WO2007097457A1

WO2007097457A1 - Composition for forming antireflection film and antireflection film

Info

Publication number: WO2007097457A1
Application number: PCT/JP2007/053627
Authority: WO
Inventors: Dai Oguro; Masatoshi Echigo
Original assignee: Mitsubishi Gas Chemical Company, Inc.
Priority date: 2006-02-27
Filing date: 2007-02-27
Publication date: 2007-08-30
Also published as: JPWO2007097457A1; JP5141549B2; TW200741353A

Abstract

Disclosed is a composition for forming antireflection films, which contains a polyphenol compound having a specific structure and a solvent. The polyphenol compound is obtained by a condensation reaction of at least one aromatic aldehyde having 6-20 carbon atoms and a compound containing 1-3 phenolic hydroxyl groups and having 6-15 carbon atoms. The polyphenol compound has a molecular weight of 400-2000, a molecular weight distribution Mw/Mn of 1-1.05, and a glass transition temperature of not less than 110˚C. An antireflection film formed on a substrate by using such a composition absorbs light reflected by the substrate and improves formability of a resist pattern which is formed on the antireflection film. Since the antireflection film has low sublimation property and high dry etching resistance, it enables to reduce line-edge roughness of the resist pattern. In addition, since such an antireflection film is soluble in an alkali developing solution, removal of the antireflection film does not require a special dry etching.

Description

Specification

Antireflection film forming composition and antireflection film

Technical field

[0001] The present invention relates to a novel composition for forming an antireflection film. This composition for forming an antireflection film contains a polyphenol compound having a specific structure.

Background art

[0002] When a resist pattern is formed on a substrate, the light is diffused to the masked part due to reflection of light from the substrate during exposure, and the shape is good and it is difficult to obtain a resist pattern! There was a problem. In addition, the reduction in resolving power in the processed photoresist is particularly noticeable when the substrate is non-planar and / or highly reflective. As one of the solutions, it has been proposed to provide an antireflection film having a property of absorbing radiation reflected from the substrate surface under the resist film to be formed on the substrate.

In order to form such an antireflection film, a composition having a high optical density at an exposure wavelength has been used. As such a composition for forming an antireflection film, an organic composition is used in consideration of film formation cost and conductivity, and is composed of, for example, a polyamic acid (co) polymer or a polysulfone (co) polymer and a dye. Organic compositions have been proposed (see, for example, Patent Document 1). The antireflection film formed from this composition has no electrical conductivity, and the composition dissolves in a general solvent, so no special equipment is required, and the substrate can be easily formed as in the case of the resist composition solution. Can be applied. However, antireflective coatings composed of polyamic acid (co) polymers and polysulfone (co) polymers and dye power cannot sufficiently prevent halation and standing waves due to the limited amount of dye added, and resist coating As a result, the resist pattern cross-sectional shape deteriorates, such as omission defects and skirting, and the dye has sublimation properties, which contaminates the exposure apparatus.

[0004] Thus, a composition containing a halogenated bisphenol A type resin and a resin containing an anthracene structure has been proposed (see Patent Document 2). However, when an antireflection film is formed using this composition, the upper photoresist layer is developed with an alkaline aqueous solution to form a resist pattern, and then the antireflection film exposed at the portion where the photoresist layer is removed. Remove Therefore, it was necessary to perform a dry etching operation. As a result, the number of work steps increases and the photoresist layer deforms during dry etching. In addition, the uniformity of the film is important for the formation of a fine resist pattern, but the resin materials conventionally used for the formation of an antireflection film have a large molecular weight and a relatively wide molecular weight distribution. There is a problem that the solubility in an alkali developer becomes uneven and the line edge roughness (LER) of the resist pattern becomes large. Therefore, development of an improved antireflection film and a material for forming the antireflection film for solving various problems related to the lithography process is highly desired.

[0005] Patent Document 1: JP-A 59-934488

Patent Document 2: JP 2002-333717

Disclosure of the invention

[0006] An object of the present invention is to provide a composition for forming an antireflection film that has low sublimation and high dry etching resistance, has a small line edge roughness at the time of resist pattern formation, and does not require a dry etching treatment to remove the antireflection film. To provide things.

[0007] The present invention provides the following conditions:

(a) a compound obtained by a condensation reaction of at least one aromatic aldehyde having 6 to 20 carbon atoms and a compound having 6 to 15 carbon atoms containing 1 to 3 phenolic hydroxyl groups;

(b) Molecular weight force 00-2000;

(c) molecular weight distribution MwZMn is 1-1.05; and

(d) Glass transition temperature of 110 ° C or higher

The present invention relates to an antireflective film-forming composition comprising a polyphenolic compound (A) and an organic solvent (B) that simultaneously satisfy

The present invention further relates to an antireflection film containing the above polyphenol compound (A). The present invention further relates to a method for forming an antireflection film using the antireflection film-forming composition.

BEST MODE FOR CARRYING OUT THE INVENTION

[0008] The present invention is described in detail below.

The composition for antireflection film type of the present invention has the following conditions: (a) an aromatic aldehyde having at least one kind of aromatic ring having 6 to 20 carbon atoms (hereinafter simply referred to as aromatic aldehyde) and 1 to 3 phenolic hydroxyl groups containing 6 to 15 carbon atoms. A compound obtained by a condensation reaction with a compound (hereinafter simply referred to as a low molecular phenol compound);

(b) Molecular weight force 00-2000;

(c) molecular weight distribution MwZMn is 1-1.05; and

(d) Glass transition temperature of 110 ° C or higher

The polyphenolic compound (A) and the organic solvent (B) satisfying

[0009] As the aromatic aldehyde in the present invention, benzaldehyde, tolylaldehyde, ethylbenzaldehyde, cuminaldehyde, n-propylbenzaldehyde, isobutylbenzaldehyde, t-butylbenzaldehyde, biphenylaldehyde, 4-cyclohexylbenzaldehyde, 4-propyl-4-cyclohexylbenzaldehyde, 4-butyl-4-cyclohexylbenzaldehyde, 4-pentyl— 4-cyclohexylbenzaldehyde, 4 cyanobenzaldehyde, 4-halogenobenzaldehyde, 4-hydroxybenzaldehyde, 4 salicylbenzaldehyde, 4 Norbornol penzaldehyde, 4-adamantyl benzaldehyde, 4-dicyclopentagel benzaldehyde, tert-carbcarbaldehyde, turf-rudica Rubaldehyde, turf-tricarbaldehyde, fluorenecarbaldehyde, fluorenecarbaldehyde, 4-tricyclopentylbenzaldehyde, naphthaldehyde, naphthalene aldehyde, phenanthrene carbaldehyde, phenanthrene carbaldehyde, anthracene carboaldehyde, anthracene Aromatic aldehydes such as carbaldehyde, pyrene carbaldehyde, pyrene carboaldehyde and the like can be mentioned.

[0010] As the low molecular weight phenol compound in the present invention, phenol, (C alkyl) phenol

1-6

(E.g., o-cresol, m-cresol, p-taresoles, etc., o-phenolphenol, 2-cyclohexylphenol), dialkylphenols (eg, 2,3 dimethylphenol, 2,5 dimethylphenol, 2 , 6 dimethyl phenol, 2, 6 di tert butyl phenol, etc.), trialkyl phenol, alkoxy phenol (eg, aromatics such as o-methoxyphenol), aryl reel (eg For example, o- or m-phenol, such as phenolphenol, cycloalkylphenol (such as 2-cyclohexylphenol), halogenated phenols (such as black mouth phenol, dichloro phenol, Polyphenols (eg, catechol, alkylcatechol, chlorocatechol, resorcinol, alkylresorcinol, hydroquinone, alkinohydrohydroquinone, chlororesonoresinole, chlorohydroquinone, pyrogalonore, anolequinole) Examples include pyrogallol, phloroglicinol, 1,2,4-trihydroxyphenol). The above aromatic aldehyde and low molecular weight phenol compound may be used alone or in combination of two or more. The purity is not particularly limited, but is preferably 95% by weight or more, more preferably 99% by weight or more.

[0011] The aromatic aldehyde and the low-molecular-weight phenol compound are selected depending on the application. For applications that require a fast etching rate, a compound with a low carbon atom density is selected, and conversely, a compound with a high carbon atom density is selected for an application that requires etching resistance such as a lower layer film in a multilayer process. When used for forming the lower layer film for multilayer processes using ArF exposure, the compound should be selected according to each application where the extinction coefficient is preferably 0.4 or less.

[0012] The condensation reaction between the aromatic aldehyde and the low-molecular-weight phenol compound can be carried out by a known method. In order to obtain the polyphenol compound (A) used in the present invention, special condensation reaction conditions are used. do not need. In the condensation reaction, an acid or alkali catalyst is used, but an acid catalyst is preferred. As the acid catalyst, inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as trifluoromethanesulfonic acid, paratoluenesulfonic acid and succinic acid; Lewis acids such as zinc chloride and aluminum chloride can be used. No acid catalyst is practically preferred.

In the present invention, the polyphenolic compound (A) satisfies the following conditions (b) to (d) simultaneously.

(b) Molecular weight force is 00 to 2000, preferably 600 to 1200.

(c) Quantity distribution MwZMn is 1 to 1.05, preferably 1 to 1.01.

(d) The glass transition temperature is 110 ° C or higher, preferably 110 to 250 ° C.

By satisfying the above conditions, film formability, heat resistance, film homogeneity, spin coatability, low sublimation The composition for anti-reflective films excellent in this is obtained. In the present invention, when the range is described as “a to b”, the lower limit value a and the upper limit value b are also included in the range.

[0014] The polyphenol compound (A) preferably includes a conjugated structure in which at least two benzene rings and a non-bonded electron pair of Z or hetero atom are involved. The conjugated structure includes biphenyl structure, naphthalene structure, anthracene structure, phenanthrene structure, pyrene structure, fluorene structure, acenaphthene structure, 1-keto acenaphthene structure, acenaphthylene structure, benzophenone structure, terphenyl structure, phenanthraquinone structure, More preferably, the xanthene structure and the thixanthene structural power are at least one structure selected. When the polyphenolic compound (A) has the above structure, the optical properties of the composition can be adjusted according to the exposure technique, and the resulting composition has high etching resistance.

[0015] Polyphenolic compound (A) is represented by the following formula 1:

[Chemical 1]

It is preferable to be a compound represented by

In the above formula 1, R ¹ represents a biphenyl structure, naphthalene structure, anthracene structure, phenanthrene structure, pyrene structure, fluorene structure, acenaphthene structure, 1-ketoacenaphthene structure, acenaphthylene structure, benzophenone structure, terphenyl structure, phenanthracium. It is a C1-C18 monovalent to tetravalent substituent derived from at least one structure selected from a non-structure, a xanthene structure, and a thixanthene structure.

R ² represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include For example, a straight, branched or cyclic alkyl group such as methyl, ethyl, n propyl, isopropyl, n butyl, isopropyl, sec butyl, t butyl, pentyl, hexyl, etc. Can be mentioned. Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclohexyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n propoxy group, an isopropoxy group, an n butoxy group, and a tert-butoxy group. When R ² is the above substituent, the affinity with the resist is good.

n is an integer from 1 to 4, p is an integer from 0 to 4, q is an integer from 1 to 4, and satisfies the condition 1≤p + q≤5 in each benzene ring.

However, a plurality of R ² , p, and q may be the same or different, and carbon atom a and carbon atom b may be bonded through oxygen or nitrogen.

Examples of the polyphenolic compound (A) represented by the formula 1 include the following compounds, but are not particularly limited.

[Chemical 2]

[Chemical 3]

In the formula, R ² , n, p, and q are the same as described above.

The compound of the formula 2 is preferable in that it has an appropriate extinction coefficient in exposure using a KrF and ArF excimer laser, and is excellent in etching resistance and economy. Examples of the polyphenol compound (A) of the formula 2 include the following compounds [Chemical Formula 5]

(However, R ² , p and q are the same as above.)

Examples of the organic solvent (B) include ethylene glycol monomethyl ether, ethylene glycol monoethylenoateolate, methinoreserosonolebuacetate, ethinoreserosonolebacetate, diethyleneglycolenomonomethinoatenole, diethyleneglycolenomonomono Echinoreete nore, Propylene glycol, Propylene glycol monomethinole ether, Propylene glycol nomonomethylenoate acetate, Propylene glycol nopropinoate etherate, Toluene, Xylene, Methyl ethyl ketone, Cyclopentanone, Cyclohexanone, 2-hydride Ethyl loxypropionate, 2-hydroxy-2-methylpropionate, ethyl acetate, ethyl acetate, 2-hydroxy-3-methylbutanoate, 3-methoxypropionate, 3-methoxypropionate, 3-ethoxypropionate Ethyl, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl acetate, butyl lactate and cyclohexanone can be used. These organic solvents may be used alone or in combination of two or more.

[0021] Further, a high-boiling solvent such as propylene glycol monobutyl ether, propylene glycol monobutinorele monoteracetate or the like may be mixed. Among the above-mentioned solvents, propylene glycolenomonomethinoreether (PGME), propylene glycolenomonomethinoatenoreacetate (PGMEA), lactate ethyl (EL), butyl lactate and cyclohexanone have improved leveling properties. The viewpoint power is preferable. In particular, PGMEA and EL are preferred for practical use.

[0022] The blend ratio of the polyphenolic compound (A) and the organic solvent (B) in the composition for forming an antireflection film (polyphenolic compound (A) Z organic solvent (B)) is 0.1 to 30Z 70 to 99.9 force S, preferably 0.5 to 20/80 to 99.5 force S, more preferably 1 to: LO / 90 to 99 force S, more preferably.

[0023] The composition for forming an antireflective film may contain a resin having a repeating unit obtained by novolakizing the polyphenol compound (A). Intermixing can be prevented by containing the rosin. The content of the resin (B) is preferably 0 to 80 with respect to 100 parts by weight of the composition for forming an antireflection film (the total amount of the polyphenol compound (A) and the organic solvent (B), the same applies hereinafter). Part by weight, more preferably 0 to 50 parts by weight.

[0024] The composition for forming an antireflection film of the present invention may contain a cross-linking agent having at least two cross-linking functional groups. Examples of the crosslinking agent include a melamine crosslinking agent, a substituted urea crosslinking agent, and a polymer crosslinking agent containing an epoxy group. Preferred are methoxymethyl isopropyl glycoluril, methoxymethylated melamine and the like, and particularly preferred is tetramethoxymethyl. Luglycoluril or hexamethoxymethylol melamine. The addition amount of the crosslinking agent varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is preferably 0 with respect to 100 parts by weight of the composition for forming an antireflection film 001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.1 to 5.0 parts by weight.

[0025] The composition for forming an antireflection film of the present invention may contain an acid generator. As the acid generator, it is preferable that the acid generator is at least one selected from the group forces which are represented by the following formulas (11) to (18).

[0026] [Chemical 6]

In formula (11), R ″ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydride. X— represents a sulfonate ion or a halide ion having an alkyl group, aryl group, halogen-substituted alkyl group or halogen-substituted aryl group.

The compound represented by the formula (11) includes trisulfosulfo-trifluoromethanesulfonate, trisulfosulfo-munonafluoro-n-butanesulfonate, diphenylsulfo-sulfonium-nonafluoro-n-butane. Sulfonate, triphenylsulfo-fluoro-monooctane sulfonate, diphenyl 4--methyl phenol sulfo-trifluoromethane sulfonate, di 2, 4, 6 trimethyl phenol sulfo-trifluoromethane sulfonate, diphenol 4-t —Butoxyphenyl sulfo-umtrifluor L-methanesulfonate, diphenyl 4-t butoxyphenyl sulfo-fluoro-nonafluoro —n-butane sulfonate, di-phenol 4-hydroxysulfo-mu-trifluoro methane sulfonate, bis (4-fluorophenol) 4-hydroxyphenol sulfo-fluorotrifluoromethane Sulfonate, diphenyl 4-hydroxyphenyl sulfo-fluoro-monofluoro- _n -butane sulfonate, bis (4-hydroxyphenol) mono-sulfo-fluorotrifluoromethane sulfonate, tri (4-methoxyphenol) sulfo-fluorotrifluoromethane Sulfonate, tri (4 fluorophenyl) sulfo-trifluoromethanesulfonate, triphenylenosnorephonium ρ tonorenosulfonate, triphenenoresnolephone benzenesulfonate, Phenol 2, 4, 6 Trimethylphenol p-Toluenesulfonate, Diphenyl 2, 4, 6 Trimethylphenol sulfo-um 2 trifluoromethyl sulfonate, Diphenyl 2, 4, 6 Trimethylphenol Rusulfo-Mu 4 Trifluoromethylbenzenesulfonate, diphenyl 2,4,6 Trimethylphenol sulfone-2,4 Difluorobenzenesulfonate, Diphenyl 2,4,6 Trimethylphenol sulfone Muhexafluorobenzenesulfonate, diphenylnaphthosulfo-muutrifluoromethanesulfonate, diphenol 4-hydroxyphenol sulfone-p-toluenesulfonate, trisulfosulfone 10-camphorsulfonate , Diphe-Nole 4-Hydroxy Phenol-Noles Norehonium 10 Camphors Norephone and Cyclo ( 1,3-Perfluoropropanedisulfone) It is preferably at least one selected from the group consisting of imidates.

[Yi 7]

In formula (12), R ¹⁴ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydride. Represents a mouth xyl group or a halogen atom. X— is the same as described above. The compound represented by the above formula (12) is bis (4-tert-butylphenol) iodine trifluoromethanesulfonate, bis (4tert-butylphenol) iodide-munonafluoro-n butanesulfonate. Bis (4 t-butylphenol) tert-butyl perfluoro-n-octane sulfonate, bis (4 tert-butylphenol) tert-p-toluene sulfonate, bis (4 tert-butylphenol) Iodonium benzene sulfonate, bis (4 t-butylphenol) Iodonium 2 trifluoromethylbenzene sulfonate, bis (4 t-butylphenol) odonumu 4 trifluoromethylbenzenesulfonate, bis (4 t-butylphenol) -Le) Jodonium-2, 4-Difluorobenzenesulfonate, Bis (4 t-butylphenol) Jodhonium hexafluorobenzenesulfone Bis (4t butylphenol) 10-camphor sulfonate, diphenol trifluoromethanesulfonate, diphenol-munonafluoro-n-butane sulphonate, diphenylenoperfuno Leoro n—Octans norephonate, Difenenoredonium ρ Tonorenosenorephonate, Difenenorenodonium Benzenesnorephonate, Difenidrenodonum 10—Camphors norephonate, Difenodiorneum 2 Trifluoromethyl benzene sulfonate, diphenol rhododonium mu 4 Trifluoromethino benzene sulphonate, diphenyl rhododonium 2, 4 Diphenolo benzene senophonate, diphenol oleo benzene sulphonate, di ( Four Trifluoromethylphenol) odo-um trifluoromethanesulfonate, di (4 trifluoromethylphenol) odo-munonafluoro- _n -butanesulfonate, di (4 trifluoromethylphenol) N) Octane sulfonate n-octanesulfonate, di (4 trifluoromethylphenol) odo-um p-toluenesulfonate, di (4 trifluoromethylphenol) Preferably, at least one selected from the group consisting of mbenzenesulfonate and di (4 trifluoromethylphenol) jordan 10-camphorsulfonate.

[Chemical 8]

Formula (13) Q is an alkylene group, an arylene group or an alkoxylen group, R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. The compound represented by the formula (13) is: N (Trifluoromethylsulfo-loxy) succinimide, N— (Trifluoromethylsulfo-loxy) phthalimide, N— (Trifluoromethylsulfo-loxy) diphenylmaleimide, N— (Trifluoromethylsulfo-loxy) Bicyclo [2. 2. 1] hepto-5-1,2,3 dicarboximide, N— (trifluoromethylsulfo-loxy) naphthylimide, N— (10-camphorsulfo-loxy) succinimide, N— (10-camphorsulfo -Luoxy) phthalimide, N— (10—force N-sulfo-Luoxy) diphenylmaleimide, N— (10 Camphorsulfo-loxy) bicyclo [2. 2. 1] hepto-5-en-1,3-dicarboximide, N— (10—force n-sulfo-loxy) naphthylimide, N— (n-octanesulfo-loxy) bisi Chloro [2. 2. 1] hepto-5-ene 2,3 dicarboximide, N— (n-octanesulfo-loxy) naphthylimide, N— (p-toluenesulfo-loxy) bicyclo [2.2.1] hepto 5-2, 3 Dicarboximide, N- (p Toluenesulfo-loxy) naphthylimide, N- (2-Trifluoromethylbenzenesulfo-loxy) bicyclo [2.2.1] heptoe 2, 3 Dicarboximide, N— (2 trifluoromethylbenzenesulfo-loxy) naphthylimide, N— (4-Trifluoromethylbenzenesulfoloxy) bicyclo [2.2.1] heptone 2, 3 Zika Boxyimide, N— (4-Trifluoromethylbenzenesulfo-ruxoxy) naphthylimide, N— (Perfluoro-benzenesulfo-ruxoxy) bicyclo [2.2.1] Hepto-5-1,2,3 dicarboxyimide, N — (Perfluorobenzenesulfo-loxy) naphthylimide, N— (1-Naphthalenesulfo-loxy) bicyclo [2. 2. 1] heptone 5 1,2,3 dicarboxyl N- (1-Naphthalenesulfo-loxy) naphthylimide, N- (Nonafluoro-n-butanesulfo-loxy) bicyclo [2.2.1] hepto-5-en-1,3-dicarboxyimide, N- (Nonafluoro-n —Butanesulfo-loxy) naphthylimide, N- (perfluoro- _n —octanesulfo-loxy) bicyclo [2.2.1] hepto-5-en-2,3-dicarboximide and N (perfluoro-n-octanesulfo-loxy) naphth It is preferable that the group power consisting of tilimide is at least one selected.

[0029] [Chemical 9]

In formula (14), R ^lbs may be the same or different and are each independently an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.

The compound represented by the formula (14) is diphenyldisulfone, di (4 methylphenol) disulfone, dinaphthyldisulfone, di (4 tertbutylbutyl) disulfone, di (4-hydroxyphenyl) disulfone, Selected from the group consisting of di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2fluorophenyl) disulfone and di (4 trifluoromethylphenol) disulfone At least one type is preferred.

[0030] [Chemical 10]

In the formula (15), R ¹⁷ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted A heteroaryl group or an optionally substituted aralkyl group.

The compound represented by the above formula (15) includes α (methylsulfo-luoxyimino) phenylacetonitrile, at- (methylsulfo-luxitimino) -4-methoxyphenylsulfatonitrile, α- (trifluoromethylsulfo-luoxyimino) -phenol. -Lucetonitrile, α- (Trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (Ethylsulfo-ruxitimino) -4-methoxyphenylacetonitrile, at- (Propylsulfo-Luoxyimino) -4 Methylphenylacetonitrile and α (Methylsulfo-Luoxyimino) -4 Bromophenolacetonitrile power is preferably at least one type selected.

[0031] [Chemical 11]

In formula (16), R ^ia may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The number of carbon atoms in the halogenated alkyl group is preferably 1-5.

[0032] [Chemical 12]

In formulas (17) and (18), R ¹⁹ and R ^2Q are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopentyl group, A cycloalkyl group such as a xyl group, an alkoxyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group, or an aryl group such as a phenol group, a tolyl group, or a naphthyl group, preferably a carbon atom number 6 ~: L0 group. L ¹⁹ and L ² ° are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazido-4-sulphonyl group, a 1,2-naphthoquinonediazido5-sulfol group, and 1,2. -1,2-quinonediazidosulfol groups such as naphthoquinonediazido 6-sulfol group are preferred! /. In particular, 1,2-naphthoquinonediazido 4-sulfol group and 1,2-naphthoquinonediazido 5-sulfol group are preferable. p is an integer from 1 to 3, q is an integer from 0 to 4, and l≤p + q≤5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenyl group, a group represented by the following formula (19), a carbo group, an ester group, an amide group or an ether group. Y ¹⁹ is a hydrogen atom, an alkyl group or an aryl group, and X ^2Q is independently a group represented by the following formula (20).

[Chemical 13]

In formula (20), each independently represents an alkyl group, a cycloalkyl group or an aryl group, R ²² represents an alkyl group, a cycloalkyl group or an alkoxyl group, and r represents an integer of 0 to 3.

[0034] Other acid generators include bis (p-toluenesulfol) diazomethane, bis (2,4-dimethylmethylsulfol) diazomethane, bis (tert-butylsulfol) diazomethane, bis (n- Butylsulfol) diazomethane, bis (isobutylsulfol) diazomethane, bis (isopropylsulfol) diazomethane, bis (n-propylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (isopropylsulfo- ) Diazomethane, 1,3-bis (cyclohexylsulfo-ruzomethylsulfol) propane, 1,4-bis (phenolsulfo-luazomethylsulfol) butane, 1,6-bis (phenol) -Lulsulfol-luazomethylsulfol) hexane, 1,10-bis (cyclohexylsulfol-lulazomethylmethylsulfol) decane Bissulfol diazomethanes, 2- (4-methoxyphenol) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- (bis 卜(Hydroxymethyl) -1, 3, 5- 卜 riadine, 卜 ris (2,3-dibromopropyl) -1, 3, 5- 卜 lyazine, tris (2,3-dibromopropyl) isocyanurate and other halogen-containing triazines Derivatives and the like.

[0035] Among the above acid generators, an acid generator having an aromatic ring is more preferable. The sulfonate ion having an X-force aryl group or a halogen-substituted aryl group represented by the formula (11) or (12) is preferred. An acid generator having a sulfonic acid ion having an aryl group is more preferable, and di-trimethyltrisulfurium-p-toluenesulfonate, triphenylsulfo- p-toluene is particularly preferable. Sulfonate is particularly preferred.

[0036] The acid generator may be used alone or in combination of two or more. In the composition of the present invention, the amount of the acid generator used is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, more preferably 100 parts by weight of the polyphenol compound (A). 1 to 15 parts by weight.

[0037] The antireflection film-forming composition of the present invention may contain other polymers for the purpose of controlling the absorbance. Examples of such a resin include phenol resin, naphthol resin having high transparency at 193 nm, naphthol-modified xylene resin, phenol-modified naphthalene resin, dicyclopentagen resin, (meth) acrylate Examples of the resins include naphthalene rings such as resin, butyl naphthalene resin, polyacenaphthylene, phenanthrenequinone ring, fluorene ring, and biphenyl ring, and resins including heterocyclic rings such as thiophene and indene. .

[0038] In addition to the above, a light-absorbing agent, a rheology adjusting agent, an adhesion aid, a surfactant, and the like can be added to the composition for forming an antireflection film of the present invention, if necessary.

As the light absorber, for example, commercially available light absorbers described in “Technical dye technology and market” (published by CMC) and “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry), for example, CI Disperse Yellow 1, 3 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Disperse Violet 43; C.I.Disperse Blue 96; CI Fluorescent Brightening Agent 112, 135 and 1 63; CI SolventOrenge 2 and 45; CI Solvent Red 1, 3 8, 23, 24, 25, 2 7 and 49; CI Pigment Green 10; CI Pigment Brown 2 and the like can be suitably used. The light-absorbing agent is preferably blended in an amount of 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the composition for forming an antireflection film.

[0040] The rheology modifier mainly improves the fluidity of the composition for forming an antireflection film, In the first step, it is added for the purpose of enhancing the filling property of the composition for forming an antireflection film into the hole. Specific examples include phthalate esters such as dimethyl phthalate, jetyl phthalate, disobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, Adipic acid esters such as cutyl decyl adipate; Maleic acid esters such as dinormal butyl maleate, jetyl malate, dino-malmalate; Oleic acid esters such as methyl oleate, butyrate, tetrahydrofurfurolate, and normal butyl stearate, glyceryl stearate Mention may be made of stearic acid esters such as rate. The rheology modifier is preferably blended in an amount of less than 30 parts by weight per 100 parts by weight of the composition for forming an antireflection film.

[0041] The adhesion auxiliary agent is added mainly for the purpose of improving the adhesion between the substrate or resist and the composition for forming an antireflection film, and in particular for preventing the resist from peeling during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; trimethylmethoxysilane, dimethylolegetoxysilane, methinoresinmethoxysilane, dimethylenolevinoleethoxysilane. , Alkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; buttrichlorosilane, γ —Silanes such as chlorotripropylsilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyl trimethoxysilane; benzotriazole, benzo Heterocyclic compounds such as imidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazolethiouracil, mercaptoimidazole, mercaptopyrimidine; 1, 1-dimethylurea, Mention may be made of urea compounds such as 1,3-dimethylurea and thiourea compounds. The adhesion assistant is preferably added in an amount of less than 5 parts by weight, more preferably less than 2 parts by weight, based on 100 parts by weight of the composition for forming an antireflection film.

[0042] The antireflection film-forming composition of the present invention is blended with a surfactant in order to prevent the occurrence of pinholes, strains, etc., to reduce surface unevenness, and to further improve the coatability. Can. As the surfactant, a non-ionic surfactant and a fluorine-based surfactant are preferably used. Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octyl phenol ether, Polyoxyethylene alkylaryl ethers such as polyoxyethylene nouryl phenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbi Sorbitan fatty acid esters such as tan trioleate and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polio Shi sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate and the like. Examples of fluorosurfactants include EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), MegaFac R08, R30, LS-14 (manufactured by Dainippon Ink Chemical Co., Ltd.), Florard FC430 FC431 (Sumitomo 3EM), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.). In addition, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used. The amount of these surfactants to be added is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, per 100 parts by weight of the composition for forming an antireflection film. These surfactants can be added alone or in combination of two or more.

Next, the antireflection film forming method of the present invention will be described. The antireflection of the present invention is applied to a substrate used in the manufacture of a precision integrated circuit device, for example, a silicon Z dioxide-silicon coating, a glass substrate, a transparent substrate such as an ITO substrate, by an appropriate coating method such as a spinner or a coater. A film-forming composition is applied. After evaporating the solvent, it is baked at 80 to 350 ° C for 10 seconds to 120 minutes to crosslink and cure to form an antireflection film. Baking promotes the crosslinking reaction and prevents mixing with the resist layer formed on the antireflection film. Since the antireflection film of the present invention has high absorbance and high etching resistance, a thin film can be formed and miniaturization can be achieved. Yes. The thickness of the antireflection film is preferably 0.03 to 20 m, more preferably 0.05 to 15 ^ m, and still more preferably 0.01 to 3. O / zm. The content of the polyphenol compound (A) in the antireflection film is preferably 50 to: LOO% by weight.

[0044] Next, on the antireflection film, in the case of a two-layer process, a silicon-containing resist layer or a single-layer resist layer made of a hydrocarbon compound, and in the case of a three-layer process, a silicon-containing intermediate layer and a silicon-free single layer. A layer resist layer is formed. After forming the resist film, a good resist pattern shape can be obtained by exposing through a predetermined mask, developing, rinsing and drying. If necessary, post exposure bake (PEB) can be performed.

[0045] As the resist applied to the upper layer of the antireflection film, a negative type or a positive type deviation can be used. These resists include a positive resist composed of novolak resin and 1,2-naphthoquinonediazide sulfonate; a group that decomposes with a photoacid generator and acid to increase the alkali dissolution rate of the resist compound. Chemically amplified resist that also has binder power; Chemically soluble resist composed of alkali soluble binder, photoacid generator, and low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of resist compound; photoacid generation A binder having a group that decomposes with an acid to increase the alkali dissolution rate of the resist compound, and a chemically amplified resist composed of a low molecular weight compound that decomposes with an acid to increase the alkali dissolution rate of the resist. Yes, for example, trade name APEX-E manufactured by Shipley. The antireflective film of the present invention does not cause a mixing phenomenon with the positive photoresist layer! , So I like it!

[0046] As a developer for the positive photoresist film formed on the antireflection film of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc. inorganic alkalis; Echiruamin, primary amines such as n- propylamine; Jechiruamin, di _n - secondary amines such as Buchiruamin; Toryechiruamin, tertiary amines such as methyl Jechiruamin; dimethylethanolamine § Min, triethanolamine § Min Alcohol amines such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, quaternary ammonium salts such as choline, etc .; aqueous solutions of cyclic amines such as pyrrole and piperidine may be used. it can. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a non-one may be added to the aqueous solution. Among these A preferred developer is an aqueous solution of a quaternary ammonium salt, more preferably an aqueous solution of tetramethyl ammonium hydroxide and choline. Since the antireflective film also has good solubility in the developer, the exposed antireflective film is removed simultaneously with the development of the photoresist film. Therefore, it is preferable in the process because it is not necessary to add a process for removing the antireflection film.

[0047] The antireflection film-forming composition of the present invention is applied on a resist layer that can be used as a BARC (Bottom Antireflective Coating) agent to be applied below the resist layer, and is applied on the antireflection film or immersion exposure. It can also be used as a T ARC (Top Antireflective Coating) agent that has a function of preventing the outflow of resist components into the solution.

[0048] Further, the antireflection film of the present invention has a function of preventing reflection of light, a function of preventing the interaction between the substrate and the resist, and a material generated when the resist material or the resist is exposed depending on the formation conditions. Demonstrates the function to prevent adverse effects on the substrate. Furthermore, when applying a resist or the like on a stepped substrate (step substrate) on which a pattern has already been formed, the step of the substrate is filled and flattened, whereby a resist film or the like applied on the substrate is flattened. It can also be used as a flat film for making the film thickness uniform.

[0049] When it is necessary to further flatten the antireflection film of the present invention, a polyphenol compound is used.

It is preferable that the glass transition temperature (Tg) of (A) is slightly lowered so that some flow occurs at the time of baking and becomes insoluble in the resist solvent after it is completely solidified.

Example

[0050] The following examples illustrate preferred embodiments of the present invention. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0051] Each evaluation was performed by the following methods.

(A) Evaluation of polyphenol compounds

(1) Molecular weight

GC—MASS / AMSUM! /, Manufactured by JEOL Ltd. was measured using PE—Bio LC-MASS / Mariner.

(2) Molecular weight distribution The measurement was performed under the following conditions using a gel permeation 'chromatography (GPC) apparatus Sho dex-11 manufactured by Showa Denko K.K.

Solvent: Hexafluoroisopropano monool containing 2 mmol% sodium trifluoroacetate

Sample concentration: Approximately 0.05 wt%

Detector: RI (Refractive Index Detecter)

Calibration: Standard polymethylmetatalylate

(3) Glass transition temperature, crystallization temperature and crystallization calorific value measurement

About 10 mg of the sample was put in an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C. Zmin in a nitrogen gas stream (50 mlZmin). After quenching, the temperature was raised again to the melting point or higher at a temperature rising rate of 20 ° C Zmin in a nitrogen gas stream (30 mlZmin). After further rapid cooling, the temperature was raised again to 400 ° C at a rate of 20 ° CZmin in a nitrogen gas stream (30 mlZmin), and differential scanning calorimetry was performed using DSCZTA-50WS manufactured by Shimadzu. The temperature at the midpoint where the discontinuity appears in the baseline (where the specific heat changed to half) was the glass transition temperature (Tg), and the temperature of the exothermic peak that appeared after that was the crystallization temperature. The area power of the region surrounded by the exothermic peak and the baseline was also calculated as the calorific value, and was used as the crystallization calorific value. The case where the glass transition temperature was 110 ° C or higher was designated as A, and the case where the glass transition temperature was below 110 ° C was designated as C. A (glass transition temperature)-(crystallization temperature) is 70 ° C or higher, and A is less than 70 ° C.

[0052] (4) Safe solvent solubility

Each polyphenol compound or poly-4-hydroxystyrene to propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, L-ethyl acetate, butyl acetate, cyclohexanone, 3-methylmethoxypropionate and propionate The dissolution test was performed at 23 ° C. When the above solvent was dissolved at 5 wt% or more, A, when 0.1-5 wt% was dissolved, B, when C was less than 0.1 wt%, and C was the force when it was not dissolved.

[0053] (5) Film formability test

The PGME3 weight ^_0/0 solution of the polyphenol compound or poly 4-hydroxy styrene, Supinko on a silicon wafer was treated with a surface treatment agent (silane coupling agent) The antireflection film having a film thickness of about 200 nm was formed by spin coating. It was heated on a hot plate at 110 ° C for 3 minutes, and the state of the antireflection film was observed. The case of whitening or irregularities on the surface was designated as C, the case of partial whitening or irregularities on the surface of the surface was designated as B, and the case where surface flatness was good without whitening was designated as A.

[0054] (4) UV'visible absorption spectrum

The PGME3 weight ^_0/0 solution of the polyphenol compound or poly 4-hydroxy styrene and spin coated on a silicon substrate, to form an antireflection film having a thickness of 200nm by beta 90 seconds at 110 ° C. Absorption at a wavelength of 193 nm was measured with a JA Woolum Inc. Incident Angle Variable Spectroscopic Ellipsometer (VAS E). Refractive index n and extinction coefficient k were obtained by approximating the measured values using a general oscillator module and fitting with a Gaussian vibrator.

[0055] (B) Evaluation of antireflection film

(1) Silicon substrate adhesion

When the formed antireflective film did not peel off the silicon wafer force, A was given, and when it was peeled off, C was given.

[0056] (2) Dissolution rate in alkaline developer

The formed antireflection film was immersed in a 2.38% by weight aqueous solution (23 ° C) of TMAH (tetramethylammonium hydroxide), and the dissolution rate was determined by the change in the antireflection film thickness before and after immersion. Less than lOAZsec is A, and more than lOAZsec is C.

[0057] (3) Formability of resist film

When a resist (made by SAL60K Shipley Co., Ltd.) was applied on the formed anti-reflection film, C was the intermixed one and A was the one that was not.

[0058] (4) Antireflection effect

When the formed antireflection film was irradiated with an excimer laser of 248 nm, the extinction coefficient was 1.5 or more and A was less than 1.5.

[0059] Synthesis Example 1

Synthesis of 2,7bis [bis (2, 3, 5 trimethyl 4 hydroxyphenol) methyl] naphthalene (101) [Chemical 14]

2, 3, 6-trimethylphenol 195g (l. 6mol) (manufactured by Kanto Chemical Co., Ltd.) and 2, 7—naphthalenedialdehyde 40. Og (0.2 mol) (Mitsubishi Gas Chemical 2, 7-naphthalene) Using dimethyl rubonate as a raw material, synthesized according to JP 2003-155259), heated to about 60 ° C and dissolved. To this, 0.2 ml of sulfuric acid and 1.6 ml of 3-mercaptopropionic acid were added and reacted with stirring. After confirming that the conversion rate reached 100% by liquid chromatography, 100 ml of toluene was collected. The solid precipitated after cooling was filtered under reduced pressure, stirred and washed with hot water at 60 ° C, and purified by silica gel column chromatography to obtain the desired product. The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement (400 MHz, d-DMSO, internal standard TMS). The results are shown in Tables 1 and 2. Table 3 shows the evaluation results of the obtained polyphenolic compound.

Synthesis example 2

Synthesis of 2, 6-bis [bis (2-isopropyl 4-hydroxy 5-methylphenol) methyl] naphthalene (102)

[Chemical 15]

The synthesis was carried out in the same manner as in Synthesis Example 1 except that 2,7 naphthalenedialdehyde was replaced with 2,6 naphthalenedialdehyde and trimethylphenol was replaced with thymol manufactured by Kanto Steel. Synthesis example 3

9—Synthesis of [bis (2, 3, 5 trimethyl 4-hydroxyphenol) methyl] phenanthrene (103)

[Chemical 16]

The synthesis was performed in the same manner as in Synthesis Example 1 except that 2,7 naphthalenedialdehyde was replaced with 9 formylphenanthrene.

Synthesis example 4

Synthesis of 1 [bis (4-hydroxyphenyl) methyl] pyrene (104)

[Chemical 17]

Synthesis was performed in the same manner as in Synthesis Example 1 except that 2,7 naphthalenedialdehyde was replaced with 1-formylpyrene.

Synthesis example 5

Synthesis of 4-bis [bis (4-hydroxyphenyl) methyl] biphenyl (105)

[Chemical 18]

Synthesis was performed in the same manner as in Synthesis Example 1 except that 2,7 naphthalenedialdehyde was replaced with 4,4'-biphenyldialdehyde.

Synthesis example 6

Synthesis of 4, 4 ', monobis [bis (2,5 dimethyl 4-hydroxyphenol) methyl] terfal (10 6)

[Chemical 19]

Synthesis was carried out in the same manner as in Synthesis Example 1 except that 2,7 naphthalenedialdehyde was replaced with 4,4 'and terdialdehyde.

Comparative synthesis example 1

Synthesis of 1, 3, 5 tris [bis (2, 3, 5 trimethyl 4 hydroxyphenol) methyl] benzene (107)

[Chemical 20]

The synthesis was performed in the same manner as in Synthesis Example 1 except that 2,7 naphthalenedialdehyde was replaced with 1, 3, 5 benzenetrialdehyde.

Comparative synthesis example 2

Synthesis of 4 [bis (4-hydroxyphenyl) methyl] biphenyl (108)

[Chemical 21] (108)

The synthesis was carried out in the same manner as in Synthesis Example 1 except that 2,7-naphthalenedialdehyde was replaced by 4-bialdehyde from Mitsubishi Gas Chemical.

Reference example 1

Poly-hydroxystyrene having a molecular weight of 8000 (Al compound 109) manufactured by Aldrich was used as a reference compound.

[Chemical 22]

[table 1]

[ε 挲] [οζοο] t''6'H2'HO: fiL-99'HAI ' ^t ldiS e'HT'HO 801 z

0 · 8- Δ'Η9'ΗΟ: 6'9-99'H6'¾d [: 9 S'HS'HO.'Z'ZT S'Ht'S ' ^a W LOT \ i'6'Η t-'HO' .S LL 9'U0Z ^ d'9f9'llZ'llD'B Zl Z'mZ ^ n 901 9

SOT S

f6'HZ'HO: r8-S '' H6 'd: ir ^ 9'9'H8'qd: S'S'in'HO 0ΐ P

6'H 'HO: I'8

-S L'H6'aqdiT A-9-9'HZ'¾: e'9'HI'HO.'Z'3-T'3'H8T ' ³ I¾ εοτ ε

L L '' UO

: 6 A-e: SS-3 T'H9e'9I¾ ζοι z

L L'm'UO

I'S'H9S'aw ΤΟΐ l

69 1 8 806 ZL 9 02 S8 τ 0Z 9Z 80ΐ Z

6, i ε Z9 8S 01 fLL ZL 18 9 OL Z9 Λ0Ι ΐ '.9' 99 ∎ 8 Z9 '9 Z9 fS f OS Z9 901 9

0 'L I fS S9 6 66, 9 9 88 f 9f 9f SOT S

s e 0 88 66 • L εο e 00 7,8 Z OZ 6Z 0ΐ t-

9 'L e 98 36 • 9 00 • L 90 98 z 09 εε εοτ ε

6 Ί I S8 e 8 m 0 ', 8 9 € 8 f 09 Z9 zo \ z

'L 0 88 6 9S' L oz- 68 f Z 9f ΙΟΐ x

H O O H 0 O H 0

LZ9 £ S0 / L00ZdT / 13d LS L60 / L00Z OAV Table 3

Glass transition crystallization glass transition

Compound M w / Safety solvent

Temperature Temperature Temperature One crystal Molecular weight Filmability No. M n Solubility

Evaluation at conversion temperature

Synthesis example

1 101 156 A n.d.A 692 1.0 A A

2 102 122 A n.d.A 748 1.0 A A

3 103 122 A n.d.A 431 1.0 A A

4 104 140 A n.d.A 400 1.0 A A

5 105 135 A n.d.A 662 1.0 A A

6 106 146 A n.d.A 738 1.0 A A Comparative synthesis example

1 107 125 A n.d.A 820 1.01 A A

2 108 79 C n.d.A 352 1.0 A A Reference example

1 109 177 A n.d. A 8130 1.6 A A n.d .: Not confirmed

[0071] Examples 1 to 6 and Comparative Examples 1 to 3

The PGMEA solutions of the polyphenol compounds (101 to 108) and poly (4-hydroxystyrene) (reference compound 109) obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 and 2 were treated with a surface treatment agent (silane coupling). The film was spin-coated with a spin coater on a silicon wafer that had been treated with (agent) to form a film with a film thickness of about 0.5 / zm. Subsequently, it was heated on a hot plate at 110 ° C. for 3 minutes to obtain an antireflection film. Table 4 shows the evaluation results of the obtained antireflection film.

[0072] [Table 4] Table 4

Silicon Power Resistant 瞜 Anti-reflective Compound No.

Substrate adhesion Dissolution rate Formability Effect Example

1 101 A A A A

2 102 A A A A

3 103 A A A A

4 104 A A A A

5 105 A A A A

6 106 A A A A

Comparative example

1 107 A A A C

2 108 A A A A

3 109 A A A C

[0073] Examples 7 to 14: 14 and Comparative Examples 4 to 7 Compounds 101-109 and m- cresol one novolak resin (Mw: 8800) (hereinafter, climb click hereinafter) was dissolved at a concentration of PGME (propylene glycol monomethyl ether) 5 wt ^_0/0, respectively, 0 .: m Each of the antireflective film forming solutions was prepared by filtering through a filter made of fluororesin.

Next, the antireflection film-forming solution was spin-coated on a silicon substrate and baked at 300 ° C. for 90 seconds to form an antireflection film having a thickness of 200 nm. The refractive index n and extinction coefficient k of each antireflection film were measured. The results are shown in Table 5 of A AAAAAAAA CCC.

[Table 5] Table 5

Polyph πnol compound Tachibana agent Acid generator Solvent

(K part) (K part) (Mass part) (Mass part)

Example

7 1 0 1 (5) ― One P GME A (9 5

8 1 0 1 (5) Two-strength rack (0.5) T P S 1 0 9 (0. 1) P GME A (9 5

9 1 0 1 (2.5) ―-P GME A (9 5

Novolac (2.5)

1 0 1 0 2 (5)--P GME A (9 5

1 1 1 0 3 (5) One P GME A (9 5

1 2 1 0 4 (5) One ― P GME A (9 5

1 3 1 0 5 (5) ― One P GME A (9 5

1 4 1 0 6 (5) ―-P GME A (9 5 Comparative example

4 1 0 7 (5) One-P GME A (9 5

5 1 0 8 (5) ― ― P GME A (9 5

6 1 0 9 (5) ― ― P GME A (9 5

7 Novolac (5) — — P GME A (9 5 Nikarak: Sankara Chemical's Nikarak M X 270

TP S 109: Triphenylsulfo-munonafluo Cimethanesulfonate

[Table 6] Table 5 (continued)

Intermixing Refractive index n Extinction coefficient k Example

7 2 1 0. 56

8 33 0. 38

9 25 0. 6 1

34 0. 48

4 1 0. 53

1 2 53 0. 32

1 3 34 0. 2 7

1 4 50 0. 23

Comparative example

4 53 0. 2 6

5 20 0. 70

6 1 5 0. 5 6

1 9 0. 80 Examples 15-16 and Comparative Example 8

Compound 101 (Example 15), Compound 101 and m- cresol one novolac榭脂(Mw: 8800) of 1: Coating 1 mixture (Example 16) 5 wt ⁰ / ^oPGME solution thickness 300nm of SiO on the substrate

2

An anti-reflective film having a thickness of 80 nm was formed by betaning at 300 ° C. for 120 seconds. On top of that, a resist solution consisting of 5 parts by weight of compound 110, 1 part by weight of TPS 109, 2 parts by weight of tributylamine, and 92 parts by weight of PGMEA is applied and betated at 130 ° C for 60 seconds. A 200 nm thick photoresist layer was formed.

[Chemical 23]

Similarly, the resist solution is not formed on the SiO substrate except that no antireflection film is formed.

2

The solution was applied to form a photoresist layer (Comparative Example 8).

Next, the photoresist layer was exposed with an electron beam lithography apparatus (manufactured by Elio-Tass; ELS-7500, 50 keV) and beta-treated at 115 ° C. for 90 seconds. 2.38 mass ^_0/0 tetramethylammonium - developed for 60 seconds at Umuhi Dorokishido (TMAH) aqueous solution to obtain a positive pattern. Table 6 shows the limit resolution of the obtained line and space and the electron beam dose at that time. In addition, the line edge roughness (LER) is evaluated at the SEM terminal PC V5 offline measurement for Hitachi Semiconductor at any 300 points in the length direction (0.75 m) of the 1: 1 line-and-space limit resolution. Using software (manufactured by Hitachi Science Systems, Ltd.), the distance between the edge and the reference line was measured. The standard deviation (3σ) was calculated from the measurement results. The results are shown in Table 6.

A: LER (3 a) ≤ 4.5 nm (good LER)

C: 4.5 nm <LER (3 σ) (not good LER)

[Table 7] Table 6

Resolution Sensitivity LER

Example 1 5 6 0 nni L & S 1 2 il C / cm ² A Example 1 6 6 0 n 11 i L & S 1 2 il C / cm ² A Comparative Example 8 8 0 nni L & S 2 6 il C / cm ² C

[0075] Next, etching was performed under the following conditions.

Etching device: manufactured by Elio-Tas

Voltage: 400V

Current density: 0.9mA / cm ²

Time: 2min

Ar gas flow rate: CF gas flow rate: O gas flow rate = 10: 1: 1 (volume ratio)

4 2

The cross section of the pattern was observed with an electron microscope (S-4800) manufactured by Hitachi, Ltd.

¾πί.

[0076] In Examples 15 and 16, the resist shape after development and the shape of the antireflection film after etching were good, but in Comparative Example 8, the LER was larger and the pattern shape was rounded, which was insufficient. there were.

Industrial applicability

[0077] Composition force for forming an antireflection film of the present invention The obtained antireflection film not only has a high antireflection effect, but also fills the unevenness of the substrate to form a flat surface. Therefore, the film thickness of a coating film such as a resist applied thereon becomes uniform, and a good resist pattern can be formed. In addition, since it has low sublimation and high dry etching resistance, the line edge roughness of the resist pattern is small. Furthermore, since it dissolves in an alkaline developer, a separate dry etching process is not required to remove the antireflection film.

Claims

The scope of the claims

[1] The following conditions:

(b) Molecular weight force 00-2000;

(c) molecular weight distribution MwZMn is 1-1.05; and

(d) Glass transition temperature of 110 ° C or higher

Anti-reflective coating composition comprising polyphenolic compound (A) and organic solvent (B) satisfying

[2] The composition of the antireflection film according to claim 1, comprising a conjugated structure in which at least two benzene rings and a non-bonded electron pair of Z or hetero atom are involved. object.

[3] The conjugated structure is selected from biphenyl, naphthalene, anthracene, phenanthrene, pyrene, fluorene, acenaphthene, 1-keto acenaphthene, acenaphthylene, benzophenone, terphenyl, phenanthraquinone, xanthene, and thixanthene. The composition for antireflection coating according to claim 2, wherein the composition is derived from at least one compound.

[4] The polyphenol compound (A) is represented by the following formula 1:

[Chemical 1]

(In the formula, R ¹ is biphenyl structure, naphthalene structure, anthracene structure, phenanthrene structure, pyrene structure, fluorene structure, acenaphthene structure, 1-ketoacenaphthene structure, acenaphthylene structure, benzophenone structure, terphenyl structure, phenanthraquinone Structure, xanthene structure, and thixanthene structural force represents a C1-C18 monovalent to tetravalent substituent derived from at least one selected compound;

R ² represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;

n is an integer from 1 to 4;

p is an integer from 0 to 4;

q is an integer from 1 to 4;

L≤p + q≤5 in each benzene ring; a plurality of R ² , p, and q may be the same or different; carbon atom a and carbon atom b are bonded via oxygen or nitrogen. May be)

The composition for forming an antireflective film according to claim 1 represented by:

[5] 4. The antireflection film-forming composition of wherein R ¹ is from 1 to 4 monovalent substituents derived naphthalene force in formula 1.

[6] The polyphenolic compound (A) is represented by the following formula 2:

[Chemical 2]

(Wherein R ² , n, p and q are the same as above)

6. The composition for forming an antireflection film according to claim 5, which is represented by:

2. The composition for forming an antireflection film according to claim 1, wherein the organic solvent (B) is propylene glycol monomethyl ether acetate, lactic acid or cyclohexanone. [8] The composition for forming an antireflection film according to [1], further comprising a resin having a repeating unit obtained by converting the polyphenolic compound (A) into a novolak form.

9. The composition for forming an antireflection film according to claim 1, further comprising a crosslinking agent and an acid generator.

[10] The antireflection film obtained as described in [1].

11. The antireflection film according to claim 10, wherein the content of the polyphenol compound (A) is 50 to: LOO wt%.

[12] The following conditions:

(b) Molecular weight force 00-2000;

(c) molecular weight distribution MwZMn is 1-1.05; and

(d) Glass transition temperature of 110 ° C or higher

A step of applying a composition containing a polyphenolic compound (A) and an organic solvent (B) that simultaneously satisfy the following conditions; after evaporating the organic solvent (B), at 80 to 350 ° C for 10 seconds to A method for forming a resist layer having an antireflection film as a lower layer, comprising a step of baking for 120 minutes to form an antireflection film; and a step of forming at least a resist layer on the antireflection film.