 1-butanol, 2-butanol' 1 2-pentyl Alcohol, 3-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-yl-1-butanol, 2,4-dimethyl-3-pentanol, and the like. The polyvalent alcohol group is, for example, ethylene glycol, propylene glycol or the like. The alkyl ethers of the polyvalent alcohol include, for example, ethylene glycol monomethyl-ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether 'propylene glycol monomethyl ether, propylene glycol monoethyl Ether, etc. Examples of the alkyl ether acetate of the polyvalent alcohol include, for example, ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol monomethyl ether B. Acid esters, etc. The ethers are, for example, dipropyl ether 'diisopropyl ether' butyl methyl ether, butyl ethyl ether, butyl propyl ether, dibutyl ether 'diisobutyl ether, tert-butyl- Methyl ether, tertiary butyl ethyl ether, tertiary butyl propyl ether, di-tertiary butyl ether, dipentyl ether, diisoamyl ether, cyclopentyl methyl ether, cyclohexylmethyl Ether, cyclopentyl ethyl ether, cyclohexyl ethyl ether, cyclopentyl propyl ether, cyclopentyl-2-propyl ether, cyclohexyl propyl ether 'cyclohexyl-2-propyl ether, cyclopentyl Butyl ether, cyclopentyl-tertiary butyl ether, cyclohexyl butyl ether, cyclohexyl-tertiary butyl ether and the like. Examples of the cyclic ether include tetrahydrofuran, dioxane and the like. As the higher hydrocarbon, there are, for example, decane, dodecane, undecane and the like. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and the like. -25- 200903172 Examples of the ketone include acetone, methyl ethyl ketone 'methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone 'diacetone alcohol and the like. The esters are, for example, ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Ethyl oxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Ethyl propionate, methyl 3-ethoxypropionate, and the like. Among these, preferred are monovalent alcohols, ethers, cyclic ethers, alkyl ethers of polyvalent alcohols, alkyl ether acetates of polyvalent alcohols, and higher hydrocarbons. Further, these solvents may be used singly or in combination of two or more. Further, in the composition (I) for forming an antireflection film of the present invention, an interface agent can be further blended for the purpose of improving coatability, defoaming property, leveling property and the like. For the interface activity, for example, BM-1 000, BM-11 〇〇 (above, BMCh emi), megafuck F 1 4 2 D, same as F 1 72 , same as F 1 73 , and F 1 83 can be used. [above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.): 丨F1 u 〇rad FC- .13 5 , with FC170C, with FC-430 &gt; FC- 43 1 C or above, Sumitomo 3M Company, Safron S -1 1 2, with S- 11 3, with S -13 1 'same as S- 141 [above, Asahi Glass Co., Ltd.], SH- 28PA, same 190, same 193' SZ-6032, SF8428 [above, TorayDow Corning Poly Oxide Company Manufactured, commercially available fluorine-based surfactants such as EMULGEN A-60, 104P, 3 06P (manufactured by Kao Corporation). -26- 200903172 In addition, these surfactants may be used singly or in combination of two or more. In addition, the amount of the surfactant to be added is preferably 5 parts by mass or less based on 1 part by mass of the resin for forming the upper antireflection film. In the present invention, the upper anti-reflection film-forming composition (1) is a resin for forming an anti-reflection film, and the like, in the solvent, for example, 0.1 to 15% by mass (preferably 0 · 1) It is preferable to dissolve the solid concentration of the polymer to a concentration of ~10% by mass, for example, by filtering with a filter having a pore diameter of about 20 nm. Further, the refractive index (η値) in the wavelength 193 urn of the film formed by using the composition (1) for forming the overlayer antireflection film of the present invention is preferably 15 or less, more preferably 1.25 to 1.45, particularly preferably 1.25. 1.4. When the refractive index is 1.5 or less, the reflection of light in the laminate is suppressed, so that the effect of reducing the low on-wave is good. Further, this refractive index can be measured by an elliptical symmetry after coating the upper anti-reflection film forming composition (1) on a tantalum wafer having a diameter of 8 inches. [3] Method of Forming Photoresist Pattern (1) The method for forming a photoresist pattern (1) of the present invention comprises: (1) a step of forming a photoresist film on a substrate (hereinafter referred to as "step (1)"), and 2) a step of forming an upper anti-reflection film on the resist film by forming a composition (1) for forming an upper anti-reflection film (hereinafter referred to as "step (2)"), and -27-200903172 (3) a step of irradiating the region of the resist film formed by the upper anti-reflection film with radiation, and performing exposure (hereinafter referred to as "step (3)") &gt; and (4) performing the step of developing and removing the upper anti-reflection film [ It is called "step (4)"]. In this step (1), a photoresist film can be formed on the substrate. Specifically, the obtained photoresist film is subjected to spin coating, flow casting coating, roll coating, or the like in a predetermined film thickness to coat the substrate. The preliminary baking (hereinafter referred to as "prebaking") is carried out to volatilize the solvent in the coating film to form a photoresist film. For the substrate, for example, a silicon wafer, an aluminum-coated wafer, or the like can be used. In addition, in order to maximize the potential of the formed photoresist film, for example, as disclosed in Japanese Patent Publication No. Hei 6-2424, the organic or inorganic system can be prevented on the substrate used. The reflective film is formed in advance. The photoresist composition solution is not particularly limited and may be appropriately selected in accordance with the purpose of use of the photoresist. For example, a chemically enhanced photoresist composition such as an acid generator may be dissolved in a suitable solvent, for example, to a solid component concentration of 〇1 to 20% by mass, for example, for example. The modulated photoresist composition solution can be filtered using a filter having a pore size of about 30 nm. Alternatively, a commercially available photoresist solution can be used as it is. Further, the photoresist composition solution may be either positive or negative, and a positive photoresist composition solution is preferred. In a chemically amplified positive photoresist, the acid dissociable organic group in the polymer -28-200903172 can be dissociated by the action of an acid generated by exposure to an acid generator, for example, a carboxyl group is produced, and as a result, relatively The solubility of the alkali developing solution in the exposed portion of the photoresist is increased, and the exposed portion is dissolved and removed by the alkali developing solution to obtain a positive resist pattern. In the step (2), the upper antireflection film forming composition (I) is used, and an upper antireflection film is formed on the photoresist film. Further, as for the composition (I) for forming an upper antireflection film, the above description can be applied as it is. Specifically, the obtained upper anti-reflection film is subjected to spin coating of the upper anti-reflection film-forming composition (I) in a predetermined film thickness, and is subjected to flow casting (f 1 〇 wcasting) coating, light coating, or the like. A suitable coating method can form an upper anti-reflection film by firing after coating on the photoresist film. The thickness of the upper anti-reflection film is closer to λ /4m (λ is the wavelength of the radiation, m is the refractive index of the upper anti-reflection film), and the reflection suppression effect can be obtained at the upper interface of the photoresist film. Become bigger. Therefore, it is preferable to bring the thickness of the upper anti-reflection film closer to this. Further, in the present invention, in the step (1), the pre-baking after the application of the photoresist composition solution, and the treatment of the upper film forming composition after the step (2) are applied, and the steps are performed, in order to perform the steps. Abbreviations can be omitted. In the step (3), radiation is applied to a region (set region) of the photoresist film formed by the upper anti-reflection film to perform exposure. The radiation can be suitably selected in accordance with the composition of the photoresist film or the combination of the photoresist film and the upper anti-reflection film. For example, it is possible to use visible light; ultraviolet rays such as g-line and i-line; far ultraviolet rays such as excimer lasers; X-rays such as synchrotron radiation; and various kinds of radiation such as charged particles of electron beams. Among these, ArF excimer lasers (wavelength -29-200903172 193 nm) and KrF excimer lasers (wavelength 248 nm) are preferred, especially ArF excimer lasers. Further, in order to improve the resolution of the photoresist film, the pattern shape, the developability, and the like, it is preferable to perform baking (hereinafter referred to as "PEB") after the exposure. The firing temperature can be suitably adjusted by the photoresist composition to be used, etc., but it is usually about 30 to 200 ° C, preferably 50 to 150 ° C. In this step (4), the removal of the upper anti-reflection film can be carried out by development. Specifically, the photoresist film can be developed by the developer, and after being washed, the desired photoresist pattern can be formed, and the upper anti-reflection film is not provided during the development or after the development. It can be completely removed by the necessity of the stripping step in other ways. In terms of the developer, there are, for example, dissolution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propyl Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine 'tetramethylammonium hydroxide' tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diaza An alkaline aqueous solution of heterobicyclo-[5,4,0]-7-undecene, 1,5-diazabicyclo-[4,3,0]-5-decane. Further, a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant may be added to the developer liquid. Further, it is 'generally' washed with water and dried after development using an aqueous alkaline solution. [4] Composition for forming an antireflection film of the upper layer (Π) -30- 200903172 The composition for forming an antireflection film of the upper layer of the present invention (II), which is soluble in the developer and contains: a polymer having an aromatic group (A) [hereinafter, simply referred to as "polymer (A)")' and a sensitive radiation linear acid generator (B) (hereinafter, simply referred to as "acid generator (B)") and having a sulfonic acid residue At least one of the compound (C) (hereinafter, simply referred to as "compound (C)") is characterized. In the composition (II) for forming an antireflection film of the upper layer of the present invention, the "polymer (A)"" is soluble in an alkali developer and has an aromatic group in particular, in the absence of the effect of the present invention. limited. The aromatic group has, for example, a phenyl group, a naphthyl group, a thienyl group and the like. Among these, especially a naphthyl group, an anthracenyl group is preferred. The polymer (A) is, for example, a repeating unit (hereinafter referred to as "repetitive unit 〇)"]' and a repeating unit shown by the following formula (ΠΙ) shown in the following formula (Π). It is preferred that at least one of the "repetitive units (11)" has a weight average molecular weight of from 1,000 to 100,000 as measured by gel permeation chromatography. [Chem. 23]

[In the formula (II), R22 to R28 each represent a hydrogen atom ' _0H' -COOH, or -31 - 200903172 [Chem. 24]

[In the formula (III), R 2 9 to R 3 5 each represent a hydrogen atom, -OH, -COOH, or -S03H] are contained in the repeating units (I) and (II) of the polymer (A), each of which may be only One type may be two or more types. Further, in the polymer (A), in order to promote the solubility of the alkali developing solution, the repeating units (I) and (II) may contain at least one of -OH, -COOH and -S03H. unit. For the specific repeating units, there are repeating units as shown in the following formulas (IV), (V), (VI) and (VII) (hereinafter, each is referred to as "repetitive unit (III)", "repeating unit" (IV), "Repeating Unit (V)" and "Repeating Unit (VI)", etc. In the present invention, it is preferred to contain at least one of the above-mentioned repeating units (111) to (V I).

-32- 200903172 [In the formula (IV), R36 represents a hydrogen atom, a methyl group, a hydroxyl group, A represents a single bond, a carbonyl group or a carbonyloxy group, B represents a single-mono bond, a linear chain having a carbon number of 1 to 20, and a branch A chain, an aromatic hydrocarbon group which may have a substituent]. Methyl or trifluoromethyl [or imino, D represents an alicyclic hydrocarbon group or

COOH (V) [In the formula (V), R3 7 represents a hydrogen atom, a methyl group, a hydroxyl group or a trifluoromethyl group] [Chem. 27]

(VI) Alkyl group or carbon number 1 [In the formula (VI), R3 8 represents a hydrogen atom, and a fluorinated alkyl group having a carbon number of 1 to 12 to 1 2] [Chem. 28]

-33- 200903172 [In the formula (VII), 'R3 9 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, P represents a single bond, a carbonyl group or a carbonyloxy group, and Q represents a single bond, and the carbon number is 丨20. a linear, branched, alicyclic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and each of R 4 ' and R 41 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine having a carbon number of 1 to 4 Alkyl]. Here, in the D of the formula (IV), the linear hydrocarbon group having a carbon number of 1 to 20, a branched chain, an alicyclic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, for example, a methylene group or a vinyl group, Propylene group, 1,3-propenyl group or 1,2-propenyl group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethyl group, octamethyl group, hexamethylene group, decylene group Base, eleven methyl group, dodecyl group, thirteen-methylene group, tetradecyl group, fifteen-methylene group, hexadecanyl group, heptamethyl group, 18-methyl group, Nineteen methylene group, 1-methyl-1,3-propenyl, 2-methyl-1,3-propenyl, 2-methyl-1,2-propenyl, 1-methyl-1,4 a saturated chain hydrocarbon group such as a butenyl group, a 2-methyl-1,4-butenyl group, a methine group, an ethylene group, a propylene group or a 2-propylene group; Tolylene, etc., such as propynyl, 1,3-cyclobutenyl, etc., cyclopentenyl, 1,3-cyclopentenyl, etc., cyclopentenyl, I, 4-cyclohexenyl, etc. a monocyclic hydrocarbon ring group such as a cyclohexenyl group such as a cyclohexenyl group such as a cyclohexenyl group or the like having a carbon number of 3 to 1 fluorene or the like; 1,4-arbornane (norborn) Nylene) or 2,5-arylene alkyl, such as norbornyl, 1,5-adamantyl, 2,6-adamantyl, etc. A crosslinked cyclic hydrocarbon ring group such as a hydrocarbon ring group having a carbon number of 4 to 20, a substituted or unsubstituted phenyl group, and the like. The appropriate monomer side of the repeating unit (III) represented by the formula (IV) can be given -34-200903172, for example, ethylene sulfonic acid 'allyl sulfonic acid, (meth)acrylic acid 1. ethyl ethyl acrylate , 4-ethylene-1-benzenesulfonic acid, 2-propenylamine-2-methylpropionic acid, and the like. Further, an appropriate aspect of the repeating unit (IV) represented by the formula (V) may be given, for example, (meth)acrylic acid, ?-trifluoromethacrylic acid or the like. The alkyl group having a carbon number of 1 to 12 in R3 8 of the formula (VI) has an alkyl group, an ethyl group, a n-propyl 'isopropyl group, a n-butyl group, a 2-methylpropyl group, a propyl group, and a third aspect. a linear butyl group of n-butyl 'n-pentyl, neopentyl, n-hexyl, n-heptyl-octyl ester, 2-ethylhexyl, n-decyl, n-decyl, etc. Cycloalkyl, cyclohexyl, cycloheptyloctyl, etc. cycloalkyl 'bicyclo[2.2.1]heptan-2-yl,bicyclo[2.2 alk-2-yl, adamantyl-1 -yl, adamantane -2 - alicyclic and the like. Further, in the case of the fluorinated alkyl group having 1 to 12 carbon atoms in the R38, there may be a part of a hydrogen atom having 1 to 12 carbon atoms, or all of the fluorine atom. The Q of the formula (VII) has a linear chain of 1 to 20 carbon atoms, a branched chain alicyclic group or an aromatic hydrocarbon group which may have a substituent, and a group 'vinyl group, 1,3-propenyl group or 1,2-propenyl, etc., propylene-based methylene group, 'pentamethylene group, hexamethylene group, heptamethyl group, octamethyl group, methyl group, decyl group, eleven methyl group, twelve Support group, thirteen-based 'tetradecylene, fifteen-methylene group, hexadecanyl group, heptadecyl 'octadecyl group, nineteen methyl group, 1-methyl-1,3- Propylene, keto-1,3.propenyl, 2-methyl-I,2-propenyl, benzyl-1,4-butene sulfonate monomer such as methyl 1-methyl, or, XES. Bad 2] octane group such as this sub-form, methyl, tetra, 9-methylmethyl 2-methyl, -35- 200903172 2 -methyl-1,4-butenyl 'methine, ethylene a saturated bond-like nicotinyl group such as a propylene group or a 2-propylene group, a cyclopentenyl group such as a propargyl group 1, 1, 3-cyclobutenyl group such as a tolylene group, Cyclo, 3-cyclopentenyl, etc., cyclopentenyl, cyclohexenyl, etc.; 1,4-cyclohexenyl, etc.; 1,5-cyclooctenyl a monocyclic hydrocarbon ring group such as a cycloalkenyl group having a carbon number of 3 to 10, such as a cycloalkenyl group; an imide group such as an I, 4-pyrene or a 2,5-norbornyl group; a crosslinked cyclic hydrocarbon ring of a hydrocarbon ring such as a 2,4 ring carbon number of 4 to 20, such as an alkyl '1,5-adamantyl' 2,6-adamantyl group or the like Base, substituted, unsubstituted phenylene, and the like. Further, in the R4Q and R41 of the formula (VII), the alkyl group having 1 to 4 carbon atoms is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or a 2-methylpropyl group. 1-methylpropyl, tertiary butyl and the like. Further, in the case of the fluorinated alkyl group having 1 to 4 carbon atoms in the R4 () and R41, for example, a part of a hydrogen atom of the alkyl group having 1 to 4 carbon atoms or a group substituted by a fluorine atom may be used. Further, R4 &lt;3 and R41 may be the same or different. Further, in terms of a monomer which can impart a repeating unit (VI) represented by the formula (VII), there is, for example, (meth)acrylic acid (1,1,ditrifluoro-2-trifluoromethyl-2-hydroxyl) - 3-propyl) ester, (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) (meth)acrylate, (meth)acrylic acid (1,1) , 1-trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl)ester, (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2.hydroxyl- 4·pentyl)ester, 2-{[5-(1',1',1'-trifluoro-21-trifluoromethyl-2'-hydroxy)propyl]bicyclo[2-. 1] heptyl} ester, 3-{[8-(Γ,Γ,1·-trifluoro-2'-trifluoromethyl-2'-hydroxy)propyl]tetracycline-36-(meth)acrylate 200903172 [6.2.1 ·13'6·02,7] Twelfth} ester. In particular, the polymer (Α) preferably contains at least a repeating unit represented by the following formula (VIII) and a repeating unit represented by the following formula (IX). In this case, the standing wave effect as an antireflection film can be further reduced, and the solubility with respect to the alkali developer can be improved. [化29]

(VI) cf3 (κ) o^oh Further, in the polymer (Α), the total content of the repeating units (1) and (11) is not particularly limited, and the polymer is A) In the case where the full-repetition unit is made 1% mol%, it is preferably 20 to 80 mol%, more preferably 3 to 70 mol%, and particularly preferably 4 to 6 m. %. When the content ratio is 20 to 80% by mole, the standing wave effect as an antireflection film can be sufficiently reduced, and sufficient transmittance is obtained at a wavelength of 193 nm, so that a good pattern can be obtained while suppressing the sensitivity. Increase. Further, the total of the repeating units (ΙΠ) to (IV) of the solubility of the alkali developing solution is not particularly limited. In the polymer (A), the total repeating unit is made 1% by mole. In the case of 2 0 to 8 0 mol%, more preferably -37-200903172 is 30 to 70 mol%, and particularly preferably 40 to 60 mol%. When the content ratio is from 20 to 80 mol%, sufficient solubility with respect to the developer can be obtained, and the occurrence of the residue or the dross can be suppressed at the time of development. The weight average molecular weight (hereinafter referred to as "Mw") measured by the gel permeation chromatography (GPC method) of the polymer (A) is from 1,000 to 100,000, preferably from 1,500 to 10,000, more preferably from 2,000 to 7,000. . If the Mw is less than 1 ,, there is a possibility that the film formation energy is not very high. On the other hand, in the case of more than 100,000, a sufficient dissolution rate with respect to the developer cannot be obtained, and there is a dissolving substance or The possibility of dross occurring. Further, the polymer (A) is, for example, a hydroperoxide, a dialkyl peroxide or a didecyl peroxide, which is a polymerizable unsaturated monomer corresponding to each of the repeating units. A radical polymerization initiator such as an azo compound can be produced by polymerization in a suitable solvent in the presence of a chain transfer agent as needed. In terms of the solvent used for the polymerization, there are olefins such as n-pentane, n-hexane, n-heptane, n-octane, n-decane, n-decane, etc.; cyclohexane, cycloheptane, cyclooctane , a cycloalkane such as decahydronaphthalene, takabe, etc.; aromatic hydrocarbons such as benzene 'toluene' xylene, ethylbenzene, cumene; chlorobutanes, bromohexanes, dichloroethanes , halogenated hydrocarbons such as hexamethylene dibromide or chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; acetone, 2-butanone, 4- a ketone such as methyl-2-pentanone or 2-heptanone; an ether such as tetrahydrofuran, dimethoxyethane or diethoxyethane; and the like. These solvents may be used singly or in combination of two or more. Further, the reaction temperature in the polymerization is usually 40 to 120 ° C', preferably 50 to 100 t, and the reaction time is usually 1 to 24 hours', preferably 3 to 12 hours. Further, in the composition (II) for forming an antireflection film of the present invention, the "acid generator (B)" is exposed by radiation such as visible ultraviolet rays, ultraviolet rays, electron beams, X-rays or the like. The substance in which the acid occurs. In the acid generator (B), for example, a halogen compound such as a chloro compound, a maple compound, a sulfonate compound, a quinone diazide compound or the like can be given. Specific examples of the acid generator (B) include, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, Triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2_(3_tetracyclo[4.4.〇.l2 '5.l7'1Q]dodecyl)-1,1-difluoroethanesulfonate, triphenylsulfonium n,n-bis(nonafluoro-n-butanesulfonate) imidate, triphenyl camphor Sulfonate, 4-cyclohexylphenyldiphenylphosphonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyl diphenyl鎏Perfluoro-n-octane sulfonate, 4-cyclohexylphenyldiphenyl fluorene 2-bicyclo[2.2.1]heptan-2-yl-1,1,2,2-tetrafluoroethane sulfonate 4-cyclohexylphenyldiphenylfluorene 2-(3-tetracyclo[4.4.0.12'5.17'1Q]dodecy)-1,1-difluoroethanesulfonate, 4-cyclohexylphenyl Diphenyl hydrazine, hydrazine-bis(nonafluoro-n-butane sulfonium) imidate, 4-cyclohexylphenyl diphenyl camphorsulfonate, 4-tris-butylphenyldiphenylphosphonium trifluoride Methanesulfonate, 4-tris-butylphenyldiphenylphosphonium hexafluoro- Butane sulfonate, 4-tris-butylphenyldiphenylphosphonium perfluoro-n-octane sulfonate, 4-tertiary butylphenyldiphenyl fluorene 2--39- 200903172 Double ring [2.2. 1]Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate '4-tris-butylphenyldiphenylphosphonium 2-(3-tetracyclo[4.4.0.12, 5.17, 1G ]12-yl)-1,1-difluoroethanesulfonate, 4-tris-butylphenyldiphenylphosphonium, hydrazine-bis(nonafluoro-n-butanesulfonate) imidate, 4-tri Butyl phenyl diphenyl camphorsulfonate, tris(4-3-tributylphenyl)phosphonium trifluoromethanesulfonate, tris(4-tributylphenyl)phosphonium hexafluoro-n-butyl Alkane sulfonate, tris(4-tert-butylphenyl)phosphonium perfluoro-n-octane sulfonate, tris(4-tributylphenyl)phosphonium 2-bicyclo[2.2.1]heptan-2- 1,1,2,2-tetrafluoroethanesulfonate, tris(4-tributylphenyl)phosphonium 2-(3-tetracyclo[4.4.0.12'5.17'1G]dodecylate) -1,1_difluoroethane sulfonate, tris(4-tributylphenyl)anthracene, fluorene-bis(nonafluoro-n-butanesulfonyl) imidate, tris(4-tertiary butyl) Phenyl) camphor sulfonate, diphenyl iodine trifluoromethane sulfonate, diphenyl iodine hexafluoro-n-butyl Alkane sulfonate, diphenyl iodine perfluoro-n-octane sulfonate, diphenyl iodine 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane Sulfonate, diphenyl iodide 2-(3-tetracyclo[4.4.0.12'5.17'1Q]dodecyl)-oxime, iota-difluoroethane sulfonate, diphenyl iodine N, N - bis(nonafluoro-n-butane sulfonium) imidate, diphenyl sulfonium sulfonate, bis (4-tert-butylphenyl) key-switched trifluoromethyl sulfonate 'double (4 - three) Butyl phenyl) iodine hexafluoro-n-butane sulfonate, bis(4-tert-butylphenyl) iodine gun perfluoro-n-octane sulfonate, bis(4-tertiary butyl benzene Iodine iodine 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, bis(4-tributylphenyl) iodine gun 2-(3 - four rings [4.4·0·12, 5.17'1()] dodecyl)-1,1-difluoroethanesulfonate, bis(4-tributylphenyl) iodine gun N,N- Bis(nonafluoro-n-butanesulfonyl) imidate, bis(4-tributylphenyl)iodonium sulfonate, -40- 200903172 1-(4-n-butoxynaphthalen-1-yl) Tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene hexafluoro-n-butane Sulfonate ' 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene gun perfluoro-n-octane sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrogen Thiophene 2-2-cyclo[2,2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene 2-(3-tetracyclo[4.4.0.12'5"7,1 Q]dodecyl)-1,1-difluoroethanesulfonate, 1-(4-pytoxynaphthalen-1-yl) Tetrahydrothiophene, Ν-bis(nonafluoro-n-butanesulfonyl)imid ate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene mothyl sulfonate, 1-( 3,5-Dimethyl-4-hydroxyphenyl)tetrahydrothiophene trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene hexafluoro-positive Butane sulfonate ' 1-(3,5-dimethyl-4-transphenyl)tetrahydrothiophene perfluoro-n-octyl sulfonate ' 1-(3,5-dimethyl-4 -hydroxyphenyl)tetrahydrothiophene key 2-bicyclo[2.2.1]heptan-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 丨-(a),5·dimethyl_4_ Phenyl phenyl) tetrahydrothiophene gun 2-(3-tetracyclo[4.4.0.12, 5.17,1()]dodecyl)-1,1-difluoroethanesulfonate ' 1-(3,5 - Dimethyl-4-hydroxyphenyl)tetrahydrothiophene key N,N- Bis(nonafluoro-n-butanesulfonyl) imidate, dimethyl-4·hydroxyphenyl)tetrahydrothiophene mothyl sulfonate, N-(trifluoromethanesulfonate) amber imine, N-( Nonafluoro-n-butane sulfonium oxy) succinimide, N-(perfluoro-n-octane sulfonium oxy) amber quinone imine, N (2-bicyclo[2.2.1]hept-2-yl-1, 1,2,2-tetrafluoroethane, sulfonium oxide, sulfonium imine, N-(2-(3-tetracyclo[4.4.0,12,5.17,1. ]12基)_1, 卜, difluoride, sulfonate, sulfoxime, acetonitrile, N-(camphorsulfonate) amber, imine, N-(trifluoromethanesulfonyloxy)bicyclo[2·21 Geng 5_ene-2,3·dicarboxyfluorene-41 - 200903172 Amine, N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]heptinium imine, N-(perfluoro- N-octanesulfonyloxy)bicyclo[2.2. dicarboxy quinone imine, N-(2-bicyclo[2.2.1]hept-2-yl-1,]sulfonyloxy)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxyfluorene y y [4.4.0.12, 5.17, oxime. ] Twelve bases -1,1-difluoroethane [2.2.1] hept-5-ene-2,3-dicarboxylimenide, N-(樟朋[2.2.1]hept-5-ene -2,3-dicarboxylimine, etc. The acid generator (B) may be used singly or in combination. Further, the content of the acid generator (B) is 〇·1 with respect to the amount of the polymer. Preferably, it is 0.1 to 5 parts by mass, more preferably 0.1 to 5 parts by mass. The content is 0.1 to 15. While reducing the defect of the probe, the content of the good photoresist acid generator (B) can be obtained. The effect of the probe defect is not sufficient when the amount is less than 0.1 part by mass. On the other hand, in the case of the case, the top loss of the developed photoresist pattern is obtained to obtain a rectangular photoresist pattern. The compound for forming an antireflection film of the upper layer is a compound having a sulfonic acid residue, and is not particularly limited, and is preferably, for example, the following general formula (1). [Chem. 31] -5-ene-2 ,3-dicarboxyl 1]hept-5-ene-2,3-.,2,2-tetrafluoroethane oxime, N-(2- (3-tetrazed oxime) bis-ring I sulfonyl) double ring In combination with two or more kinds of the compound (A), it is 100 mass% to 10 parts by mass, and in the case of a mass portion, the shape of the case 3. Further, : The shape will decrease by more than 15 parts by mass F, and it will be difficult to form the compound (II). The compound (C) shows the compound as R21! Z -fS〇3H) (I) -42- 200903172 (1), R21 represents a linear or branched chain of a carbon number of 1 to 10, an alicyclic alkyl group having 3 to 2 carbon atoms or a derivative thereof, a hydroxyl group, a residue, an alkyl ether a group, an alkoxycarbonyl group, or an alkylcarbonyloxy group, and Z is a linear, branched, alicyclic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and m is 0 to 4; An integer, η represents an integer from 1 to 4. In addition, R2 1 is a case where there are plural numbers, which may be the same or different from each other. In the formula (1), the linear group or the branched chain of the carbon number of 1 to 10 of R21 has, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methyl. Propyl, 1-methylpropyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl and the like. Further, in the formula (1), the alicyclic alkyl group having a carbon number of 3 to 20 in R21 or a derivative thereof may be, for example, nor formamidine, tricyclodecane, tetracyclododecane, ordination or cycloding. a cycloaliphatic ring derived from a cycloalkane or the like, which is formed by a cycloalkane or the like, such as a methyl group. A linear, branched or cyclical base of ethyl 'n-propyl' isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, etc. One or more of the substituted groups may be substituted with one or more groups such as a hydroxyl group, a carboxyl group, a hydroxyalkyl group, a cyano group, a cyanoalkyl group or the like. Further, in the oxime of the formula (1), a linear chain having a carbon number of 4 to 12, a branched chain, and an alicyclic hydrocarbon group are, for example, a 1-methyl-1,3-propenyl group, a 2-methyl group. -1,3-propenyl, 1,4-butenyl, 1-methyl-1,4-butenyl, 2-methyl-I,4.butenyl, I,5-pentenyl, 1,1-dimethyl-1,4-butenyl, 2,2-dimethyl-1,4-butenyl, 1,2-dimethyl-1,4-butenyl, anthracene, 6 _hexenyl; -43- 200903172 1,3_cyclobutenyl and the like cyclobutenyl, 1,3-cyclopentenyl and the like cyclopentenyl '1,4-cyclohexenyl, etc. a monocyclic hydrocarbon ring group such as a cyclohexenyl group such as a hexenyl group, a 1,5-cyclooctenyl group or the like: a 1,4-norbornyl group or a 2,5-norbornyl group or the like. A crosslinked cyclic hydrocarbon ring group such as a flavonyl group, a 1,5-adamantyl group, a rudomantyl group such as a 2,6-adamantyl group or the like. Further, the aromatic hydrocarbon group which may have a substituent in Z of the formula (1) may, for example, be a phenyl group, a naphthyl group or a thienyl group. Specific examples of the compound (C) include, for example, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid 'heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, and dodecafluoropentanesulfonic acid 'decafluorotrifluorosulfonic acid. , fifteen fluoroheptane sulfonic acid, heptafluorooctane sulfonate 'octafluorofluoro sulfonic acid, fluoromethane sulfonic acid, difluoromethane sulfonic acid, 1, 1 · difluoroethane sulfonic acid ' 2,2 , 2-trifluoroethanesulfonic acid, 1,1-difluoropropanesulfonic acid ' 1,1,2,2-tetrafluoropropanesulfonic acid, 3,3,3-trifluoropropanesulfonic acid, 2,2, 3,3,4,4,4-heptafluorobutanesulfonic acid, 3,3,4,4,4-pentafluorobutanesulfonic acid, etc., fluorosulfonic acid, methanesulfonic acid 'ethanesulfonic acid, Propane sulfonic acid, isopropane sulfonic acid, butane sulfonic acid 'isobutane sulfonic acid, 1,1-dimethylethane sulfonic acid, pentane sulfonic acid, b methylbutane sulfonic acid ' 2 _ methyl butyl Alkane sulfonic acid, 3-methylbutane sulfonic acid, neopentane sulfonic acid, hexane sulfonic acid, heptane sulfonic acid, octane sulfonic acid, decane sulfonic acid, phenolic sulfonic acid, etc. Benzenesulfonic acid, 2-toluenesulfonic acid, 3-toluenesulfonic acid, 4-toluenesulfonic acid, 4-ethylbenzenesulfonic acid, 4-propylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-(three level Benzosulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-1,3,5-trimethylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 4-chlorobenzenesulfonic acid, 4- Bromobenzenesulfonic acid, 4-fluorobenzenesulfonic acid, 2,3,4,5,6-pentafluorobenzenesulfonic acid, 4-hydroxybenzenesulfonyl-44 - 200903172 acid, 2-hydroxybenzenesulfonic acid, 3-hydroxybenzene Sulfonic acid, 3 - sulfosalicylic acid ' 4 - sulfosalicylic acid, 5-sulfosalicylic acid ' 1-naphthyl acid extended ' 2 - naphthyl sulfonic acid, cyclohexyl sulfonic acid, 2-hydroxyl ring Hexyl sulfonic acid ' 3 -hydroxycyclohexyl sulfonic acid ' 4 - sulfobenzoic acid, 4-sulfoaniline and other aryl sulfonic acids, benzyl sulfonic acid, phenethyl sulfonic acid, etc. Cyclic sulfonic acids such as acid, '2-hydroxybenzenesulfonic acid' of 3-benzenesulfonic acid '3-sulfosalicylic acid' 4-sulfosalicylic acid, 5-sulfosalicylic acid '1_Naphthylsulfonic acid, 2-naphthylsulfonic acid, cyclohexylsulfonic acid, 2-hydroxycyclohexylsulfonic acid '3-hydroxycyclohexylsulfonic acid, poly(4-styrenesulfonic acid)' polyethylene naphthalene Sulfonic acid, etc. The compound (C) may be used singly or in combination of two or more. Further, the content of the compound (C) is preferably from 1 to 15 parts by mass relative to 100 parts by mass of the polymer (A). More preferably, it is preferably from 1 to 10 parts by mass. 5 parts by mass. This content is in the range of 0" to 15 parts by mass, and the defect of the probe can be reduced while obtaining a good resist pattern shape. Further, the content of the film is less than 1 part by mass. The effect of reducing the defect of the probe may be insufficient. On the other hand, in the case of more than 15 parts by mass, the top loss of the resist pattern after development is remarkably increased. It will be difficult to obtain a rectangular photoresist pattern. Further, the composition (II) for forming an antireflection film of the upper layer of the present invention may contain a surfactant for the purpose of improving coatability, defoaming property, leveling property and the like. For the surfactant, for example, BM-1 000, BM-1100 (above, BM Chemi), megafuck F142D, F172, F173, and F183 [above, oil sold in Japan] - 200903172 Ink Chemical Industry Co., Ltd., Fluorad FC-135, with FC170C, with FC-430, FC-431 (above, Sumitomo 3M), Safron S-112, with S-113, with S-131, same S-141 (above, Asahi Glass Co., Ltd.), SH-28PA, same 190, same 193, SZ-6032, SF8428 [above, Toray Dow Corning Polyoxo Co., Ltd.], EMULGEN A-60, 10 4P, 30 6P [above A fluorine-based surfactant sold in the market under the trade name of Kao Corporation. Further, these surfactants may be used singly or in combination of two or more. The content of the surfactant is preferably 5 parts by mass or less based on 100 parts by mass of the polymer (A). In the present invention, the composition of the anti-reflective film for the formation of the anti-reflection film is usually 0.1 to 15% by mass, preferably 0.1 to 1% by mass. After it is dissolved in a solvent, it is preferably used, for example, by filtering with a filter having a pore diameter of about 2 〇 nm. In the solvent, when the composition for forming an overlayer antireflection film of the present invention is applied onto a photoresist film, interspinning with the photoresist film is performed, and the lithography performance is hardly caused. Degraded person. Examples of such a solvent include, for example, monovalent alcohols, polyvalent alcohols, alkyl ethers of polyvalent alcohols, alkyl ether acetates of polyvalent alcohols, ethers, cyclic ethers, and higher hydrocarbons. Aromatic hydrocarbons, ketones, esters, water, etc. The monovalent alcohol is preferably a monovalent alcohol having 4 to 8 carbon atoms. Specifically, there are, for example, 2-methyl-propanol, 1-butanol '2-butanol, pentyl alcohol '2-pentanol, 3-pentanol, 3-methyl-2-pentanol, 4 -Methyl-2-pentanol '2-B-46 - 200903172, based on 1-butanol, 2,4-dimethyl-3-pentanol, and the like. Examples of the polyvalent alcohol include ethylene glycol, propylene glycol and the like. The alkyl ethers of the polyvalent alcohol include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether 'ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol single Methyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol single B Ether and the like. Examples of the alkyl ether acetate of the polyvalent alcohol include, for example, ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol monomethyl ether B. Acid esters, etc. The ethers are, for example, dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, dibutyl ether, diisobutyl ether, tert-butyl- Methyl ether, tertiary butyl ethyl ether, tertiary butyl propyl ether, di-tertiary butyl ether, dipentyl ether, diisoamyl ether, cyclopentyl methyl ether, cyclohexylmethyl Ether, cyclopentyl ethyl ether, cyclohexyl ethyl ether, cyclopentyl propyl ether, cyclopentyl-2-propyl ether, cyclohexyl propyl ether, cyclohexyl-2-dipropyl ether, cyclopentyl Butyl ether, cyclopentyl-tertiary butyl ether 'cyclohexylbutyl ether, cyclohexyl-tertiary butyl ether and the like. Examples of the cyclic ether include tetrahydrofuran, dioxane and the like. Examples of the higher hydrocarbons include, for example, decane &apos;dodecane&apos; undecane. Examples of the aromatic hydrocarbons include benzene'toluene xylene. Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone 'diacetone alcohol and the like. In terms of the ester, there are, for example, ethyl acetate 'butyl acetate, ester ' 2 -trans group-47-200903172 ethyl propionate, methyl 2-hydroxy-2-methylpropionate 2 -hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate 'ethyl hydroxyacetate' methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate 3-ethyl 3-methoxypropionate '3-Ethyloxypropionate, 3-ethoxypropionate, and the like. Among these, preferred are monovalent alcohols, ethers, cyclic ethers, alkyl ethers of polyvalent alcohols, alkyl ether acetates of polyvalent alcohols, and higher hydrocarbons. Further, these solvents may be used singly or in combination of two or more. Further, the refractive index (n?) at a wavelength of 193 nm of the film formed by using the composition for forming an overlayer antireflection film of the present invention is preferably 1.5 or less, more preferably 1.25 to 1.45, particularly preferably 1.25 to 1.4. . When the refractive index is 1.5 or less, reflection of light in the laminate can be suppressed, and the standing wave effect can be reduced. Further, this refractive index was measured by an elliptical symmetry after coating the upper anti-reflection film-forming composition (II) on a wafer having a diameter of 8 inches. [5] Method for forming photoresist pattern (II) The method for forming a photoresist pattern (II) of the present invention comprises: (1) a step of forming a photoresist film on a substrate (hereinafter referred to as "step (1)"), and (2) a step of forming an upper anti-reflection film forming composition (II), forming an upper anti-reflection film on the resist film (hereinafter referred to as "step (2)"), and (3) the upper anti-reflection film The portion of the resist film to be formed is irradiated with radiation of -48-200903172, and the step of performing exposure (hereinafter referred to as "step (3)")' and (4) is performed by developing and removing the upper anti-reflection film (hereinafter, It is called "step (4)"]. In this step (1), a photoresist film is formed on the substrate. Specifically, a suitable coating method such as spin coating, flow casting coating, roll coating, or the like is performed on the substrate so that the obtained photoresist film has a set film thickness. After the application, "pre-baking (hereinafter referred to as "prebaking (PB)") is carried out, and a photoresist film is formed by volatilizing the solvent in the coating film. For the substrate, for example, a wafer coated with a tantalum wafer or aluminum can be used. In addition, in order to maximize the potential of the formed photoresist film, for example, an anti-reflection of an organic or inorganic system is used on the substrate to be used, as disclosed in Japanese Patent Publication No. Hei 6-145245. The film is prepared for preforming. The photoresist composition solution is not particularly limited and may be appropriately selected in accordance with the purpose of use of the photoresist. In the case of the specific photoresist composition solution, for example, a chemically enhanced photoresist composition such as an acid generator is dissolved in a suitable solvent, for example, at a solid content concentration of 0.1 to 20% by mass. For example, a photoresist composition solution prepared by filtering with a filter having a pore size of about 3 Onm can be used. In addition, commercially available photoresist solutions can be used as they are. Further, the photoresist composition solution may be either a positive type or a negative type, and a positive type photoresist composition solution is preferred. In the chemically amplified positive resist-49-200903172, the acid dissociable organic group in the polymer is dissociated by the action of an acid generated by exposure from an acid generator, for example, a carboxyl group is generated, and the result is a photoresist exposure portion. When the solubility of the developer is changed, the exposed portion is dissolved and removed by the developer, and a positive resist pattern can be obtained. In the step (2), the upper anti-reflection film-forming composition (II) is used, and an upper anti-reflection film can be formed on the photoresist film. Further, the above description of the composition for forming an upper antireflection film can be applied as it is. Specifically, the upper anti-reflection film obtained is subjected to spin coating, flow casting coating, roll coating, etc., to form the upper anti-reflection film-forming composition (II) so as to have a predetermined film thickness. After the coating method is applied onto the photoresist film, the upper anti-reflection film can be formed by firing. The thickness of the upper anti-reflection film is closer to λ /4m (λ is the wavelength of the radiation, m is the refractive index of the upper anti-reflection film), and the reflection suppression effect can be changed at the upper interface of the photoresist film. Big. Therefore, it is preferable to bring the thickness of the upper anti-reflection film closer to this. Further, in the present invention, in the step (1), the prebaking after the coating of the photoresist composition is applied, and the treatment of any of the coating of the upper film forming composition in the step (2) is carried out, It may be omitted for the sake of simplification of the steps. In the step (3), the region (setting region) of the photoresist film formed by the upper anti-reflection film is irradiated with radiation to perform exposure. The radiation can be suitably selected in accordance with the composition of the photoresist film or the combination of the photoresist film and the upper anti-reflection film. For example, visible light; g-ray, i-ray, etc.; ultraviolet light such as excimer laser; synchronous-50-200903172 accelerator radiation, etc.; various radiations of charged particle lines such as electron beams can be selected . Among these, ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser is preferable. Further, in order to improve the resolution, pattern shape, developability, and the like of the photoresist film, it is preferable to perform baking after exposure (hereinafter referred to as "PEB"). The firing temperature can be suitably adjusted depending on the photoresist composition to be used, etc., but it is usually about 30 to 200 ° C, preferably 50 to 150 ° C. In this step (4), the removal of the photoresist film and the upper anti-reflection film can be simultaneously performed by development. Specifically, the photoresist film can be developed by a developing solution, and after the cleaning, the desired photoresist pattern can be formed, and the upper anti-reflection film is not subjected to other routes during the development or cleaning after development. The stripping step can be completely removed. In terms of the developer, for example, dissolving sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propyl Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diaza An alkaline aqueous solution of heterobicyclo-[5,4,0]-7-undecene, 1,5-diazabicyclo-[4,3,0]-5-decane. Further, in the developing solution, a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after development using an aqueous alkaline solution, it is generally washed with water and dried. [Embodiment] Hereinafter, the present invention will be described more specifically by way of examples. However, the invention is not limited by any of the embodiments. 1. Examples 1 to 8 and Comparative Example 1, 2 [1 -1] Synthesis of upper antireflection film-forming resin Hereinafter, each polymer [polymer (A-1) to (A-8) and polymer) A synthesis example of (a-1) to (a-2)] will be described. Further, the evaluation of the physical properties of the respective polymers obtained in the respective synthesis examples can be carried out in the next step. (1) M w using GPC column (G2000HXL: 2, G3000HXL: 1 support, G4000HXL: 1 support) made by Tosoh, at a flow rate of 1.0 ml/min, dissolving solvent tetrahydrofuran, column temperature 40 °C analysis conditions, by It was determined by gel permeation chromatography using monodisperse polystyrene as a standard. (2) Copolymerization ratio] The area ratio of the peaks derived from the side chain groups of the respective monomers in the absorption spectrum of H-NMR and &quot;C-NMR, and the copolymerization ratio of each monomer was determined. &lt;Synthesis Example 1 &gt; 30 g of tetrahydrofuran (THF) was placed in a separable flask equipped with a stirrer, a thermometer and a cooling tube, and 6-vinyl-2-naphthol 2_28 8 was added after foaming for 15 minutes of nitrogen gas. 8 g, 1-vinylnaphthalene 8.2945g' α-trifluoro-52- 200903172 methacrylic acid 9.4167g ' 2,2,-azobis(dimethyl 2-methylpropionate) 1. 8 5 7 7 g , so that the internal temperature is raised to 4 5 . (1. After 1 hour, the internal temperature was raised to about 70 ° C and refluxed for 8 hours, and then cooled to 25 ° C. Then 'vacuum was dried and the solvent was removed to obtain a copolymer. Mw is 2.7χΐ〇3, which is 6_ethylene-2_naphthol/; [_vinylnaphthalene/α-trifluoromethacrylic acid copolymerization ratio (mol%) is 1 0/40/5 0. This copolymerization The substance acts as "polymer (Α-1)". [Chem. 32]

&lt;Synthesis Example 2 &gt; In a separable flask equipped with a stirrer 'thermometer and a cooling tube, 30 g of methanol was charged. After a nitrogen gas was foamed for 15 minutes, 6-vinyl-2·naphthoquinone 1 · 4 9 1 was added. 3 g,2-vinyl naphthalene 9.4 5 7 6 g, methacrylic acid 9. 〇5 〇〇g, 2,2'-azobis(2-methylpropionic acid dimethyl)242〇9g, internal temperature Warm to 45 °C. After 1 hour, the internal temperature was raised to about 7 Torr &lt;t, and it was refluxed for 8 hours, and then cooled to 25. (:. Next, vacuum drying and solvent removal to obtain a copolymer. The copolymer Mw is ΐ9.5χ1〇3,6-vinyl-2-naphthol/2-vinylnaphthalene/methylacrylic acid copolymerization The ratio (% by mole) was 5/35/6 〇. This copolymer was used as -53-200903172 as "Polymer (A-2)".

(A-2) &lt;Synthesis Example 3 &gt; A separable flask equipped with a stirrer, a thermometer, and a cooling tube was charged with 30 g of methyl isobutyl ketone (hereinafter referred to as "MIBK"), and nitrogen gas was emitted for 15 minutes. After soaking, add 8.1297 g of 2·vinylnaphthalene, 4.6866 g of 6-vinyl-2-naphthol 〇:-trifluoromethyl acrylate 7.3837 §, 2,2,-azobis(2-methylpropionic acid dimethyl The base ester was 4.5521 g, and the internal temperature was raised to 45 °C. After 1 hour, the internal temperature was raised at 90 ° C for 8 hours, and then cooled to 2 5 ° C. Then vacuum drying was carried out and the solvent was removed to obtain a copolymer. The copolymer Mw was 3.1×10 3 , and the copolymerization ratio (mol%) of 2-vinylnaphthalene/6-vinyl-2-naphthol/difluoromethylpropionic acid was 4〇/20/4〇. This copolymer was referred to as "polymer (Α-3)". -54- 200903172 [Chem. 34]

&lt;Synthesis Example 4 &gt; In a mixer, a thermometer, and a cooling tube, separable release of MIBK 30g, after 15 minutes of nitrogen gas foaming, 'Add 6_B

The phenol was 8.9514 g, α-trifluoromethacrylic acid H. 〇 4 86 g, 2J (dimethyl 2-methylpropionate) 4.541 g, and the internal temperature was raised to 45 ° C. Thereafter, the internal temperature was raised at 90 ° C for 8 hours, and then cooled to then 'vacuum drying and the solvent was removed to obtain a copolymer. The copolymer 'Mw was 2_6χ1〇3,6-vinyl-2-naphthol The copolymerization ratio of the /α-based acrylic acid (% by mole) was 4 〇 / 6 〇. This is a total of "polymer (Α-4)". [Chem. 35] (Α-4) i bottle, containing ene-2-naphthalene-azo double 1 hour 25 . . 〇_Trifluoromethyl: as -55- 200903172 &lt;Synthesis Example 5 &gt; 50 g of methyl ethyl ketone was placed in a separable flask equipped with a stirrer 'thermometer and a cooling tube', and after nitrogen gas foaming for 15 minutes Add 6-vinyl-2-naphthol 4.7373g' α-trifluoromethacrylic acid 3.8981g, cis-butyl dianhydride 1.3 3 00g, 2,2·-azobis(2-methylpropionic acid dimethyl ester ) l_3 646g, the internal temperature is raised to 45 ° C. After 1 hour, the internal temperature was raised and the reaction was carried out at 70 ° C for 8 hours, and then cooled to 25 ° C. Subsequently, 3 g of a 1% aqueous solution of oxalic acid was gradually dropped. The internal temperature was raised to 70 ° C and the reaction was carried out for 2 hours. Thereafter, the reaction liquid was washed with water (5 g of water 3 times) to carry out vacuum drying, and the solvent was removed to obtain a copolymer. The copolymer had a copolymerization ratio (mol%) of Mw of 3.5xl03'6-vinyl-2-naphthol/?-trifluoromethylene acrylate/maleic acid of 40/40/20. This copolymer was referred to as "polymer (Α-5)". [化36]

(Α-5) &lt;Synthesis Example 6 &gt; A separable flask equipped with a stirrer, a thermometer and a cooling tube was charged with MIBK 3 0 g, and after 6 minutes of nitrogen gas foaming, 6-vinyl-2-pyrophenol was added. 7.8742 g, α-trifluoromethacrylic acid 8.0992 g, 4,4,5,5,6,6,7, -56- 200903172 7,7-nonafluoro-2-hydroxyheptyl acrylate 4.02668,2,2 '-Azobis(dimethyl 2-methylpropionate) 3.9946 g, and the internal temperature was raised to 45 °C. After 1 hour, the internal temperature was raised to 90. (: After 8 hours of reaction, cooling to 25 ° C °, followed by vacuum drying and solvent removal to obtain a copolymer. The copolymer, Mw 3.3 x 10, 6-vinyl-2-naphthoquinone / α-three The copolymerization ratio (% by mole) of fluoromethacrylic acid / 4,4,5,5,6,6,7,7,7-nonafluoro-2-hydroxyheptyl acrylate was 40/5 0/1 0. This copolymer was referred to as "polymer (Α-6)". [Chem. 37]

(Α-6) &lt;Synthesis Example 7 &gt; A separable flask equipped with a stirrer, a thermometer and a cooling tube was charged with 30 g of MIBK, and after foaming with nitrogen gas for 15 minutes, 2-vinylnaphthalene was added to 2.6936 g of 6-ethylene- 2-naphthol 4.45 97g, 8.0992g of α-trifluoromethacrylic acid, 4,4,4-trifluoro-3-hydroxy-bmethyl-3-trifluoromethylbutyl methacrylate 12.84467g, 2,2'- 3.0 165 g of azobis(2-methylpropionate) was heated to an internal temperature of 45 °C. After 1 hour, the internal temperature was raised and the reaction was carried out at 90 ° C for 8 hours, and then cooled to 25 ° C. Next, vacuum-57-200903172 was dried and the solvent was removed to obtain a copolymer. -Naphtholate polymerizes this copolymer, Mw is 2.9xl03,2-vinylnaphthalene/6-ethylene-2/4,4,4-trifluoro-3-hydroxy-1-methyl-3-trifluoromethyl The copolymerization ratio (% by mole) of butyl methylpropane was 2 0/3 0/5 0. This copolymer was referred to as "object (A-7)". [化38]

&lt;Synthesis Example 8 &gt; In a separable flask equipped with a stirrer, a thermometer and a cooling tube, into a MIBK 30g', a nitrogen gas foaming was carried out for 15 minutes, and then 6.7017 g of α-trifluoromethyl acrylate (6.9790 g) was added. Sulfuryl acrylate 2.4193 g, 2,2'-azobis(2-methylpropionate) 4.3 026 g, and the internal temperature was raised to 45 °C. After 1 hour, the internal temperature was allowed to react at 90 ° C for 8 hours, and then cooled to 25 ° C. Next, drying is carried out and the solvent is removed to obtain a copolymer. The copolymer, Mw is a copolymerization ratio of 3.1χ103,6-vinyl-2-naphthol/α-trisacrylic acid/sulfoethyl methacrylate (mole 50/40/1 0. This copolymer is used as "Polymer (Α_8)"., 2-naphthylmethyl dimethyl warming vacuum fluoromethyl%) is -58- 200903172 [化39]

&lt;Synthesis Example 9 &gt; A separable flask equipped with a stirrer, a thermometer, and a cooling tube was charged with 60 g of 'isopropyl alcohol i〇g, and after nitrogen gas foaming for 15 minutes, 3-(perfluoro- n-Butyl) 2 - hydroxypropyl acrylate i7.4 〇 92 g, 2 - propyl decylamine-2-methylpropane sulfonic acid 259 〇 8 g, 2, 2, azobis [N-(2-carboxylate) 2.1588 g of ethyl)-2-methylpropionamide] hydrate. After raising the internal temperature to 45 C ° for 1 hour, the internal temperature was raised to 6 〇t, and after 8 hours of reaction, it was cooled to 25. (:. Next, vacuum drying and solvent removal were carried out to obtain a copolymer. The copolymer 'Mw was 4.5 x 3 〇 3,2-propenylamine-2 -methylpropane phthalic acid / 3-(perfluoro-positive The copolymerization ratio (mol%) of butyl)-2-hydroxypropyl acrylate was 20/80. This copolymer was referred to as "polymer (a_丨)". -59- 200903172 [Chem. 40]

〇 j-OH

HN

(a-1) F3C(F2C)3

S03H &lt;Synthesis Example 1 〇&gt; A separable flask equipped with a stirrer, a thermometer, and a cooling tube was charged with 60 g of methanol and 10 g of isopropyl alcohol, and after being purged with nitrogen gas for 15 minutes, 3-(all) was added. Fluorine-n-hexyl)-2-hydroxypropyl acrylate 1 8.5 59 1 g, 1.4409 g of ethylenesulfonic acid, 2,2,-azobis[N-(2-carboxyethyl)-2-methylpropionate The amine hydrate was 2.3014 g, and the internal temperature was raised to 45 t. After 1 hour, the internal temperature was raised to 60 °C and further reacted for 8 hours, and then cooled to 25 °C. (:. Then 'vacuum under vacuum and remove the solvent to obtain a copolymer. The copolymer 'Mw is 3.9 x 3 , 3, ethylene sulfonic acid / 3 - (perfluoro-n-hexyl)-2-hydroxypropyl acrylate The copolymerization ratio (% by mole) was 2 Å / 8 Å. This copolymer was referred to as "polymer (a-2)".

Ο |~ΟΗ (a-2) F3C(F2C)3 -60- 200903172 [1-2] Modulation of composition (1) for forming an upper antireflection film &lt;Examples 1 to 8 &gt; 100 parts by mass of each polymer, 4-methyl-2-pentanol was added, and after solid content concentration of 1% by mass, the membrane was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain the respective upper layer antireflections of Examples 1 to 8. A composition for film formation. &lt;Comparative Example 1, 2 &gt; In 100 parts by mass of each polymer shown in the Table, 1-butanol was added to have a solid content concentration of 1% by mass, and then filtered through a membrane condenser having a pore diameter of 0.2 μm to obtain a comparative example. Each of the upper anti-reflection film forming compositions of 1 to 2. [Table 1] Polymer refractive index (193 nm) Developability pattern shape standing wave effect Example 1 Α-1 1.47 Good and good Example 2 Α-2 1.44 Good and good Example 3 Α-3 1.42 Good m Good example 4 Α-4 1.46 Good and good Example 5 Α-5 1.46 Good and good Example 6 Α-6 1.43 Good m Good Example 7 Α-7 1.46 Good Good Good Example 8 Α-8 1.45 Good Good Good Comparative Example 1 a-1 1.57 Good and insufficient, Comparative Example 2 a-2 1.56 Good m Insufficient -61 - 200903172 [1-3] Measurement of refractive index The composition for forming an upper antireflection film of each of the examples and the comparative examples was used. The refractive index (wavelength 1 93 nm) of the formed film was measured in the following manner. The results are summarized in Table 1. &lt;Measurement Method of Refractive Index&gt; The composition of the upper anti-reflection film forming composition is spin-coated on a wafer having a diameter of 8 inches so that the thickness of the anti-reflection film formed is in the range of 26 to 33 nm. . Thereafter, the refractive index of the film was measured using J. A. Wo 〇 11 am C 〇 ., : [ n c . ellipsoid symmetry "VUV_ VASE". [I-4] Evaluation of performance The composition for forming an upper anti-reflection film in each of the examples and the comparative examples was formed into a resist pattern to evaluate the performance as an anti-reflection film. The results of the evaluation are summarized in Table 1. (1) The photoresist pattern is formed by spin coating on a wafer having a diameter of 8 inches, and a spin-coating of an ArF excimer laser chemically amplified positive resist ASR, trade name "ARX1682J". 1 1 〇 °C hot plate for 60 seconds pre-baking to form a photoresist film with a thickness of 0.19 μηη. Then, on the resist film, each of the upper anti-reflection film forming compositions of the examples and the comparative examples was spin-coated so that the thickness of the antireflection film formed was in the range of 26 to 3 3 nm. . Next, using a scanner "NSRS306C" (wavelength I93 nm) manufactured by Nikon Corporation, the exposure was performed for a set time. Immediately after the exposure, the film was exposed to a hot plate at 115 ° C for 60 seconds and then baked. Thereafter, it was developed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25 ° C for 1 minute, washed with water, and dried to form a photoresist pattern. (2) Evaluation of performance of the upper anti-reflection film &lt;Developability&gt; The left or right of the residue of the upper anti-reflection film or the photoresist film is left to the left or right by a scanning electron microscope, and no residue or development remains. The developability is good. &lt;Pattern shape> The cross-sectional shape of the photoresist was observed by a scanning electron microscope in a 160 nm-L/lS pattern, and the shape (b) was made in the cross-sectional shapes (a) to (f) shown in Fig. 1, The situation in (c) and (d) is good. &lt;Standing wave effect&gt; After forming a photoresist film in a film thickness of 0.18 to 0.24 μm in a range of 0.18 to 0.24 μm in a range of 0.18 to 0.24 μm, the upper layer antireflection is formed as described above. membrane. Next, exposure is performed by changing the exposure amount with respect to each wafer using the aforementioned reduced projection exposure machine. Thereafter, baking and development were carried out after the exposure as described above to form a photoresist pattern. Next, the photoresist film having a thickness of 〇.19 um was observed by a scanning electron microscope, and the exposure amount of the pattern of 160 nm - 1 L / lS - 63 - 200903172 was measured at 160 nm - 1 L / lS. Thereafter, using the obtained exposure amount, the wafer size was observed in each of the wafers, and the size of the pattern was measured in a mask of 160 nm - 1 L / lS. Next, the maximum 値 of the obtained pattern size is taken as Emax, and the minimum 値 is taken as Emjn, and S値 of the following formula (variation of the dimensional change accompanying the change in film thickness &gt; 丫乍 is an index of the standing wave effect, and is made In the case of being smaller than 3 5, the standing wave effect is good. S = (E - E ) max min [1 - 5 ] The effects of the examples are as shown in Table 1, and the upper layers of the first to eighth embodiments are used. In the case of the composition for forming an antireflection film, it was confirmed that the standing wave effect can be sufficiently reduced. 2. Examples 9 to 17 and Comparative Examples 3 to 5 [2-1] Synthesis of Polymer (A) Hereinafter, each polymer The synthesis example of the polymer (A-9) to (A-11) is described. The physical properties of each of the polymers obtained in the synthesis examples ("Mw" and "copolymerization ratio"), and the above [1] -1] Measured in the same manner. <Synthesis Example 1 1 &gt; A separable flask equipped with a stirrer, a thermometer and a cooling tube was charged with tetrahydrofuran (hereinafter referred to as THF) 30 g, and foamed with nitrogen gas for 15 minutes. After adding 2-0.4 dimethyl naphthalene 10.4809 g, α-trifluoromethacrylic acid tert-butyl 9.5 8 9 1 g, 2, 2, azobis(2-methylpropionic acid dimethyl ester 1.8779g, -64- 200903172 The internal temperature was raised to 45 ° C. After 1 hour, the internal temperature was raised to about 70 ° C and refluxed for 8 hours, then cooled to 25 ° C. Then, vacuum drying was carried out. The solvent was removed to obtain a copolymer. The copolymer 'Mw was 3.5 χ 103, and the copolymerization ratio (mol%) of 2-vinylnaphthalene / α-trifluoromethacrylic acid was 50/50. (Α-9)". [Chem. 42]

&lt;Synthesis Example 1 2 &gt; In a separable flask equipped with a stirrer, a thermometer, and a cooling tube, 30 g of methyl ethyl ketone, after foaming with nitrogen gas for 15 minutes, charged with 8.9840 g of 2-vinylnaphthalene, α-trifluoro 8.1 5 96 g of methacrylic acid, 2.8600 g of maleic anhydride, and 122 g of 2,2'-azobis(dimethyl 2-methylpropionate) 2. The internal temperature was raised to 45 ° C. After 1 hour, the internal temperature was raised to 70 ° C for 8 hours, and then cooled to 25 ° C. Next, 3 g of a 1% aqueous solution of oxalic acid was gradually dropped, and the internal temperature was raised to 7 (TC was reacted for 2 hours. Thereafter, the reaction liquid was washed three times with water 5 〇g), and the solvent was removed by vacuum drying. To obtain a copolymer. -65- 200903172 The copolymer, Mw is 3.8xl03, the copolymerization ratio of 2-vinylnaphthalene / α-trifluoromethacrylic acid / maleic acid (% by mole) is 40/40/20 This copolymer is referred to as "polymer (Α-10)".

(Α-10)

ΗΟ &lt;Synthesis Example 1 3 &gt; In a separable flask equipped with a stirrer 'thermometer and a cooling tube, and charged with THF 3 0 g ', after nitrogen gas foaming for 15 minutes, 2-vinyl naphthalene 9.3 063 g, α-trifluoromethane was added. 9 3 9 1 5 g of methacrylic acid, 1. 3 000 g of 2 sulfoethyl methacrylate, 2,2,- azobis(dimethyl 2-methylpropionate) 1. 8 5 2 8 g 'The internal temperature is raised to 4 5 艽. After 1 hour, the internal temperature was raised to about 7 〇 ° C and refluxed for 8 hours, and then cooled to 25 ° C. Next, vacuum drying was performed and the solvent was removed to obtain a copolymer. The copolymer &apos; Mw was 3.7x1 〇3,2-vinylnaphthalene/α-trifluoromethyl acrylate-2-sulfoethyl methacrylate copolymerization ratio (mol%) was 45/50/5. This copolymer was referred to as "polymer (Α_η)". -66 - 200903172 [Chem. 44]

[2-2] Composition for forming an upper antireflection film (Preparation of I〇&lt;Examples 9 to 17&gt; 100 parts by mass of each polymer (Α) shown in Table 2, and an acid generator shown in Table 2 was added ( After Β) and the compound (C), 4-methyl-2-pentanol was added to have a solid component concentration of 1%, and then filtered through a membrane filter having a pore diameter of 22 μm to obtain Examples 9 to 17 Each of the upper anti-reflection film forming compositions. <Comparative Examples 3 to 5 &gt; Each of the polymers (A) shown in Table 2 was added in a mass ratio of 4 - methyl-2-pentanol to solid content. After the concentration was 1%, the film for the upper antireflection film formation of Comparative Examples 3 to 5 was obtained by a membrane filter having a pore size of 0.2 μm. -67- 200903172 [Table 2] Polymer (8) (Part) Acid generator ¢) (Part) Example 9 Α-9Π00) Example 10 Α-9Π00) B-2(3) Example 11 Α-9Π00Ί Unloading Example 12 Α-9(100) Bl(3) Example 13 Α- 9Π00) B-U3) Example 14 Α-9Π00) B-2(3) Example 15 Α-9Π00) • Example 16 A-lOflOO') _ Example 17 Α-ιοαοο') B-2(3) Comparative Example 3 Α-9(100) _ Comparative Example 4 Α-10Π00) Comparative Example 5 A-im ⑽ -

Further, the details of the examples and comparative examples in Table 2 are as follows. <Acid generator (B) &gt; (B-1): Triphenylsulfonium trifluoromethanesulfonate (B-2): Triphenylsulfonium nonafluorobutanesulfonate <Compound (C) &gt; ( ^1): 5-sulfosalicylic acid (C·2): determination of the refractive index of camphorsulfonic acid [2.3] The use of each of the upper antireflection film forming groups in the examples and comparative examples-68-200903172 The refractive index (wavelength 193 nm) of the film formed by the object was measured in the same manner as the above [1 - 3]. The results are summarized in Table 2. [2-4] Evaluation of performance In the examples and the comparative examples, a photoresist pattern was formed for each of the upper anti-reflection film forming compositions, and the performance of the antireflection film was evaluated. The evaluation results are shown in Table 3. (1) Formation of photoresist pattern A photoresist pattern was formed in the same manner as the above [I-4]. (2) Performance evaluation of the upper anti-reflection film In the same manner as the above [1 _4], "developability", "pattern shape" and "standing wave effect" were performed. Further, the "probe defects" are also evaluated as described below. &lt;Probe Defect&gt; After the spin-coating of a chemically amplified positive resist (manufactured by JSR, trade name: ARX1682J) of ArF excimer laser on a wafer having a diameter of 8 inches, 1 1 A hot plate of 0 ° C was pre-baked for 60 seconds to form a photoresist film having a thickness of 1919 μm. Then, a solution of each of the antireflection film forming compositions is applied onto the resist film, and spin coating is applied to set the thickness of each of the antireflection films to be in the range of 26 to 33 nm. Next, a scanner NSRS 3 06C (wavelength: 193 nm) manufactured by Nikon Corporation was used, and the exposure for the probe defect inspection was performed for a set time, and immediately after the exposure, the exposure was performed on a hot plate at 1 15 ° C for 60 seconds. Bake. Thereafter, it was developed using a 2.38% by mass of -49-200903172 aqueous solution of tetramethylammonium hydroxide, and developed at 251 for 1 minute, washed with water, and dried to form a resist pattern. Next, when the defect is measured by 1^23 5 1 (reverse 1^1^1^〇〇, the case where the developed peeling defect detected is 500 or less is good, and when it exceeds 500, it is insufficient. 3] developable pattern shape standing wave effect probe defect Example 9 Good Good Good Good Example 10 Good Good Good Good Example 11 Good Good Good Good Example 12 Good Good Good Good Example 13 Good Good Good Good Example 14 Good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good, good [2-5] Effects of the Examples As is apparent from Table 3, in the case of using the composition for forming an upper antireflection film of each of Examples 9 to 17, it was confirmed that the standing wave effect and the probe defect can be sufficiently reduced. [Simple description of the drawing] [Fig. 1] A schematic diagram showing the sectional shape of the pattern. -70-

Claims (1)

200903172 X. Patent Application No. 1. The above-mentioned resin for forming an antireflection film is characterized in that it contains at least one of the units of the following formula (1) and at least one of the repeating units represented by the following formula (2). 'The weight average molecular weight measured by gel permeation chromatography is 1000 to 1 00000, and is soluble in alkali developer, R5 R4 [1] (1) R6 [In the formula (1), R1 to R7 each represent a hydrogen atom, -OH, -COOH or -S03H, and R1 to R7 are not all hydrogen atoms], [Chemical 2] In the formula (2), R8 to R14 each represent a hydrogen atom, -〇H, _C00H--S03H, and R8 to R14 are not hydrogen atoms. 2. The resin for forming an antireflection film according to the first aspect of the patent application, wherein in addition to the formula (1) and the formula (2), the repeating unit 'containing 'containing -OH, -COOH and -s〇 At least one of the 3H, the repeat unit. 3. The resin for forming an upper antireflection film according to the first aspect of the invention, which further comprises at least one of the repeating units represented by the following formulas (3) to (6), -71 - 200903172 [Chem. 3] R15 B' (3) \ D / so3h [In the formula (3), R15 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, A represents a single bond, a carbonyl group or a carbonyloxy group, and B represents a single bond or a sub Amino group, D represents a single bond or a divalent organic group having a carbon number of 1 to 12], [Chemical 4] COOH [In the formula (4), R16 represents a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group], [Chemical 5] [In the formula (5), R17 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a fluorinated alkyl group having a carbon number of 1 to 12], [Chemical 6] [In the formula (6), R18 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, -72-200903172 P represents a single bond, a carbonyl group or a carbonyloxy group, and Q represents a single bond or a carbon number of 1 to 21; The divalent organic group, R19 and R2 () each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated group having a carbon number of 1 to 4. A composition for forming an upper anti-reflection film, which comprises a resin for forming an anti-reflection film of an upper layer according to any one of claims 1 to 3, and a solvent. A method for forming a photoresist pattern, comprising: (1) a step of forming a photoresist film on a substrate, and (2) using a composition for forming an antireflection film on the upper layer of the fourth aspect of the patent application, a step of forming an upper anti-reflection film on the photoresist film, (3) a step of exposing the radiation to the region of the photoresist film formed by the upper anti-reflection film, and (4) performing development and removing the upper layer The step of the anti-reflection film. 6. A composition for forming an upper antireflection film, comprising: a polymer (A) which is soluble in an alkali developer and has an aromatic group, and a linear acid generator (B) having a sulphur and a sulphur At least one of the compound (C) of the acid residue. (1) The composition for forming an antireflection film of the upper layer of the sixth aspect of the patent application, wherein the compound (c) having the sulfonic acid residue is a compound represented by the following formula (1), [Chem. 7] (r21L^ ^ m Z —(-SO3H) ( i ) [A linear or branched chain alkyl group of the formula "I" wherein R21 represents a carbon number of ～10, an alicyclic alkyl group having a carbon number of 3 to 20 or a derivative thereof , a hydroxyl group, a carboxyl group, an alkyl group - 73 - 200903172 ether group, alkoxycarbonyl group, or alkylcarbonyloxy group, Z represents a linear, branched, alicyclic hydrocarbon group having 4 to 12 carbon atoms or may have The aromatic hydrocarbon group of the substituent, m is an integer of 〇~4, η is an integer of 1 to 4, and 'r1 is the same or different from each other in the case of a plural number. 8 · If the scope of application is 6 or 7th composition for forming an antireflection film of the upper layer, wherein the polymer (A) contains a repeating unit represented by the following formula (Π), and at least a repeating unit represented by the following formula (III) One's weight average molecular weight determined by the waist-penetration chromatography is 1000~100000, [Chem. 8] (Π) [In the formula (II), R22 to R28 each represent a hydrogen atom, -OH, -COOH, or -SChH] '[9] [In the formula (III), each of R29 to R35 represents a hydrogen atom, ??, -C?OH, or -S?3H]. 9 The composition for forming an antireflection film of the upper layer of the eighth aspect of the patent application, wherein the polymer (Α) further comprises at least one of the repeating units represented by the following formula (Ιν)~(VII)-74-200903172 Species, [10] (IV) In the formula (IV), R36 represents a hydrogen atom, a group, A represents a single bond, a carbonyl group or a carbonyloxy group, a linear chain of 1 to 20 carbon atoms, and an aromatic hydrocarbon group which may have a substituent] 11] Methyl, hydroxymethyl or trifluoromethyl, B represents a single bond or imino group, D represents a branched chain, alicyclic hydrocarbon group or R37 COOH (V) [In the formula (V), R3 7 represents a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group], [Chemical 12] OR·* OH (VI) [In the formula (VI), R3 8 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 12 or a fluorinated group having a carbon number of 1 to 12] -75 - (VI) 200903172 [Chemical 13 ] [In the formula (νπ), 'R39 represents a hydrogen atom, a methyl group, a methyl group or a trifluoromethyl group, P represents a single bond, a _ group or a lyophilic group, and Q represents a single bond, a carbon number (3), a direct bond, a branched, alicyclic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, and R40 and R41 each represent a hydrogen atom, an alkyl group having a carbon number of 44 or a fluorinated alkyl group having a carbon number of i to 4. 10. The composition for forming an antireflection film of the upper layer according to any one of claims 6 to 9 wherein the polymer (A) contains a repeating unit represented by the following formula (VIII), and the following formula ( IX) shows the repeat unit. [Chem. 14] (W) [Chem. 15] 0 into OH 11. A method for forming a photoresist pattern, comprising: (1) a step of forming a photoresist film on a substrate; (2) using any one of claims 6 to 10 of the patent application scope a step of forming an upper anti-reflection film on the resist film by the composition for forming an upper anti-reflection film, -76 - 200903172 (3) irradiating the region of the resist film formed by the upper anti-reflection film with radiation a step of exposing, and (4) performing the step of developing the upper anti-reflection film. -77-