WO2007114253A1 - Composition for under-resist film and under-resist film using same - Google Patents

Abstract

Disclosed is a composition for an under-resist film which enables to reduce bottom trailing of a resist pattern, while improving the shape of the resist pattern. Also disclosed is an under-resist film obtained by using such a composition. Specifically disclosed is a composition for an under-resist film containing a siloxane polymer, in which composition a certain amount of a quaternary ammonium compound is also contained.

Description

 Specification

 Composition for resist underlayer film and resist underlayer film using the same

 Technical field

 The present invention relates to a resist underlayer film composition used for a resist underlayer film that is used as an antireflection film when a resist pattern is formed on a substrate, and a resist underlayer film using the same.

 Background art

 In the manufacture of semiconductor elements, pattern formation on a substrate is performed by a lithography process.

 In recent years, high integration of semiconductor elements on circuit boards has progressed. However, as high integration progresses, standing waves generated during the exposure process cause fluctuations in the size of the noturn. Yes. As a method of suppressing this standing wave, a method of adding a light absorber to the resist composition, a method of laying an antireflection film on the upper layer of the formed resist layer, or a lower layer of the resist layer, and the like have been proposed.

[0003] In order to form a finer pattern, it is required to reduce the thickness of the antireflection film and the resist layer. However, with the thin film of the resist layer, it becomes difficult to perform accurate etching, so that it is difficult to process the substrate with high accuracy. Therefore, a resist underlayer film (node mask) having a function as an antireflection film and a Z or organic bottom layer are formed between the film to be processed such as a substrate to be processed and the resist layer, and the base layer is formed. A process of dry etching a film to be processed such as a plate, an oxide film or an interlayer insulating film is performed.

 [0004] For this resist underlayer film composition, it has been proposed to use a silicon-based material for the problem of the etching selectivity with respect to the resist layer (see, for example, Patent Documents 1 and 2).

 Patent Document 1: JP 2004-310019 A

 Patent Document 2: JP-A-2005-18054

 Disclosure of the invention

Problems to be solved by the invention [0005] In the resist underlayer film materials disclosed in Patent Documents 1 and 2, there is a problem that tailing occurs in a resist pattern formed on the resist underlayer film formed from the resist underlayer film material. Has occurred. When such tailing occurs, there arises a problem that the pattern cannot be transferred to a desired shape when the resist underlayer film is etched.

 [0006] In view of the above problems, the present invention reduces resist pattern tailing and improves the shape of the pattern, and a resist underlayer film and composition using the same. An object is to provide a strike underlayer film.

 Means for solving the problem

[0007] By adding a quaternary ammonium compound to the resist underlayer film composition, the present inventors can reduce the tailing of the resist pattern and improve the shape of the pattern. The inventors have found that this is possible and have completed the present invention.

[0008] The present invention provides a resist underlayer film composition containing a siloxane-based polymer and a quaternary ammonium compound.

 Further, a resist underlayer film obtained by applying this resist underlayer film composition and beta-treating at a predetermined temperature is provided.

 The invention's effect

 [0009] According to the present invention, by adding a quaternary ammonium compound to the resist underlayer film composition, the bottoming of the resist pattern can be reduced and the shape of the pattern can be improved. It has become possible.

 Brief Description of Drawings

 FIG. 1 is a diagram showing a process of forming a resist pattern using the resist underlayer film composition according to the present invention.

 Explanation of symbols

 [0011] 20 substrates

 22 Resist underlayer

24 resist film BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described in detail. The resist underlayer film composition according to the present invention comprises (A) a siloxane polymer (hereinafter also referred to as (A) component) and (B) a quaternary ammonium compound (hereinafter also referred to as (B) component). And containing.

[0013] [(A) Siloxane polymer]

 The resist underlayer film composition according to the present invention contains (A) a siloxane-based polymer. In the resist underlayer film composition according to the present invention, the (A) siloxane polymer preferably has a structural unit represented by the general formula (a-1).

 [Chemical 1]

[Wherein R ⁵ represents a light absorbing group, R ⁶ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and r is 0 or 1. ]

[0014] The light absorbing group is a group having absorption in a wavelength range of 150 to 300 nm. Examples of the light absorbing group include groups having a light absorbing portion such as a benzene ring, an anthracene ring, and a naphthalene ring. The light absorbing part is interrupted by one or more —0— and —O (CO) — !, but may be bonded to the Si atom of the main skeleton via an alkylene group having 1 to 20 carbon atoms. May be. In addition, one or more light absorbing portions such as a benzene ring, an anthracene ring, and a naphthalene ring may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a hydroxy group. Among these light absorbing groups, a benzene ring is preferable. In addition to the above light absorbing group, a group having a light absorbing portion having a Si—Si bond can also be used. Further, these light absorbing portions may be included in the main skeleton of the siloxane polymer. Examples of the light-absorbing group include a furyl group, a naphthyl group, a methyl furol group, an ethyl furol group, a tolyl group, a black fouling group, a bromophenol group, and a fluorophenyl group; benzyl And a aralkyl group such as a group, a phenethyl group, a naphthylmethyl group, a diphenylmethyl group, a triphenylmethyl group, and a 1-methyl-1-phenylethyl group. Among them, phenyl Groups are preferred. In particular, when a phenyl group is used, light absorption can be improved. Further, the (A) siloxane-based polymer preferably has at least one of the structural units represented by the general formula (a-2).

[Chemical 2]

R ⁷

 1 Si 1 0 (3_s) / 2

[Wherein R ⁷ represents a hydrogen atom, an alkyl group, or a monovalent organic group having at least one functional group selected from carbonyl, ester, rataton, amide, ether, and -tolyluca, and R ⁸ represents Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and s is 0 or 1. ]

 These siloxane polymers may be used alone or in a combination of two or more.

 (A) It is preferable to use a siloxane copolymer having a mass average molecular weight of 4000 or more, more preferably 8000 or more. By using the component (A) having a mass average molecular weight of 4000 or more, it is possible to improve the film formability of the resist underlayer film that also forms the composition for the resist underlayer film of the present invention. The mass average molecular weight of component (A) is preferably 50000 or less, more preferably 30000 or less. (A) Mass of component By making an average molecular weight into 50000 or less, the applicability | paintability of the composition for resist underlayer films of this invention can be improved.

 Further, as the component (A), a mixture of a siloxane polymer having a mass average molecular weight of less than 4000 and a siloxane polymer having a mass average molecular weight of 4000 or more is also preferable. The siloxane polymer having a mass average molecular weight of less than 4000 preferably has a mass average molecular weight of 300 to 3,000. As a result, it is possible to further reduce the tailing of the resist pattern formed on the resist underlayer film on which the composition force for the resist underlayer film is also formed.

This siloxane-based polymer having a mass average molecular weight of less than 4000 is The force is also preferably 70% by mass, more preferably 30 to 60% by mass.

<0016> <(A) Method for producing siloxane copolymer>

 (A) A method for producing a siloxane-based copolymer can be obtained by hydrolyzing and copolymerizing each monomer containing a predetermined structural unit. The amount of water in the hydrolysis reaction is preferably 0.2 to 10 moles per mole of monomer. At this time, known catalysts such as metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases may be appropriately added.

 [0017] Specific examples of the metal chelate compound include tetraalkoxy titanium, trialkoxy mono (acetylacetate) titanium, tetraalkoxy zirconium, trialkoxy mono (acetylacetate) zirconium, and the like. It is done. Examples of organic acids include acetic acid, propionic acid, oleic acid, stearic acid, linoleic acid, salicylic acid, benzoic acid, formic acid, malonic acid, phthalic acid, fumaric acid, citrate, and tartaric acid. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, methylsulfonic acid, tosylic acid, trifluoromethanesulfonic acid, and the like.

 [0018] Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, Examples thereof include monomethyl jetanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

[0019] Of these, ammonia, organic amines, etc. are used so as not to open the epoxy group or oxetal group contained as a crosslinking group during polymerization, and to prevent contamination by alkali or metal impurities. It is preferable to use a basic catalyst. Among them, it is preferable to use a tetraalkyl ammonium hydroxide. The epoxy group Ya Okiseta - so as not Le group with ring opening, it is preferable to set the system to the _P H7 above atmosphere. These catalysts can be used alone or in combination of two or more.

[0020] As a reaction operation, first, each monomer is dissolved in an organic solvent, and water is added to perform hydrolysis. Start the reaction. The catalyst may be added to water or in an organic solvent.

 [0021] The organic solvent used in the reaction is preferably an insoluble or insoluble solvent in water. Specifically, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl 2-n-amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether , Propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and mixtures thereof are preferred.

 [0022] Next, the catalyst is neutralized, and the organic solvent layer is separated and dehydrated. This is because the remaining water causes the condensation reaction of the remaining silanol to proceed. Use a known dehydration method such as adsorption using a salt such as magnesium sulfate or molecular sieve, or azeotropic dehydration while removing the solvent.

 [0023] Next, an organic solvent hardly soluble or insoluble in the above water is added, and the organic solvent layer is separated and washed with water to remove the catalyst used for hydrolysis condensation. At this time, it may be neutralized if necessary. Subsequently, the separated organic solvent layer is dehydrated to obtain (A) a siloxane copolymer.

 [0024] [(B) Quaternary ammonium compound]

 The resist underlayer film composition according to the present invention contains (B) a quaternary ammonium compound. Conventionally, ammonia compounds and amine compounds have been excluded as one of the causes of resist pattern deterioration with time and resist pattern tailing.

 However, according to the present invention, by adding a predetermined amount of the quaternary ammonium compound, the tailing of the resist pattern formed on the resist underlayer film is reduced, and the pattern shape is improved. Is possible.

 [0025] (B) Specifically, the quaternary ammonium compound is preferably a quaternary ammonium compound represented by the following general formula (b-1).

 [Chemical 3]

[In the formula, R ¹ to R ⁴ are each independently a hydrocarbon group and are counter-on. ]

[0026] Examples of the "hydrocarbon group" of R ¹ to R ⁴ include linear, branched, or cyclic saturated or unsaturated hydrocarbon groups. These may have a substituent.

 Examples of linear and branched hydrocarbon groups include methyl, methylene, ethyl, ethylene, propyl, propylene, isopropyl, n-butyl, isobutyl, isopropylene, second Butyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, A decyl group, an isodecyl group, etc. are mentioned.

 [0027] Examples of the cyclic hydrocarbon group include a cyclic alkyl group and an aryl group.

 Examples of the cyclic alkyl group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as cycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane and the like. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one hydrogen atom from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Can be mentioned.

 Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a tolyl group, a chlorophenol group, a bromophenyl group, a fluorophenyl group, and the like.

 [0028] Examples of the substituent include an OH group and an alkoxy group having 1 to 3 carbon atoms.

[0029] Among them, those in which the total carbon number of R ¹ to R ⁴ is 10 or more are preferable. By setting the total number of carbon atoms to 10 or more as described above, the tailing of the resist pattern formed on the resist underlayer film can be reduced and the pattern shape can be improved.

In addition, it is preferable that at least one of R ¹ to R ⁴ is a hydrocarbon group having 8 or more carbon atoms. Thereby, the tailing of the resist pattern formed on the resist underlayer film can be further reduced.

The total carbon number of R ¹ to R ⁴ is preferably 25 or less. As a result, tailing can be further reduced. [0030] X- of the counter-on is OH-, Cl_, Br ", F-, alkyl carboxylic acid cation, aryl carboxylic acid cation, aralkyl carboxylic acid cation, etc. It is preferable.

 [0031] The amount of (B) quaternary ammonia compound added is 0 with respect to 100 parts by mass of component (A).

It is more preferred that it is from 01 to 10 parts by weight, and from 0.1 to 5 parts by weight.

0. Most preferred to be from 1 to 3 parts by weight U.

 By making the amount added 0.01 parts by mass or more, the crosslinking density of the component (A) can be increased. Further, when the addition amount is 10 parts by mass or less, the temporal stability of the resist underlayer film composition can be improved.

[0032] The resist underlayer film composition of the present invention may contain the following components (C), (D), and (E).

[0033] [(C) Organic acid]

 The resist underlayer film composition according to the present invention preferably contains (C) an organic acid. By adding this (C) organic acid, it is possible to prevent deterioration of the resist underlayer film composition with time due to the addition of the component (B).

[0034] Examples of the organic acid (C) include organic carboxylic acids, organic phosphonic acids, and organic sulfonic acids. Examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid and stearic acid; unsaturated aliphatic monocarboxylic acids such as oleic acid and linoleic acid; oxalic acid, Aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid and maleic acid; oxycarboxylic acids such as lactic acid, darconic acid, malic acid, tartaric acid and succinic acid; aromatics such as benzoic acid, mandelic acid, salicylic acid and phthalic acid Carboxylic acids are mentioned.

 As these organic acids, malonic acid is particularly preferable.

[0035] The amount of (C) the organic acid added is 0.01 to 10 parts by mass and 0.1 to 5 parts by mass with respect to 100 parts by mass of component (A). More preferred is 0.1 to 3 parts by weight, most preferred.

By making the addition amount 0.01 parts by mass or more, the temporal stability of the resist underlayer film composition can be further improved. By adding less than 10 parts by mass (B) Inhibition of components can be suppressed.

 [0036] The mass ratio of component (C) to component (B) is preferably in the range of 10: 100 force to 75: 100, and in the range of 20: 100 to 60: 100. It is more preferable.

 By setting the mass ratio within this range, the tailing of the resist pattern formed on the resist underlayer film is reduced, the pattern of the pattern is improved, and the temporal stability of the resist underlayer film composition is further improved. be able to.

 [0037] [(D) Solvent]

 The composition for resist underlayer film according to the present invention also contains (D) a solvent (hereinafter also referred to as component (D)). Specifically, monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, hexanetriol, and ethylene glycol Norenomonochinenoetenore, Ethyleneglycolenomonoetinoreetenore, Ethyleneglycololemonopropinoreetenore, Ethyleneglycololemonobutinoreetenore, Diethyleneglycolenomonomonomethinoreethenore, Diethyleneglycolenomonoetinorenoetole, Diethylene glycol monopropyl ether, diethylene glycol nomonomono butinole etherenole, propylene glycol monomethyl ether, propylene glycol Monoethyl alcoholate such as monoethylenoate, propylene glycolenomonopropinoreateenole, propylene glycolenole monobutyl ether, esters such as methyl acetate, ethyl acetate, butyl acetate, and ethyl lactate, acetone, methyl ether Ketones such as tilketone, cycloalkylketone, and methylisoamylketone, ethylene glycol dimethyl ether, ethylene glycol oleo chinenoateol, ethylene glyconoresive pinole ethenole, ethylene glycol dibutyl ether, propylene glycol dimethyl ether (PGDM), propylene glycol Jetinore ter, propylene glycol dibutinore ter, diethylene glycol dimethyl ether, diethylene glycol methyl ether, die Alcohols and ethers in which all the alcoholic hydroxyl groups such as glycol Jefferies chill ether was alkyl Eterui spoon and the like.

[0038] These organic solvents may be used alone or in combination of two or more. Adjust this solvent so that the components other than the solvent are 0.5 mass% to 10 mass%. It is more preferable to adjust the amount to 1 to 6% by mass. By making it within this range, the coating property of the resist underlayer film composition can be improved.

 [0039] [(E) Crosslinking agent]

 The resist underlayer film composition according to the present invention also contains (E) a crosslinking agent (hereinafter also referred to as component (E)). (E) The addition of a crosslinking agent can improve the film formability of the resist underlayer film. As the crosslinking agent, those generally used may be used.

 [0040] Specifically, epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol nopolac type epoxy resin, etc. Etc. Further, divinyl benzene, divinyl sulfone, triacryl formal, glyoxal or polyhydric alcohol acrylate or methacrylate is also used.

 [0041] Further, compounds having two or more reactive groups such as a compound substituted with at least two forces of S-aminol group or lower alkoxymethyl group of melamine, urea, benzoguanamine, glycoluril, etc. It is done.

 [0042] Examples of the compound in which at least two of the melamine amino groups are substituted with a methylol group or a lower alkoxymethyl group include hexamethylol melamine, hexamethoxymethyl melamine, and 1 to 6 hexamethylol melamines. Methylated compounds and mixtures thereof, hexamethoxyethyl melamine, hexacyloxymethyl melamine, compounds in which 1 to 5 methylol groups of hexamethylol melamine are acyloxymethylated or mixtures thereof Etc.

 [0043] Examples of the compound substituted with at least two strong methylol groups or lower alkoxymethyl groups of urea amino groups include tetramethylol urea, tetramethoxymethyl urea, tetramethoxy shetilurea and tetramethylol urea. Examples thereof include a compound having a methylol base S methoxymethyl group or a mixture thereof.

[0044] Examples of compounds in which at least two of the amino groups of benzoguanamine are substituted with a methylol group or a lower alkoxymethyl group include tetramethylolguanamine, tetramethoxymethyldiaminamine, and tetramethylolguanamine. Toximethylated compounds and mixtures thereof, tetramethoxyethyldaanamine, tetracyloxyguana Examples thereof include compounds in which four methylol groups are acyloxymethylated, and mixtures thereof, such as amine and tetramethylolguanamine.

 [0045] Examples of the compound in which at least two of the amino groups of glycoluryl are substituted with a methylol group or a lower alkoxymethyl group include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyldarlicururyl, tetramethylol. A compound in which four of the methylol groups of glycoluril have four methoxymethyl groups, or a mixture thereof, a compound in which one to four of the methylol groups of tetramethylol glycoluril are acyloxymethylated, or a mixture thereof Is mentioned.

 [0046] These crosslinking agents may be used alone or in combination of two or more.

 The amount of the crosslinking agent added is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of component (A), and the 0.5 mass part force is more preferably 40 parts by mass.

 [0047] [(F) Acid generator]

 The resist underlayer film composition according to the present invention may contain (F) an acid generator (hereinafter also referred to as (F) component). (F) By adding an acid generator, the crosslinking efficiency can be further improved. Examples of such an acid generator include those that generate an acid by light or heat.

 [0048] Photosensitive acid generators include onium salts, diazomethane derivatives, darioxime derivatives, bissulfone derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, and ヒ ド ロ キ シ -hydroxyimide compounds. Known acid generators such as sulfonate ester derivatives can be used.

[0049] O - © The unsalted, triflumizole Roo b methanesulfonic acid tetramethylammonium - © beam, Nonafuru O Rob Tan sulfonate tetramethylammonium - © beam, nona full O Rob Tan acid tetra _η Buchiruanmo - © beam, Nonafluorobutane sulfonic acid tetraphenyl ammonium, ρ -Toluenesulfonic acid tetramethyl ammonium, trifluoromethanesulfonic acid diphenol rhododonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) -Rhododonium, p-toluenesulfonic acid diphenylodium, p-toluenesulfonic acid (p- tert-butoxyphenyl) phenol, trifluoromethanesulfonic acid triphenylsulfurone, trifluoromethanesulfonic acid (P-tert-butoxyphenyl) Ethyl sulfone, trifluoromethanesulfonic acid bis (p-tert butoxyphenyl) Phenol sulfone, trifluoromethanesulfonic acid tris (p- tert butoxyphenyl) snorephonium, p Triphenol-nolesnorephonium, p-tonoleensnorephonic acid (p-tert-butoxyphenyl) diphenylsulfone, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenolsulfo -PuM, p Toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfone, Nonafluorobutanesulfonic acid triphenyl sulfone, Butanesulfonic acid triphenyl sulfone, Trifluoromethane Trimethyl sulfone sulfonate, ρ-trimethyl sulfone-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2 —Oxocyclohexyl) sulfo, p-Toluenesulfonate cyclohexylmethyl (2-oxocyclohexyl) sulfurium, trifluoromethanesulfonate dimethylformsulfur, p Toluenesulfonate dimethylphenol Sulfosulfur, trifluoromethanesulfonic acid dicyclohexylphenyl sulfone, p-toluenesulfonic acid dicyclohexylphenol sulfone, trifluoromethanesulfonic acid trinaphthylsulfum, trifluoromethanesulfonic acid Cyclohexylmethyl (2-oxocyclohexyl) sulfone, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfone, ethylene bis [methyl (2-oxo Cyclopentyl) sulfo-umtrifluoromethanesulfonate], 1, 2 , Naphthyl carboxymethyl tetrahydrothiophene um triflate and the like. Diazomethane derivatives include bis (benzenesulfol) diazomethane, bis (p-toluenesulfol) diazomethane, bis (xylenesulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, and bis (cyclopentylsulfol). ) Diazomethane, bis (n-butylsulfol) diazomethane, bis (isobutylsulfol) diazomethane, bis (sec butylsulfol) diazomethane, bis (n-propylsulfol) diazomethane, bis (isopropylsulfol) diazomethane Bis (tert-butylsulfo) diazomethane, bis (n-amylsulfo) diazomethane, bis (isoamylsulfo) diazomethane, bis (sec-amylsulfo) diazomethane, bis (tert-amylsulfo) diazo Methane, 1-cyclohex Rusuruho - Lou 1-(tert Buchirusuruho - Le) Jiazometan, 1 - cyclohexane Kishirusuruho - Le - 1-(tert - Amirusuruho - Le) Jiazometan, 1 - tert —Amylsulfo-Lu 1 (tert-butylsulfo) diazomethane and the like.

[0051] Glyoxime derivatives include bis-O- (p toluenesulfol) _-a -dimethylglyoxime, bis-mono-O- (p toluenesulfol) _a -diphenyldaroxime, bis-O- (p Toluenesulfol) One dicyclohexylglyoxime, bis-I O— (p Toluenesulfol)-2, 3—Pentangiform gurioxime, bis-O— (p Toluene sulphononiole) 2—Methylolone 3 , 4 Pentanedione glyoxime, bis-mono-O- (n-butanesulfol) α-dimethyldarioxime, bis-Ο- (η-butanesulfol)-a-diphenylglyoxime, bis-mono-O- (n— Butanesulfoyl) α-dicyclohexinoredarixime, bis Ο— (η—butansnorephoninole)-2, 3-pentanedione glyoxime, bis 一 — (η-butanesulfol) 2-methyl 3, Four Nantungori oxime, bis-Ο- (methanesulfol) a-dimethyldarioxime, bis-Ο- (trifluoromethanesulfol)-α-dimethyldarioxime, bis- 0- (1, 1, 1-tri full O Roe Tan sulfo - Le) _alpha - dimethyl Dali oxime, bis - O- (tert Butansu sulfo - Le) - _a - dimethyl Dali oxime, bis one O- (per full O b octane sulfo - Le) - a- Dimethyldarioxime, bis—O— (cyclohexanesulfol) at—dimethylglyoxime, bis—O— (benzenesulfol) oc—dimethyldarioxime, bis- 0- (p fluorobenzenesulfol ) Α-dimethyldarioxime, bis-Ο- (ρ- tert butylbenzenesulfol) α-dimethyldarioxime, bis キ (xylenesulfol) α-dimethyldarioxime, bis O-(camphorsulfonyloxy - Le) a chromatography dimethyl Dali oxime, and the like.

[0052] Examples of the bissulfone derivative include bisnaphthylsulfurmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfolmethane, bisisopropylsulfurmethane, -Rumethane, bisbenzenesulfol methane and the like.

[0053] Examples of the β-ketosulfone derivative include 2-cyclohexylcarbo-l 2- (ρ toluenesulfol) propane, 2-isopropylcarboluol 2- (ρ toluenesulfol) propane, and the like.

Disulfone derivatives include diphenyldisulfone derivatives and dicyclohexyldisulfone. And disulfone derivatives such as phon derivatives.

 Examples of nitrobenzyl sulfonate derivatives include -trobenzyl sulfonate derivatives such as p-toluenesulfonic acid 2,6 di-trobenzyl and p-toluenesulfonic acid 2,4 dinitrobenzil.

 Examples of sulfonic acid ester derivatives include 1,2,3 tris (methanesulfo-loxy) benzene, 1,2,3 tris (trifluoromethanesulfonyloxy) benzene, 1,2,3 tris (p-toluenesulfo-loxy) Examples thereof include sulfonic acid ester derivatives such as benzene.

Examples of sulfonic acid ester derivatives of N-hydroxyimide compounds include N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propanesulfone Acid ester, N-hydroxysuccinimide 2-Propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p Methoxybenzene sulfonic acid ester, N-hydroxysuccinimide 2-black ethane sulfonic acid ester, N-hydroxysuccin Midobenzenesulfonic acid ester, N hydroxysuccinimide 2, 4, 6 Trimethylbenzenesulfonic acid ester, N hydroxysuccinimide 1 Naphthalene sulphonic acid ester, N Hydroxyl succinimide 2-Naphthalene sulphonic acid ester, N hydroxy-2-phenol -Rusuccinimide methanesulfonate ester, N-hydroxymaleimide methanesulfonate ester, N-hydroxymaleimide ethanesulfonate ester, N-hydroxy-2-phenolmaleimide methanesulfonate ester, N-hydroxyglutarimide methanesulfonate ester, N Hydroxyglutarimide benzene sulfonate, N Hydroxy phthalimide methane sulfonate, N Hydro phthalimide benzene sulfonate, N Hydro Shifutaruimidoto Riffle O b methanesulfonate ester, N - hydroxyphthalimide p - toluenesulfonate ester, N-hydroxynaphthalimide methanesulfonate ester, N-hydroxynaphthalimide benzenesulfonate ester, N-hydroxy-one 5-norbornene one 2, 3- Examples thereof include dicarboximide methane sulfonate, N-hydroxy-5-norbornene 2,3 dicarboximide trifluoromethane sulfonate, N-hydroxy 5-norbornene-2,3 dicarboximide p-toluene sulfonate, and the like.

 [0055] These acid generators may be used alone or in combination of two or more. The addition amount of the acid generator is 0.1 to 50 parts by mass, and more preferably 0.5 parts by mass and 40 parts by mass with respect to 100 parts by mass of component (A).

 [0056] The method for producing a composition for a resist underlayer film according to the present invention can be obtained by mixing necessary components among the components (A) to (F). The obtained resist underlayer film composition is preferably filtered with a filter.

 [0057] [Method for forming resist underlayer film]

 In order to form a resist underlayer film using the resist underlayer film composition according to the present invention, a spin coater, a slit nozzle coater, etc. are formed on a film to be processed (in some cases, a bottom layer formed on the film to be processed). What is necessary is just to apply | coat using, and to heat after drying. For the heating, one-step heating or a multi-stage heating method can be used. When using the multi-stage heating method, for example, heat at 100 ° C to 120 ° C for 60 seconds, between 120 seconds, between 200 ° C and 250 ° C for 60 seconds to 120 seconds. Is preferred.

 [0058] The thickness of the resist underlayer film thus formed is preferably 15 nm to 200 nm. Thereafter, a resist film composition is provided on the resist underlayer film, for example, with a lOOnm force of 300 nm thickness to produce a resist film.

 [0059] [Pattern Forming Method]

 The resist underlayer film formed from the resist underlayer film composition according to the present invention is preferably used as an intermediate layer of a multilayer resist process such as a three-layer resist process.

Examples of the pattern forming method using the resist underlayer film according to the present invention include the following methods.

[0060] As shown in FIG. 1 (a), the lower layer film composition is applied onto the substrate 20 by using a spin coat method or the like, and beta is formed at a predetermined temperature to form the lower layer film 26 (bottom layer). To do. Then below A resist underlayer film composition is applied onto the layer film 26 by using a spin coating method or the like, and beta is formed at a predetermined temperature to form the resist underlayer film 22. Next, the resist film composition is applied by spin coating or the like in the same manner as described above. Next, pre-beta is performed at a predetermined temperature to form a resist film 24. The pre-beta conditions are 150 ° C to 300 ° C, preferably 30 to 300 seconds! /.

 Next, the resist underlayer film 22 is etched using the resist film 24 with the pattern formed as a mask, and the resist pattern is transferred to the resist underlayer film 22 (see FIG. 1B). Using the resist film 24 and the resist underlayer film 22 as a mask, the underlayer film 26 is etched to transfer the resist pattern to the underlayer film 26 (see FIG. 1C). At this time, the resist film 24 may also be removed by etching at the same time. Next, etching is performed in the same manner as described above to form a pattern on the substrate 20 (see FIG. 1D).

 [0062] Since this lower layer film 26 acts as a mask when the substrate 20 is etched, it is required not to be mixed with the upper resist lower layer film 22 which is desired to have high etching resistance. It is desirable to cross-link with heat or acid after application by the like. Specifically, it is preferable to use a resin such as cresol novolak, naphthol novolak, catol dicyclopentagen novolak, amorphous carbon, polyhydroxystyrene, (meth) atrelate, polyimide, polysulfone or the like.

 [0063] Further, as the resist composition used for forming the resist film 24, for example, a known composition such as a mixture of a base resin, an organic solvent, and an acid generator can be used.

[0064] As the base resin, polyhydroxystyrene and its derivatives, polyacrylic acid and its derivatives, polymethacrylic acid and its derivatives, hydroxystyrene, acrylic acid, metathallic acid and their derivatives are selected. Copolymer, cycloolefin and its derivatives, maleimide, acrylic acid and its derivative power 3 or more kinds of selected copolymers, polynorbornene, and metathesis ring-opening polymer power Group power of 1 or more kinds of polymer polymers selected Can be mentioned. Note that the main skeleton remains after induction, such as acrylic acid ester for acrylic acid derivatives, methacrylic acid ester for methacrylic acid derivatives, and alkoxystyrene for hydroxystyrene derivatives. Means something. [0065] As a resist for a KrF excimer laser, a copolymer of any one of polyhydroxystyrene, hydroxystyrene, and styrene and any one of acrylic acid ester, methacrylic acid ester, and maleimide N carboxylic acid ester Is mentioned. In addition, resists for ArF excimer lasers include acrylic ester, methacrylic ester, alternating copolymer of norbornene and maleic anhydride, alternating copolymer of tetracyclododecene and maleic anhydride, Forces including norbornene and metathesis polymerization by ring-opening polymerization are not limited to these polymerization polymers.

 Example

 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

[0067] [Examples 1 to 5, Comparative Example 1]

 <Preparation of resist underlayer film composition>

 The lower layer of the resist is adjusted with a mixed solvent of propylene glycol monomethyl ether acetate: lactic acid ethyl = 6: 4 so that the total of components (A) to (C) shown in Table 1 below is 2.5% by mass. A film composition was obtained.

 [table 1]

 The abbreviations in Table 1 are as follows, and the “parts” indicate “parts by mass”.

[Chemical 4]

 [Chemical 5]

CCNII

H H Sat.

 [Chemical 6]

 (b-1): Compound of the following formula

CH CH CH C

 • · · (b— 1)

[Chemical 7]

 (b-2): Compound of the following formula

[Chemical 8]

(c 1): Malonic acid [0068] <Resist pattern formation>

 By applying a composition for forming an underlayer film containing novolac resin on a silicon wafer using a conventional resist coater and performing heat treatment at 250 ° C. for 90 seconds, a thickness of 220 nm is obtained. A bottom layer (lower layer film) was formed.

 Next, the resist underlayer film composition of Examples 1 to 5 and Comparative Example 1 described above was applied on the bottom layer, and heat treatment was performed at 250 ° C. for 90 seconds to obtain a thickness of 600 A. A resist underlayer film (450 A in Examples 4 and 5) was formed. Further, a resist composition was applied on the resist underlayer film (antireflection film) to form a resist layer, and exposed and developed with an ArF excimer laser to form a line pattern.

 As resist compositions used in Examples 1 to 5 and Comparative Example 1, those prepared by mixing the following components were used.

[0069] Fatty resin: Fatty resin having a unit represented by the following formula (C1: C2: C3 = 3: 5: 2 (molar ratio), molecular weight 10000): 100 parts by mass

 [Chemical 9]

 Acid generator: compound of the following formula · · · 1. 6 parts by mass

[Chemical 10]

[Chemical 11]

 Acid quencher: Triethanolamine… 0.3 part by mass

 Solvent: Propylene glycol monomethyl ether acetate Z lactate = 8Z2 (mass ratio)

 <Evaluation of resist pattern>

 The shape of the resist pattern formed above was evaluated. This evaluation was performed by observing the pattern and tailing of the resist pattern with SEM. As a result, each of Examples 1 to 5 showed a good pattern shape with reduced tailing in the resist pattern as compared with Comparative Example 1. In particular, Examples 4 and 5 showed particularly good pattern shapes.

Claims

 The scope of the claims

 A resist underlayer film composition comprising a siloxane polymer and a quaternary ammonium compound.

 The resist underlayer film composition according to claim 1, wherein the quaternary ammonium compound is represented by the following general formula (b-1).

 [Chemical 1]

R ²

R ¹ — Ν— R

[In the formula, R ¹ to R ⁴ are each independently a hydrocarbon group and are counter-on. ]

[3] The resist underlayer film composition according to claim 2, wherein the total number of carbon atoms in R ¹ to R ⁴ is 10 or more.

[4] At least one basic force of R ¹ to R ⁴ is a hydrocarbon group having 8 or more carbon atoms, or 2 or

3. The resist underlayer film composition as described in 3.

[5] The resist according to any one of [1] to [4], wherein the content of the quaternary ammonium compound is 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the siloxane polymer. Composition for lower layer film.

 [6] The resist underlayer film composition according to any one of claims 1 to 5, comprising an organic acid.

 [7] The composition for a resist underlayer film according to any one of claims 1 to 6, wherein the siloxane-based polymer has a structural unit represented by the following general formula (a-1).

 [Chemical 2]

[Wherein R ⁵ represents a light-absorbing group, and R. Is a hydrogen atom, hydroxyl group, alkyl having 1 to 6 carbon atoms A group or an alkoxy group, r is 0 or 1; ]

 A resist underlayer film obtained by applying the composition for a resist underlayer film according to any one of claims 1 to 7 and beta-treating at a predetermined temperature.