TW201344369A - Composition for forming resist lower layer film and method for forming pattern - Google Patents

Abstract

A composition for forming a resist underlayer film includes a polysiloxane and a solvent. The solvent includes an organic solvent having a standard boiling point of no less than 150.0 DEG C., and water. A content of the organic solvent is no less than 1% by mass and no greater than 50% by mass with respect to a total amount of the solvent. A content of water is no less than 1% by mass and no greater than 30% by mass with respect to the total amount of the solvent.

Description

Photoresist underlayer film forming composition and pattern forming method

The present invention relates to a composition for forming a photoresist underlayer film and a pattern forming method.

In the fabrication of semiconductor devices, multilayer photoresist processes have been used to achieve high buildup. In the process, a photoresist underlayer film forming composition is first applied onto a substrate to be processed to form a photoresist underlayer film, and a photoresist composition is applied onto the photoresist underlayer film to form a photoresist film. Next, the photoresist film is exposed by a masking pattern such as a reduced projection exposure apparatus (stepper), and is imaged by a suitable developing solution to form a photoresist pattern. Then, the photoresist pattern is used as a mask dry etching photoresist underlayer film, and the obtained photoresist underlayer film pattern is used as a mask to dry-etch the substrate to be processed, thereby forming a desired pattern on the substrate to be processed.

In recent years, in order to further improve the degree of integration, the pattern is made finer, and the structure or the function of the polymer contained in the composition for forming the photoresist underlayer film is also applied to the above-mentioned multilayer photoresist process. Conduct various reviews. The photoresist lower layer film which has been proposed so far is, for example, a composition for forming a photoresist underlayer film containing a hydrolysis condensate of a compound containing a specific hydrolyzable decane compound (see JP-A-2002-40668).

However, in the past, the composition for forming a lower layer film of the photoresist may cause coating defects during the formation of the coating film due to volatilization of the solvent in the nozzle during coating, and hinder the formation of a good photoresist pattern. In addition, the composition for forming a photoresist underlayer film is also required to have excellent storage stability such as an increase in the coating defect or a small change in the film thickness of the obtained coating film even after long-term storage.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2002-40668

The present invention has been made in view of the above-described circumstances, and an object of the invention is to provide a composition for forming a photoresist underlayer film which can form a photoresist underlayer film which is excellent in coating defect suppression property and storage stability.

The present invention for solving the above problems is a composition for forming a photoresist underlayer film, which comprises [A] polyoxoxane and [B] solvent, and [B] solvent contains [B1] standard boiling point of 150.0 ° C or more. Organic solvent (hereinafter also referred to as "[B1] organic solvent"), and [B2] water, [B1] the content of the organic solvent is 1% by mass or more and 50% by mass or less based on the total amount of the [B] solvent, and the [B2] water content is relative to [B] The total amount of the solvent is 1% by mass or more and 30% by mass or less.

[B] The solvent contains the [B1] organic solvent and [B2] water in the above-mentioned specific range. Therefore, when the composition for forming a lower layer film of the photoresist is used, the coating defect suppressing property and the storage stability can be excellent. Photoresist underlayer film. Although the reason why the above-described effects are exhibited by the above-mentioned constitution of the [B] agent is not clear, it is considered that, for example, a [B1] organic solvent containing a high boiling point solvent and a certain amount or more of [B2] water are contained. The solvent volatilization in the nozzle during coating is suppressed, and the occurrence of coating defects is suppressed, and the modification of the stanol group contained in the composition for forming a film under the photoresist is suppressed, and the storage stability and the like are improved.

[B1] The standard boiling point of the organic solvent is preferably 180 ° C or higher. By setting the standard boiling point of the [B1] organic solvent to the above specific range, the photoresist underlayer film forming composition can form a photoresist underlayer film which is more excellent in coating defect suppressing property and storage stability.

The organic solvent of [B1] is preferably at least one selected from the group consisting of esters, alcohols and ethers. When the organic solvent of the [B1] is used as the specific solvent, the photoresist underlayer film forming composition can form a photoresist underlayer film which is more excellent in coating defect suppressing property and storage stability.

As for the [B1] organic solvent, it is preferably a lactone or a carbonate. At least one selected from the group consisting of a compound represented by the following formula (B-1). When the organic solvent of the [B1] is used as the specific solvent, the photoresist underlayer film forming composition can form a photoresist underlayer film which is more excellent in coating defect suppressing property and storage stability.

(In the formula (B-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a mercapto group having 1 to 4 carbon atoms; R ³ is a hydrogen atom or a methyl group, and n is 1 An integer of ~4, when R ³ is a complex number, the plural R ^{3 's} may be the same or different).

[B1] The specific dielectric ratio of the organic solvent is preferably 13 or more and 200 or less. By setting the specific dielectric ratio of the [B1] organic solvent to the above specific range, the photoresist underlayer film forming composition can form a photoresist underlayer film which is more excellent in coating defect suppressing property and storage stability.

[B] The solvent preferably further contains [B3] an alcohol other than [B1] (hereinafter also referred to as "[B3] alcohol"). Thereby, the photoresist underlayer film forming composition can form a photoresist underlayer film which is more excellent in coating defect suppressing property and storage stability.

The composition for forming a photoresist underlayer film preferably further contains a [C] acid diffusion controlling agent. Thereby, the composition for forming a photoresist underlayer film can maintain the above-described effects while suppressing the diffusion of the acid from the photoresist film through the photoresist underlayer film, thereby improving pattern developability and the like.

[A] polyoxyalkylene preferably contains water represented by the following formula (i) A hydrolyzed condensate of a compound of a deuterated decane compound (hereinafter also referred to as "compound (i)").

[Formula ^{_{2] R A a SiX 4-}} a (i)

(In the formula (i), R ^A is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or a cyano group; Some or all of the hydrogen atoms may be substituted by an epoxyalkyloxy group, an epoxy group, an acid anhydride group or a cyano group, and some or all of the hydrogen atoms of the above aryl group may be substituted by a hydroxyl group, and X is a halogen atom. Or -OR ^B , but R ^B is a monovalent organic group, a is an integer of 0 to 3, and when each of R ^A and X is a plural number, the plural R ^A and X may be the same or different.

By using the hydrolysis condensate of the compound containing the compound (i) as the [A] polyoxane, the photoresist underlayer film forming composition can form a photoresist having superior coating defect suppressability and storage stability. Lower film.

The composition for forming a photoresist underlayer film of the present invention can be preferably used for a multilayer photoresist process. The photoresist underlayer film forming product has excellent coating defect suppressing properties and storage stability.

Further, the pattern forming method of the present invention has the steps of: forming a photoresist underlayer film on the substrate to be processed using the photoresist underlayer film forming composition, using a photoresist composition on the photoresist underlayer film Forming a photoresist film a step of irradiating the radiation through the mask, thereby exposing the photoresist film, developing the exposed photoresist film to form a photoresist pattern, and using the photoresist pattern as a mask And the step of sequentially etching the photoresist underlayer film and the substrate to be processed.

In the pattern forming method, since the composition for forming a photoresist underlayer film of the present invention is used, a photoresist underlayer film excellent in coating defect suppressability can be formed. Further, even if the composition for forming a photoresist underlayer film for long-term storage is used, a good pattern can be obtained. Accordingly, the pattern forming method contributes to the formation of a finer pattern on the substrate to be processed.

Here, the "organic group" means a group containing at least one carbon atom. The "specific dielectric ratio" in the present specification means the ratio of the dielectric ratio of the [B1] organic solvent measured at 20 ° C to the dielectric ratio of vacuum. Further, the specific dielectric constant of [B1] organic solvent can be referred to the values described in "Chemical Notes Basic Revision 5". Further, the specific dielectric constant of the [B1] organic solvent which is not found in the above chemical handbook can be measured at 20 ° C according to the method described in JIS C2138.

According to the composition for forming a photoresist underlayer film and the pattern forming method of the present invention, a photoresist underlayer film excellent in coating defect suppressing property and storage stability can be formed. According to this, the composition for forming a photoresist underlayer film can be preferably Used in lithography steps that require more refinement.

<Material for forming a photoresist underlayer film>

The composition for forming a photoresist underlayer film of the present invention may contain [A] polysiloxane and [B] solvent. Further, the photoresist underlayer film forming composition may contain a [C] acid diffusion controlling body as a preferable component. Further, the photoresist underlayer film forming composition may contain other optional components as long as the effects of the present invention are not impaired. Each component is detailed below.

<[A] polyoxane>

[A] Polysiloxane is not particularly limited as long as it has a polymer having a decane bond, but is preferably a hydrolysis condensate of a compound containing a hydrolyzable decane compound represented by the above formula (i). The hydrolyzable decane compound used in the synthesis of [A] polyoxyalkylene may be used singly or in combination of two or more.

In the formula (i), R ^A is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or a cyano group. Some or all of one of the hydrogen atoms of the above alkyl group may be substituted with an epoxyalkyloxy group, an epoxy group, an acid anhydride group or a cyano group. Some or all of one of the hydrogen atoms possessed by the above aryl group may be substituted with a hydroxyl group. X is a halogen atom or -OR ^B . However, R ^B is a monovalent organic group. a is an integer from 0 to 3. When R ^A and X are each plural, the plural R ^A and X may be the same or different.

The alkyl group having 1 to 5 carbon atoms represented by the above R ^A is exemplified by a linear alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group or a n-pentyl group; an isopropyl group and an isobutyl group; a branched alkyl group such as a second butyl group, a tert-butyl group or an isopentyl group. Among these, a linear alkyl group is preferred, and a methyl group is more preferred.

The alkenyl group represented by the above R ^A is exemplified by a group obtained by removing one hydrogen atom from the olefin compound, etc., and is exemplified by a vinyl group, a 1-propen-1-yl group, a 1-propen-2-yl group, and a 1-propene-3. -yl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 1-buten-4-yl, 2-buten-1-yl, 2- Buten-2-yl, 1-penten-5-yl, 2-penten-1-yl, 2-penten-2-yl, 1-hexen-6-yl, 2-hexene-1- Base, 2-hexen-2-yl and the like.

The aryl group represented by the above R ^A is exemplified by, for example, a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group or the like. Among these, a phenyl group and a methylphenyl group are preferred. Further, the above aryl group is a concept comprising an aralkyl group.

The "epoxy group" in the above epoxyalkyloxy group includes an oxiranyl group and an oxetanyl group, and the epoxy group having an alkyl group which may be substituted for the above alkyl group is exemplified by, for example, a glycidyloxy group. Oxecyclobutylmethyloxy and the like.

The epoxy group which may be substituted for the above alkyl group is exemplified by an oxiranyl group and an oxetanyl group.

The acid anhydride group of the above-mentioned alkyl group which may be substituted is exemplified by, for example, a succinic anhydride group, a maleic anhydride group, a glutaric anhydride group or the like.

The alkyl group substituted with glycidyloxy group is exemplified by, for example, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group or the like. More preferably, these are 3-glycidoxypropyl groups.

The above alkyl group substituted with an oxetanylmethyloxy group is exemplified by, for example, 3-ethyl-3-oxetanylmethyloxypropyl group, 3-methyl-3-oxetanylmethyloxypropyl group, 3-ethyl-2-oxetanylmethyloxypropyl, 2-oxetanylmethyloxyethyl and the like. Among these, 3-ethyl-3-oxetanylmethyloxypropyl is preferred.

The alkyl group substituted with an acid anhydride is exemplified by, for example, a 2-succinic anhydride group-substituted ethyl group, a 3-succinic anhydride group-substituted propyl group, a 4-succinic anhydride group-substituted butyl group, and the like. Among these, a propyl group substituted with a 3-succinic anhydride group is preferred.

The above alkyl group substituted with a cyano group is exemplified by, for example, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl or the like.

The above aryl group substituted with a hydroxy group is exemplified by, for example, a 4-hydroxyphenyl group, a 4-hydroxy-2-methylphenyl group, a 4-hydroxynaphthyl group or the like. Among these, a 4-hydroxyphenyl group is preferred.

R ^{A is} preferably an alkyl group or an aryl group.

The halogen atom represented by X above is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.

The above-mentioned monovalent organic group represented by R ^B is exemplified by, for example, an alkyl group, an alkylcarbonyl group or the like. The above alkyl group is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group or a third butyl group, more preferably a methyl group. Further, the above alkylcarbonyl group is preferably a methylcarbonyl group or an ethylcarbonyl group.

R ^{B is} preferably an alkyl group.

As for a, it is preferably an integer of 0 to 2, more preferably 0 or 1.

Specificity of the hydrolyzable decane compound represented by the above formula (i) Examples are phenyl trimethoxy decane, 4-methylphenyl trimethoxy decane, 4-ethyl phenyl trimethoxy decane, 4-hydroxyphenyl trimethoxy decane, 3-methyl phenyl trimethyl Oxydecane, 3-ethylphenyltrimethoxydecane, 3-hydroxyphenyltrimethoxydecane, 2-methylphenyltrimethoxydecane, 2-ethylphenyltrimethoxydecane, 2-hydroxyl An aromatic ring-containing trialkoxy decane such as phenyltrimethoxydecane or 2,4,6-trimethylphenyltrimethoxydecane; methyltrimethoxydecane, methyltriethoxydecane, A Tri-n-propoxy decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, methyl tri-second butoxy decane, methyl tri-t-butoxy decane, methyl Triphenyloxydecane, methyltriethoxydecane, methyltrichlorodecane, methyltriisopropenyloxydecane, methyl cis (dimethylmethoxyoxy)decane, methyl ginseng (methoxyl) Ethoxy)decane, methyl gin (methyl ethyl ketoxime) decane, methyl ginseng (trimethyl decyloxy) decane, methyl decane, ethyl trimethoxy decane, ethyl triethoxy decane Ethyl three Propoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, ethyl tri-second butoxy decane, ethyl tri-t-butoxy decane, ethyl benzene oxychloride Base decane, ethyl ginseng (trimethyl decyloxy) decane, ethyl dichloro decane, ethyl triethoxy decane, ethyl trichloro decane, n-propyl trimethoxy decane, n-propyl three Ethoxy decane, n-propyl tri-n-propoxy decane, n-propyl triisopropoxy decane, n-propyl tri-n-butoxy decane, n-propyl tri-second butoxy decane, n-propyl Tri-t-butoxydecane, n-propyltriphenoxydecane, n-propyltriethoxydecane, n-propyltrichlorodecane, isopropyltrimethoxydecane, isopropyltriethoxy Decane, isopropyl tri-n-propoxy decane, Isopropyl triisopropoxy decane, isopropyl tri-n-butoxy decane, isopropyl tri-second butoxy decane, isopropyl tri-t-butoxy decane, isopropyl triphenyloxide Basear, n-butyltrimethoxydecane, n-butyltriethoxydecane, n-butyltri-n-propoxydecane, n-butyltriisopropoxydecane, n-butyltri-n-butoxydecane, n-Butyl-tert-butoxydecane, n-butyltri-t-butoxydecane, n-butyltriphenoxydecane, n-butyltrichlorodecane, 2-methylpropyltrimethoxydecane , 2-methylpropyltriethoxydecane, 2-methylpropyltri-n-propoxydecane, 2-methylpropyltriisopropoxydecane, 2-methylpropyltri-n-butoxy Decane, 2-methylpropyltri-t-butoxydecane, 2-methylpropyltri-t-butoxydecane, 2-methylpropyltriphenoxydecane, 1-methylpropyl Trimethoxydecane, 1-methylpropyltriethoxydecane, 1-methylpropyltri-n-propoxydecane, 1-methylpropyltriisopropoxydecane, 1-methylpropyltri n-Butoxydecane, 1-methylpropyltri-t-butoxydecane, 1-methylpropyl Tri-t-butoxydecane, 1-methylpropyltriphenoxydecane, tert-butyltrimethoxydecane, tert-butyltriethoxydecane, tert-butyltri-n-propoxydecane , t-butyl triisopropoxy decane, tert-butyl tri-n-butoxy decane, tert-butyl tri-second butoxy decane, tert-butyl tri-tert-butoxy decane, An alkyltrialkoxy decane such as tributyltriphenoxydecane, tert-butyltrichlorodecane or tert-butyldichlorodecane; vinyltrimethoxydecane, vinyltriethoxydecane, Vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-second butoxy decane, vinyl tri-t-butoxy decane, ethylene Triphenyloxydecane, allyltrimethoxydecane, Allyl triethoxy decane, allyl tri-n-propoxy decane, allyl triisopropoxy decane, allyl tri-n-butoxy decane, allyl tri-second butoxy decane Alkenyl trialkoxy decanes such as allyl tri-t-butoxy decane, allyl triphenoxy decane, etc.; tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane a tetraalkoxy decane such as tetraisopropoxy decane, tetra-n-butoxy decane, tetra-butoxy decane or tetra-butoxy decane; tetraphenoxy decane or the like Aryl decanes; oxetanyltrimethoxydecane, oxiranyltrimethoxydecane, oxiranylmethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, etc. Alkoxy-containing decanes; 3-(trimethoxydecyl)propyl succinic anhydride, 2-(trimethoxydecyl)ethyl succinic anhydride, 3-(trimethoxydecyl)propyl succinic anhydride An acid anhydride group-containing decane such as 2-(trimethoxydecyl)ethyl succinic anhydride; a tetrahalodecane such as tetrachlorosilane or the like.

Among these, tetramethoxynonane, phenyltrimethoxydecane, 4-methylphenyltrimethoxydecane, and methyltrimethoxydecane are preferred.

In the synthesis of [A] polyoxyalkylene, in addition to the hydrolyzable decane compound represented by the above formula (i), other decane compounds such as hexamethoxydioxane, hexaethoxydioxane, or the like may be used. Phenoxy dioxane, 1,1,1,2,2-pentamethoxy-2-methyldioxane, 1,1,1,2,2-pentaethoxy-2-methyldioxane, 1,1,1,2,2-pentaphenoxy-2-methyldioxane, 1,1,1,2,2-pentamethoxy-2-ethyldioxane, 1,1,1, 2,2-pentaethoxy-2- Ethyldioxane, 1,1,1,2,2-pentaphenoxy-2-ethyldioxane, 1,1,1,2,2-pentamethoxy-2-phenyldioxane, 1 1,1,2,2-pentaethoxy-2-phenyldioxane, 1,1,1,2,2-pentaphenoxy-2-phenyldioxane, 1,1,2,2 -tetramethoxy-1,2-dimethyldioxane, 1,1,2,2-tetraethoxy-1,2-dimethyldioxane, 1,1,2,2-tetraphenyl oxide 1,2-dimethyldioxane, 1,1,2,2-tetramethoxy-1,2-diethyldioxane, 1,1,2,2-tetraethoxy-1, 2-Diethyldioxane, 1,1,2,2-tetraphenoxy-1,2-diethyldioxane, 1,1,2,2-tetramethoxy-1,2-diphenyl Dioxane, 1,1,2,2-tetraethoxy-1,2-diphenyldioxane, 1,1,2,2-tetraphenoxy-1,2-diphenyldioxane, 1,1,2-trimethoxy-1,2,2-trimethyldioxane, 1,1,2-triethoxy-1,2,2-trimethyldioxane, 1,1,2 -Triphenoxy-1,2,2-trimethyldioxane, 1,1,2-trimethoxy-1,2,2-triethyldioxane, 1,1,2-triethoxy -1,2,2-triethyldioxane, 1,1,2-triphenoxy-1,2,2-triethyldioxane, 1,1,2-trimethoxy-1,2, 2-triphenyldioxane, 1,1,2-triethoxy-1,2,2-triphenyldioxane, 1,1,2-triphenoxy-1,2,2-tri Phenyldioxane, 1,2-dimethoxy-1,1,2,2-tetramethyldioxane, 1,2-diethoxy-1,1,2,2-tetramethyldioxane 1,2-Diphenoxy-1,1,2,2-tetramethyldioxane, 1,2-dimethoxy-1,1,2,2-tetraethyldioxane, 1,2 -diethoxy-1,1,2,2-tetraethyldioxane, 1,2-diphenoxy-1,1,2,2-tetraethyldioxane, 1,2-dimethoxy 1,2-,2,2-tetraphenyldioxane, 1,2-diethoxy-1,1,2,2-tetraphenyldioxane, 1,2-diphenoxy-1, 1,2,2-tetraphenyldioxane, bis(trimethoxydecyl)methane, bis(triethoxydecyl)methane, bis(tri-n-propoxydecyl)methane, bis(triisopropyl) Oxyalkylene Alkane, bis(tri-n-butoxydecylalkyl)methane, bis(tri-t-butoxydecylalkyl)methane, bis(tri-t-butoxydecylalkyl)methane, 1,2-bis(trimethoxy) Base alkyl)ethane, 1,2-bis(triethoxydecyl)ethane, 1,2-bis(tri-n-propoxydecyl)ethane, 1,2-bis(triisopropoxy) Ethylene alkyl)ethane, 1,2-bis(tri-n-butoxydecyl)ethane, 1,2-bis(tri-t-butoxydecyl)ethane, 1,2-double (three -3 -butoxyalkylalkyl)ethane, 1-(dimethoxymethyldecyl)-1-(trimethoxydecylalkyl)methane, 1-(diethoxymethyldecyl)-1 -(triethoxydecyl)methane, 1-(di-n-propoxymethyl-decyl)-1-(tri-n-propoxydecyl)methane, 1-(diisopropoxymethyl)alkyl )-1-(triisopropoxydecyl)methane, 1-(di-n-butoxymethyldecyl)-1-(tri-n-butoxydecyl)methane, 1-(di-second) Oxymethylalkylalkyl)-1-(tris-t-butoxydecylalkyl)methane, 1-(di-t-butoxymethyldecyl)-1-(tri-t-butoxydecane) Methane, 1-(dimethoxymethyldecyl)-2-(trimethoxydecyl)ethane, 1- (diethoxymethyl decyl)-2-(triethoxydecylalkyl)ethane, 1-(di-n-propoxymethyl decyl)-2-(tri-n-propoxy decyl)B Alkane, 1-(diisopropoxymethyl decyl)-2-(triisopropoxydecyl)ethane, 1-(di-n-butoxymethyl decyl)-2-(tri-n-butyl) Oxidylalkyl)ethane, 1-(di-t-butoxymethyldecyl)-2-(tri-t-butoxydecyl)ethane, 1-(di-t-butoxy) Methyl nonyl)-2-(tris-tert-butoxydecyl)ethane, bis(dimethoxymethyldecyl)methane, bis(diethoxymethyldecyl)methane, bis ( Di-n-propoxymethyl fluorenyl) methane, bis(diisopropoxymethyl decyl)methane, bis(di-n-butoxymethyl decyl)methane, bis(di-t-butoxyl) Base alkyl)methane, bis(di-t-butoxymethyl) 矽alkyl)methane, 1,2-bis(dimethoxymethyldecyl)ethane, 1,2-bis(diethoxymethyldecyl)ethane, 1,2-bis(di-n-propyl) Oxymethylalkylalkyl)ethane, 1,2-bis(diisopropoxymethyldecyl)ethane, 1,2-bis(di-n-butoxymethyldecyl)ethane, 1, 2-bis(di-t-butoxymethyldecyl)ethane, 1,2-bis(di-t-butoxymethyldecyl)ethane, bis(dimethylmethoxydecyl) Methane, bis(dimethylethoxydecyl)methane, bis(dimethyl-n-propoxydecyl)methane, bis(dimethylisopropoxydecyl)methane, bis(dimethyl Butoxyalkyl)methane, bis(dimethyl- 2,butoxyalkyl)methane, bis(dimethyl-t-butoxydecyl)methane, 1,2-bis(dimethyl Oxyalkylene)ethane, 1,2-bis(dimethylethoxydecyl)ethane, 1,2-bis(dimethyl-n-propoxydecyl)ethane, 1,2-double (dimethylisopropoxydecyl)ethane, 1,2-bis(dimethyl-n-butoxydecyl)ethane, 1,2-bis(dimethyl-second butoxyalkyl) Ethane, 1,2-bis(dimethyl-t-butoxydecyl)B , 1-(dimethoxymethyldecyl)-1-(trimethyldecyl)methane, 1-(diethoxymethyldecyl)-1-(trimethyldecyl)methane, 1 -(di-n-propoxymethyl decyl)-1-(trimethyldecyl)methane, 1-(diisopropoxymethyl decyl)-1-(trimethyldecyl)methane, 1 -(di-n-butoxymethyldecyl)-1-(trimethyldecyl)methane, 1-(di-t-butoxymethyldecyl)-1-(trimethyldecyl)methane , 1-(di-t-butoxymethyldecyl)-1-(trimethyldecyl)methane, 1-(dimethoxymethyldecyl)-2-(trimethyldecyl) Ethane, 1-(diethoxymethyldecyl)-2-(trimethyldecyl)ethane, 1-(di-n-propoxymethyldecyl)-2-(trimethyldecyl) Ethyl, 1-(diisopropoxymethyl decyl)-2-(trimethyldecyl)B Alkane, 1-(di-n-butoxymethyldecyl)-2-(trimethyldecyl)ethane, 1-(di-t-butoxymethyldecyl)-2-(trimethyl)矽alkyl)ethane, 1-(di-t-butoxymethyldecyl)-2-(trimethyldecyl)ethane, 1,2-bis(trimethoxydecyl)benzene, 1, 2-bis(triethoxydecyl)benzene, 1,2-bis(tri-n-propoxydecyl)benzene, 1,2-bis(triisopropoxydecyl)benzene, 1,2-double (tri-n-butoxyalkyl) benzene, 1,2-bis(tri-t-butoxydecyl)benzene, 1,2-bis(tris-tert-butoxydecyl)benzene, 1,3 - bis(trimethoxydecyl)benzene, 1,3-bis(triethoxydecyl)benzene, 1,3-bis(tri-n-propoxydecyl)benzene, 1,3-double (three different) Propyloxyalkyl)benzene, 1,3-bis(tri-n-butoxydecyl)benzene, 1,3-bis(tri-t-butoxydecyl)benzene, 1,3-bis(tri-) Tertiary butoxyalkyl)benzene, 1,4-bis(trimethoxydecyl)benzene, 1,4-bis(triethoxydecyl)benzene, 1,4-bis(tri-n-propoxy)矽alkyl)benzene, 1,4-bis(triisopropoxydecyl)benzene, 1,4-bis(tri-n-butoxydecyl)benzene, 1,4-bis(tri-t-butoxy)矽alkyl)benzene, 1,4- (tris-tert-butoxyalkyl)dioxane such as benzene; polycarbodecane such as polydimethoxymethylcarbane or polydiethoxymethylcarbane; benzyltrimethoxydecane, Phenyltrimethoxydecane, 4-methoxyphenyltrimethoxydecane, 4-phenoxyphenyltrimethoxydecane, 4-aminophenyltrimethoxydecane, 4-dimethylaminobenzene Trimethoxy decane, 4-ethenylaminophenyl trimethoxy decane, 3-methoxyphenyl trimethoxy decane, 3-phenoxyphenyl trimethoxy decane, 3-aminophenyl Trimethoxy decane, 3-dimethylaminophenyl trimethoxy decane, 3-ethyl decyl phenyl trimethoxy decane, 2-methoxyphenyl trimethoxy decane, 2-phenoxy benzene Base three Methoxydecane, 2-aminophenyltrimethoxydecane, 2-dimethylaminophenyltrimethoxydecane, 2-ethenylaminophenyltrimethoxydecane, 4-methylbenzyltrimethyl Oxydecane, 4-ethylbenzyltrimethoxynonane, 4-methoxybenzyltrimethoxydecane, 4-phenoxybenzyltrimethoxydecane, 4-hydroxybenzyltrimethoxydecane, 4 Other decane compounds such as aminobenzyltrimethoxydecane, 4-dimethylaminobenzyltrimethoxydecane, 4-ethenylaminobenzyltrimethoxydecane.

A conventional hydrolysis and condensation method can be used for the method of hydrolyzing and condensing a compound containing the hydrolyzable decane compound represented by the above formula (i) and other decane compound optionally used.

The content of the [A] polyoxane in the composition for forming a photoresist underlayer film is preferably 50% by mass based on the total solid content (the component other than the solvent of [B] solvent) in the composition for forming a photoresist underlayer film. More preferably, it is 55 mass% or more.

The molecular weight (Mw) of polystyrene-equivalent molecular weight (Mw) measured by gel permeation chromatography (GPC) is usually 500 to 50,000, preferably 1,000 to 30,000, more preferably 1,000 to 10,000. 15,000, and even better, 1,000 to 10,000.

In addition, in the Mw system of the present specification, a GPC column (two "G2000HXL", one "G3000HXL" and one "G4000HXL") manufactured by TOSOH Co., Ltd. is used, and a solvent: tetrahydrofuran, a column is eluted at a flow rate of 1.0 ml/min. Temperature: Analysis conditions of 40 ° C, measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.

<[B] Solvent>

[B] The solvent contains a [B1] organic solvent in an amount of 1% by mass or more and 50% by mass or less based on the total amount of the solvent of [B], and the combined dose of the solvent of [B] is 1% by mass or more and 30% by mass. The content below % contains [B2] water. Further, the [B] solvent preferably further contains a [B3] alcohol. Further, the [B] solvent may contain [B4] other solvents in addition to the [B1] organic solvent, [B2] water, and [B3] alcohol.

[B1] organic solvent

[B1] The organic solvent is an organic solvent having a normal boiling point of 150.0 ° C or more, and the content thereof is 1% by mass or more and 50% by mass or less based on the total amount of the [B] solvent. By allowing the [B] solvent to contain the [B1] organic solvent in the above specific range, it is possible to suppress the evaporation of the solvent in the nozzle during coating, and to suppress the occurrence of coating defects.

[B1] The standard boiling point of the organic solvent is preferably 160 ° C or higher, more preferably 170 ° C or higher, and still more preferably 180 ° C or higher. By setting the standard boiling point of the [B1] organic solvent to the above range, the solvent volatilization in the nozzle during coating is further suppressed, and the occurrence of coating defects is further suppressed.

[B1] The standard boiling point of the organic solvent is preferably 300 ° C or lower, more preferably 280 ° C or lower, still more preferably 250 ° C or lower, and most preferably 220 ° C or lower.

[B1] The specific dielectric ratio of the organic solvent is preferably from 13 to 200, more preferably from 15 to 150, still more preferably from 20 to 100.

By setting the dielectric constant of the [B1] organic solvent to the above range, the photoresist underlayer film forming composition can form a photoresist underlayer film which is more excellent in coating defect suppressing property and storage stability. By setting the specific dielectric ratio of the [B1] organic solvent to the above range, it is presumed that the stanol group in the [A] polyoxane can be stably present and the condensation reaction can be suppressed.

The [B1] organic solvent having a specific dielectric ratio in the above range is exemplified by, for example, ethyl acetoxyacetate (specific dielectric ratio: 16), N-methylpyrrolidone (specific dielectric ratio: 33), N, N- Dimethylacetamide (specific dielectric ratio: 39), formamide (specific dielectric ratio: 111), N-ethylacetamide (specific dielectric ratio: 135), N-methylacetamide (specific dielectric ratio: 179), decyl alcohol (specific dielectric ratio: 42), propylene carbonate (specific dielectric ratio: 63), ethyl carbonate (specific dielectric ratio: 90), dimethyl adenine (specific dielectric ratio: 47), cyclodextrin (specific dielectric ratio: 42), ethylene glycol (specific dielectric ratio: 41), glycerin (specific dielectric ratio: 47), succinonitrile (specific dielectric ratio) : 63), nitrobenzene (specific dielectric ratio: 36), γ-butyrolactone (specific dielectric ratio: 39), and the like.

[B1] The organic solvent is exemplified by, for example, an ester, an alcohol, an ether, a ketone, a guanamine solvent, or the like.

The above esters are exemplified by, for example, lactones such as β-propiolactone (boiling point: 162 ° C), γ-butyrolactone (boiling point: 204 ° C), γ-valerolactone (boiling point: 207 ° C), γ-ten Monolactone (boiling point: 286 ° C); etc.; carbonates are ethyl carbonate (boiling point: 244 ° C), propyl carbonate (boiling point: 242 ° C), etc.; 3-methoxybutyl acetate (boiling point: 172 ° C), 2-ethyl butyl acetate ( Boiling point: 160 ° C), 2-ethylhexyl acetate (boiling point: 199 ° C), benzyl acetate (boiling point: 212 ° C), cyclohexyl acetate (boiling point: 172 ° C), methylcyclohexyl acetate (boiling point: 201 ° C), n-decyl acetate (boiling point: 208 ° C), ethyl acetate (boiling point: 169 ° C), ethyl acetate (boiling point: 181 ° C), isoamyl propionate (boiling point: 156 ° C) , diethyl oxalate (boiling point: 185 ° C), di-n-butyl oxalate (boiling point: 239 ° C), ethyl lactate (boiling point: 151 ° C), n-butyl lactate (boiling point: 185 ° C), diethyl malonate Ester (boiling point: 199 ° C), dimethyl phthalate (boiling point: 283 ° C), and the like.

The above alcohols are exemplified by, for example, 3-methoxybutanol (boiling point: 157 ° C), n-hexanol (boiling point: 157 ° C), n-octanol (boiling point: 194 ° C), and second octanol (boiling point). : 174 ° C), n-nonanol (boiling point: 215 ° C), n-nonanol (boiling point: 228 ° C), phenol (boiling point: 182 ° C), cyclohexanol (boiling point: 161 ° C), benzyl alcohol (boiling point: 205 ° C Etc.; polyols are ethylene glycol (boiling point: 197 ° C), 1,2-propanediol (boiling point: 188 ° C), 1,3-butanediol (boiling point: 208 ° C), 2,4-pentanediol (boiling point: 201 ° C), 2-methyl-2,4-pentanediol (boiling point: 196 ° C), 2,5-hexanediol (boiling point: 216 ° C), triethylene glycol (boiling point: 165 ° C) Etc. Polyol partial ethers are ethylene glycol monobutyl ether (boiling point: 171 ° C), ethylene glycol monophenyl ether (boiling point: 244 ° C), diethylene glycol monomethyl ether (boiling point: 194 ° C) , diethylene glycol monoethyl ether (boiling point: 202 ° C), triethylene glycol monomethyl ether (boiling point: 249 ° C), diethylene glycol monoisopropyl ether (boiling point: 207 ° C), two ethylene Alcohol monobutyl ether (boiling point: 231 ° C), triethylene glycol monobutyl ether (boiling point: 271 ° C), ethylene glycol monoisobutyl ether (boiling point: 161 ° C), two ethylene Alcohol monoisobutyl ether (boiling point: 220 ° C), ethylene glycol monohexyl ether (boiling point: 208 ° C), diethylene glycol monohexyl ether (boiling point: 259 ° C), ethylene glycol mono 2-ethylhexyl ether (boiling point: 229 ° C), diethylene glycol mono 2-ethylhexyl ether (boiling point: 272 ° C), ethylene glycol monoallyl ether (boiling point: 159 ° C), diethylene glycol monophenyl ether (boiling point : 283 ° C), ethylene glycol monobenzyl ether (boiling point: 256 ° C), diethylene glycol monobenzyl ether (boiling point: 302 ° C), dipropylene glycol monomethyl ether (boiling point: 187 ° C), tripropylene glycol single Methyl ether (boiling point: 242 ° C), dipropylene glycol monopropyl ether (boiling point: 212 ° C), propylene glycol monobutyl ether (boiling point: 170 ° C), dipropylene glycol monobutyl ether (boiling point: 231 ° C), propylene glycol single Phenyl ether (boiling point: 243 ° C) and the like.

The above ethers are exemplified by, for example, diethylene glycol dimethyl ether (boiling point: 162 ° C), triethylene glycol dimethyl ether (boiling point: 216 ° C), diethylene glycol methyl ethyl ether (boiling point: 176) °C), diethylene glycol diethyl ether (boiling point: 189 ° C), diethylene glycol dibutyl ether (boiling point: 255 ° C), dipropylene glycol dimethyl ether (boiling point: 171 ° C), diethylene glycol Monoethyl ether acetate (boiling point: 217 ° C), ethylene glycol monobutyl ether acetate (boiling point: 188 ° C), 1,8-cineole (boiling point: 176 ° C), two different Amyl ether (boiling point: 171 ° C), anisole (boiling point: 155 ° C), ethyl benzyl ether (boiling point: 189 ° C), diphenyl ether (boiling point: 259 ° C), dibenzyl ether (boiling point: 297 ° C), phenylethyl alcohol (boiling point: 170 ° C), dihexyl ether (boiling point: 226 ° C), and the like.

Other [B1] organic solvents are listed as: N-methylpyrrolidone (boiling point: 204 ° C), N,N-dimethylacetamidine (boiling point: 165 ° C), formamide (boiling point: 210 ° C), N -ethyl acetamide (boiling Point: 206 ° C), N-methylacetamide (boiling point: 206 ° C), decyl alcohol (boiling point: 162 ° C), propyl carbonate (boiling point: 242 ° C), ethyl carbonate (boiling point: 238 ° C), Dimethyl hydrazine (boiling point: 189 ° C), cyclobutyl hydrazine (boiling point: 287 ° C), glycerin (boiling point: 290 ° C), succinonitrile (boiling point: 265 ° C), nitrobenzene (boiling point: 211 ° C), and the like.

In the above, the [B1] organic solvent is preferably at least one selected from the group consisting of esters, alcohols, and ethers, more preferably from lactones, carbonates, or the following formula (B-1). At least one selected from the group consisting of compounds.

In the above formula (B-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a mercapto group having 1 to 4 carbon atoms. R ³ is a hydrogen atom or a methyl group. n is an integer from 1 to 4. When R ³ is a complex number, the plural R ^{3 's} may be the same or different.

The above alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, and a third butyl group. Base. Among these, a methyl group, an ethyl group, and an isobutyl group are preferred.

The above fluorenyl group having 1 to 4 carbon atoms represented by R ¹ or R ² is exemplified by, for example, an ethyl group, a propyl group, a butyl group or the like. Among these, it is preferred to use an ethyl group.

[B1] The organic solvent is preferably ethylene glycol acetate or butyl digan Alcohol acetate, isopropyl diglycol, butyl diglycol, isobutyl diglycol, hexane diol, 2-ethyl hexane diol, phenyl glycol, phenyl diglycol, methyl Propyl triethylene glycol, propyl propyl diglycol, phenyl propylene glycol, dimethyl triethylene glycol, methyl acetate, ethyl acetate, γ-butyrolactone, ethyl carbonate, carbonic acid Propyl propyl ester, propylene glycol, dimethyl hydrazine, n-hexanol, ethyl acetate, γ-butyrolactone, dimethyl hydrazine, n-hexanol are preferred.

Further, the [B1] organic solvent may be used in combination of two or more kinds. [B1] The content of the organic solvent is from 1% by mass to 50% by mass based on the total amount of the solvent of [B], preferably from 1.5% by mass to 30% by mass, more preferably from 2.0% by mass to 20% by mass. More preferably, it is 3.0% by mass or more and 15% by mass or less. By setting the content of the [B1] organic solvent in the solvent of the [B] to the above range, drying of the resist underlayer film forming composition in the nozzle can be further suppressed, and generation of coating defects can be further suppressed.

[B2] water

[B] The solvent contains [B2] water. [B2] The content of water is 1% by mass or more and 30% by mass or less based on the total amount of the [B] solvent. By making the [B] solvent contain the [B2] water in the above specific range, the storage stability of the composition for forming a photoresist underlayer film can be improved. The reason why the storage stability of the resist underlayer film forming composition is improved by the [B] solvent containing the above-mentioned specific range of [B2] water is not clear, but it is considered that the formation of the resist underlayer film is suppressed. Since the stanol group contained in the composition is deteriorated, it is not easy to cause a change in film thickness over time.

[B2] The content of water relative to the total amount of [B] solvent is preferably 1.0% by mass or more and 25% by mass or less, more preferably 1.5% by mass or more and 20% by mass or less, more preferably 2.0% by mass or more and 15% by mass or less, and most preferably 2.5% by mass or more and 12% by mass or less. By setting the content of [B2] water in the solvent of [B] to the above specific range, the storage stability of the composition for forming a photoresist underlayer film can be further improved.

In addition, the content of [B2] water is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, and more preferably 0.3 parts by mass or more based on 1 part by mass of the [B1] organic solvent. 3 parts by mass or less, preferably 0.5 parts by mass or more and 2 parts by mass or less.

<[B3]Alcohols>

[B3] Alcohols are alcohols having a standard boiling point of less than 150.0 °C. By subjecting the [B] solvent to further contain [B3] alcohol, the [B3] alcohol is bonded to the stanol group of [A] polyoxyalkylene to inhibit deterioration of the stanol group. Thereby, the photoresist underlayer film forming composition can form a photoresist underlayer film which is more excellent in coating defect suppressing property and storage stability.

[B3] The alcohol is exemplified by, for example, a unit alcohol solvent: methanol, ethanol, or n-propanol; and a polyol partial ether solvent is exemplified by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether. , propylene glycol monoethyl ether, propylene glycol monopropyl ether; and the like.

Among these, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether are preferred.

The content of the alcohol (B3) is preferably 0% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less based on the total amount of the [B] solvent. By making the content of the [B3] alcohol into the above range, the solubility of the [A] polyoxane to the [B] solvent can be further improved. Further, these [B3] alcohols may be used in combination of two or more kinds.

<[B4] Other Solvents>

The solvent [B] may contain [B4] other solvents in addition to the [B1] organic solvent, [B2] water, and [B3] alcohol. [B4] Other solvents are listed, for example, ethers are diethyl ether, tetrahydrofuran; aromatic hydrocarbons are benzene, toluene, xylene; ketones are acetone, methyl ethyl ketone, methyl n-propyl Ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, cyclopentanone, 2,4-pentanedione; esters are methyl acetate, ethyl acetate, propyl acetate, acetic acid Butyl ester, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.

Among these, esters are preferred, and propylene glycol monomethyl ether acetate is more preferred.

[B4] The content of the other solvent is preferably 30% by mass or more and 90% by mass or less based on the total amount of the [B] solvent. Further, [B4] other solvents may be used in combination of two or more.

<[C] Acid Diffusion Control Body>

The composition for forming a photoresist underlayer film preferably contains [C] acid diffusion control body. The [C] acid diffusion controller is a phenomenon in which the acid generated from the photoresist film is diffused by the photoresist underlayer film by exposure, and the effect of suppressing a poor chemical reaction in the unexposed portion of the photoresist film is exhibited. The form of the [C] acid diffusion controlling agent in the composition for forming a photoresist underlayer film may be a compound form as described later (hereinafter also referred to as "[C] acid diffusion controlling agent") or as a polymer. The form in which a part is incorporated may also be in the form of both.

The [C] acid diffusion controlling agent is exemplified by, for example, an amine compound, a guanamine group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like. Among these, a compound containing a guanamine group is preferred.

The above amine compounds are exemplified by, for example, mono(cyclo)alkylamines; di(cyclo)alkylamines; tri(cyclo)alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3 -aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl) )-2-(4-hydroxyphenyl)propane, 1,4-bis(1-(4-aminophenyl)-1-methylethyl)benzene, 1,3-bis(1-(4- Aminophenyl)-1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, 1-(2-hydroxyethyl) 2-imidazolidinone, 2-quinoxalinol, N,N,N',N'-indole (2-hydroxypropyl)ethylenediamine, N,N,N',N",N"-five Methyl diethylenetriamine and the like.

The above-mentioned amine group-containing compound is exemplified by, for example, an amine compound containing N-tert-butoxycarbonyl group, an amine compound containing N-third pentyloxycarbonyl group, formamide, N-methylformamide, N, N-dimethylformamide, B Indoleamine, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-ethinyl-1-adamantyl Amine, isocyanuric acid ginseng (2-hydroxyethyl) ester, and the like. Preferably, the amine compound containing N-tert-butoxycarbonyl group or the amine compound containing N-third pentyloxycarbonyl group is more preferably N-tert-butoxycarbonyl-4-hydroxypiperidine. N-Tertiaryoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonyl-2-carboxy-4-hydroxypyrrolidine, N-tert-butoxycarbonyl-2-carboxypyrrolidine.

The above urea compounds are exemplified by, for example, urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenyl. Urea, tri-n-butyl thiourea, and the like.

Examples of the nitrogen-containing heterocyclic compound include imidazoles such as 2-phenylimidazole; pyridines; piperazines and the like.

Further, as the [C] acid diffusion controlling agent, an onium salt compound which decomposes by exposure and loses alkali which is an acid diffusion controlling property can also be used. The onium salt compound is, for example, an onium salt compound represented by the following formula (2-1), an onium salt compound represented by the formula (2-2), and the like.

In the above formula (2-1) and formula (2-2), R ⁴ to R ⁸ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom. Anb ^- is OH ^- , R ⁹ -COO ^- , R ⁹ -SO ₃ ^- or an anion represented by the following formula (3). R ^{9 is} each independently an alkyl group, an aryl group or an alkanol group.

The above onium salt compound and onium salt compound are exemplified by, for example, triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylphosphonium hydroxide, diphenyl 4-hydroxyphenylindole acetate, diphenyl-4-hydroxyphenylhydrazine salicylate, bis(4-t-butylphenyl)phosphonium hydroxide, bis(4-tert-butylphenyl) ) hydrazine acetate, bis(4-t-butylphenyl)hydrazine salicylate, bis(4-t-butylphenyl)phosphonium acetate, bis(4-tert-butylphenyl)hydrazine Salicylate, 4-tert-butylphenyl-4-hydroxyl hydroxide Phenyl phenyl hydrazine, 4-tert-butylphenyl-4-hydroxyphenyl hydrazine acetate, 4-tert-butylphenyl-4-hydroxyphenyl hydrazine salicylate, bis (4-third butyl) Phenyl phenyl) 錪 10 - camphor sulfonate, diphenyl hydrazine 10 - camphor sulfonate, triphenyl sulfonium 10 - camphor sulfonate, 4-tert-butyl phenyl. Diphenylhydrazine 10-camphorsulfonate and the like.

The [C] acid diffusion controlling agent may be used in combination of two or more. The content of the [C] acid-diffusion controlling agent is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass based on the total solid content (components other than the solvent) of the resist underlayer film forming composition. % or more and 10% by mass or less. The pattern development property is further improved by setting the content of the [C] acid diffusion controlling agent to the above range.

<Other optional ingredients>

The composition for forming a photoresist underlayer film may contain other optional components as needed, without impairing the effects of the present invention. Other optional components are exemplified by, for example, a surfactant, a storage stabilizer, and the like.

<Modulation method of composition for forming a photoresist underlayer film>

The composition for forming a photoresist underlayer film is prepared by, for example, mixing [A] polyoxoxane, [C] acid diffusion controlling agent, and optionally any other components in a specific ratio in a solvent [B]. The composition for forming a photoresist underlayer film is preferably used in a state of being dissolved or dispersed in a suitable solvent.

<Form Formation Method>

The pattern forming method of the present invention has the following steps: using the photoresist underlayer film forming composition on a substrate to be processed a step of forming a photoresist underlayer film (hereinafter also referred to as "photoresist underlayer film forming step"), a step of forming a photoresist film on the underlayer film of the photoresist using a photoresist composition (hereinafter also referred to as "resist film" a forming step"), a step of exposing the photoresist film by radiation irradiation (hereinafter also referred to as "exposure step"), and exposing the exposed photoresist film to form a photoresist pattern a step (hereinafter also referred to as "development step"), and a step of sequentially etching the photoresist underlayer film and the substrate to be processed by using the photoresist pattern as a mask (hereinafter also referred to as "dry etching step") ).

In the pattern forming method, since the composition for forming a photoresist underlayer film of the present invention is used, a photoresist underlayer film excellent in coating defect suppressability can be formed. Further, even when the composition for forming a photoresist underlayer film which has been stored for a long period of time is used, a good pattern can be obtained. Accordingly, the pattern forming method contributes to forming a finer pattern on the substrate to be processed.

[Photoresist underlayer film formation step]

In this step, the photoresist underlayer film forming composition is used to form a photoresist underlayer film on the substrate to be processed. The substrate to be processed is, for example, an insulating film such as yttrium oxide, tantalum nitride, yttrium oxynitride or polyoxynitride, and commercially available BLACK DIAMOND (manufactured by AMAT), SILK (manufactured by Dow Chemical Co., Ltd.), and LKD5109 (manufactured by JSR). An interlayer insulating film or the like which is coated with a low dielectric insulating film or the like. Moreover, the substrate to be processed can also use a wiring trench (groove) A patterned substrate such as a pin groove (through hole).

The method for forming the photoresist underlayer film can be formed by coating a surface of, for example, a substrate to be processed or other underlayer film to form a coating film of the composition, subjecting the coating film to heat treatment, or by performing ultraviolet light irradiation. It is formed by hardening by heat treatment. The method of applying the composition for forming a photoresist underlayer film is, for example, a spin coating method, a roll coating method, a dipping method, or the like. Among these, a spin coating method in which the composition for forming a photoresist underlayer film is sprayed by a nozzle is preferred. By using this method, the effects of the present invention can be fully exerted. Further, the heating temperature is usually 50 ° C to 450 ° C, preferably 250 ° C. The heating time is usually from 30 seconds to 1,200 seconds, preferably from 45 seconds to 600 seconds.

Further, another underlayer film (hereinafter also referred to as "other underlayer film") different from the photoresist underlayer film obtained by using the photoresist underlayer film forming composition of the present invention may be formed in advance on the substrate to be processed. The other underlayer film is a film which imparts an antireflection function, a coating flatness, and a high etching resistance to a fluorine-based gas such as CF ₄ . For the other underlayer film, for example, "NFC HM8005" (manufactured by JSR) or "NFC CT08" (manufactured by JSR) can be used.

The film thickness of the photoresist underlayer film is usually 5 nm or more and 200 nm or less, and is preferably 10 nm or more and 100 nm or less in order to improve pattern formability.

[Photoresist film forming step]

In this step, a photoresist composition is formed on the photoresist underlayer film obtained by the above-mentioned photoresist underlayer film formation step using a photoresist composition.

The photoresist composition is exemplified by, for example, a positive or negative chemically amplified photoresist composition containing a photoacid generator, and an alkali-soluble resin and A positive-type photoresist composition composed of a quinone-based sensitizer, a negative-type photoresist composition composed of an alkali-soluble resin and a crosslinking agent, and the like. Further, the above-mentioned photoresist composition can be suitably filtered using a filter having a pore diameter of about 0.2 μm. Further, in the pattern forming method of the present invention, a photoresist composition of a commercially available product may be used as it is.

The method of applying the photoresist composition is not particularly limited, and it can be applied by a conventional method such as a spin coating method. Further, when the photoresist composition is applied, the amount of the applied photoresist composition can be adjusted so that the obtained photoresist film has a specific film thickness.

The photoresist film can be formed by pre-baking a coating film formed by applying the photoresist composition, and volatilizing a solvent (that is, a solvent contained in the photoresist composition) in the coating film. The temperature at the time of prebaking is appropriately adjusted depending on the type of the photoresist composition to be used, but it is preferably from 30 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C. Further, another coating film such as a liquid immersion upper film may be further provided on the surface of the photoresist film. The prebaking time is preferably from 20 seconds to 300 seconds, more preferably from 40 seconds to 150 seconds. The film thickness of the photoresist film is preferably from 5 nm to 500 nm, more preferably from 10 nm to 300 nm.

[Exposure step]

In this step, the photoresist film is exposed by radiation irradiation through a mask.

The radiation used in this step is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, gamma ray, molecular beam, ion beam, etc. depending on the type of acid generator used in the photoresist composition, but Preferably, far ultraviolet rays are better, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (157 nm), Kr ₂ excimer laser light (147 nm), ArKr excimer thunder Light (134 nm), extreme ultraviolet (13.5 nm), and the like.

Further, the exposure method is not particularly limited, and it can be carried out according to a method performed in the formation of a conventional pattern. Also, a liquid immersion exposure method can also be used.

[development step]

In this step, the exposed photoresist film in the above exposure step is developed to form a photoresist pattern.

The developing liquid used in the development can be appropriately selected depending on the kind of the photoresist composition to be used. For the case of a positive-type chemically amplified photoresist composition or a negative-type photoresist composition containing an alkali-soluble resin, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, and ethyl may be used. Amine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Base ammonium, pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-oxime An alkaline aqueous solution such as an alkene. Further, these alkaline aqueous solutions may be appropriately added with a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant.

Further, examples of the negative-type chemically amplified photoresist composition or the negative-type photoresist composition containing an alkali-soluble resin include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia water, and the like. Inorganic alkalis, Primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; dimethylethanolamine An aqueous solution of an alkali such as an alcohol amine such as triethanolamine, a tetramethylammonium hydroxide, a tetraethylammonium hydroxide or a quaternary ammonium salt such as choline, or a cyclic amine such as pyrrole or piperidine.

In this step, after developing with the above developing solution, a specific photoresist pattern corresponding to the mask is formed by washing and drying.

Further, in this step, in order to improve the resolution, the pattern profile, the developability, and the like, it is preferred to perform post-baking before the development (that is, after the exposure in the exposure step). The post-baking temperature is appropriately adjusted depending on the type of the photoresist composition to be used, and is preferably from 50 ° C to 200 ° C, more preferably from 80 ° C to 150 ° C. The post-baking time is preferably from 30 seconds to 300 seconds, more preferably from 40 seconds to 150 seconds.

[dry etching step]

In this step, the photoresist pattern is used as a mask, and the underlayer film and the substrate to be processed are sequentially etched to form a pattern. Dry etching can be performed using a conventional dry etching apparatus. In addition, the gas source in the dry etching depends on the elemental composition of the object to be etched, and a gas containing an oxygen atom such as O ₂ , CO or CO ₂ , an inert gas such as He, N ₂ or Ar, Cl ₂ or BCl _{3 may be used.} A chlorine-based gas, a fluorine-based gas such as CHF ₃ or CF ₄ , a gas of H ₂ or NH ₃ , or the like. Moreover, these gases can also be used in combination.

Moreover, after the processes, there may be a step of removing the photoresist underlayer film remaining on the substrate to be processed.

[Examples]

The invention is described in detail below based on the examples, but the invention is not construed as being limited to the examples. The measurement methods of various physical property values are shown below.

[solid content concentration of solution containing [A] polyoxane]

The solid content concentration (% by mass) of the solution containing [A] polyoxyalkylene was obtained by calcining 0.5 g of a solution containing [A] polyaluminoxane at 250 ° C for 30 minutes, and measuring the mass of the solid component in the solution. Seek.

[Measurement of Mw]

GPC pipe column (G2000HXL: 2, G3000HXL: 1 and G4000HXL: 1) manufactured by TOSOH Co., Ltd., with monodisperse flow rate: 1.0 ml/min, dissolution solvent: tetrahydrofuran, column temperature: 40 °C Polystyrene was measured as a standard by gel permeation chromatography (GPC).

<[A] Synthesis of polyoxyalkylene]

Each monomer used in the synthesis of [A] polyoxyalkylene is shown below.

M-1: tetramethoxydecane (a compound represented by the following formula (M-1))

M-2: phenyltrimethoxydecane (a compound represented by the following formula (M-2))

M-3: 4-methylphenyltrimethoxydecane (a compound represented by the following formula (M-3))

M-4: methyltrimethoxydecane (a compound represented by the following formula (M-4))

[Synthesis Example 1]

0.55 g of oxalic acid was dissolved in 7.66 g of water to prepare an aqueous oxalic acid solution. Next, a cooling tube was attached to a flask in which 12.95 g of the compound (M-1), 5.80 g of the compound (M-2), 3.01 g of the compound (M-3), and 70.03 g of the propylene glycol-1-ethyl ether were placed. A dropping funnel with a prepared aqueous oxalic acid solution was fed. Subsequently, after heating to 60 ° C in an oil bath, an aqueous oxalic acid solution was slowly added dropwise, and the mixture was reacted at 60 ° C for 2 hours. After completion of the reaction, the flask to which the reaction solution was added was allowed to cool, and then set on an evaporator to remove methanol formed by the reaction to obtain 49.2 g of a solution containing polyoxyalkylene (A-1). The solid content concentration in the obtained solution was 10% by mass. Further, the polyoxyalkylene (A-1) had a Mw of 1,500.

[Synthesis Example 2 and Synthesis Example 3]

The polysiloxanes (A-2) and (A-3) were synthesized in the same manner as in Synthesis Example 1, except that the monomers of the types and amounts shown in Table 1 were used. Synthetic The Mw and solid content concentrations of each polyoxyalkylene are shown in Table 1.

<Modulation of Composition for Formation of Photoresist Underlayer Film>

The components other than the [A] polyoxane used for the preparation of the composition for forming the photoresist underlayer film are shown below.

<[B] Solvent>

B1-1: ethyl acetate

(standard boiling point: 180.8 ° C, specific dielectric ratio: 15.9)

B1-2: γ-butyrolactone

(standard boiling point: 204 ° C, specific dielectric ratio: 39)

B1-3: Dimethyl Adenine

(standard boiling point: 189.0 ° C, specific dielectric ratio: 48.9)

B1-4: n-hexanol

(standard boiling point: 157 ° C, specific dielectric ratio: 13.3)

B2: Water

B3-1: Propylene glycol-1-methyl ether

B3-2: Propylene glycol-1-ethyl ether

B3-3: Propylene glycol-1-propyl ether

B4: propylene glycol monomethyl ether acetate

<[C] Acid Diffusion Control Agent>

C-1: N-third pentyloxycarbonyl-4-hydroxypiperidine (compound represented by the following formula (C-1))

C-2: N-t-butoxycarbonyl-4-hydroxypiperidine (compound represented by the following formula (C-2))

C-3: N-t-butoxycarbonyl-2-carboxy-4-hydroxypiperidine (compound represented by the following formula (C-3))

C-4: N-t-butoxycarbonyl-2-carboxypiperidine (compound represented by the following formula (C-4))

[Example 1]

2 parts by weight of (A-1) of [A] polyoxyalkylene, 4.50 parts by mass of (B1-1) as a solvent of [B], 7.00 parts by mass of (B2) water, and 30.00 parts by mass of (B3-1) And (B4) 56.35 parts by mass, and (C-1) 0.05 parts by mass of the [C] acid diffusion controlling agent, a solution was obtained. Next, the solution was filtered through a filter having a pore size of 0.2 μm to prepare a composition for forming a photoresist underlayer film.

[Examples 2 to 16 and Comparative Examples 1 to 2]

In the same manner as in Example 1, except that each component of the type and the content shown in Table 2 was mixed, the composition for forming a resist underlayer film was prepared. Also, "-" indicates that the component is not used.

The composition of each of the photoresist underlayer film formations prepared was evaluated as follows. The results are shown in Table 3.

[Coating defect inhibition at the time of coating film formation]

The composition of each of the resistive underlayer film forming compositions prepared above was applied onto the surface of the tantalum wafer by a spin coating method using an applicator/developer (CLEAN TRACK ACT12, manufactured by Tokyo Electronics Co., Ltd.), and then on a hot plate. The film was dried at 220 ° C for 60 seconds, thereby forming a photoresist underlayer film having a film thickness of 30 nm. Subsequently, the number of coating defects was measured by a surface defect observation apparatus (KLA2800, manufactured by KLA TENCOL). When the number of coating defects was 100 or less, it was evaluated as "?", and when the number of coating defects was 101 or more and 150 or less, it was evaluated as "○", and when the number of coating defects exceeded 150, it was evaluated as "x".

[Evaluation of Storage Stability (1)] (Inhibition of film thickness variation over time)

Each of the photoresist underlayer film forming compositions was applied onto the surface of the tantalum wafer at a number of revolutions of 2,000 rpm for 20 seconds using a spin coater, followed by drying at 250 ° C for 60 seconds on a hot plate to form each light. Block the underlayer film. The film thickness at the 50-point position of each formed underlayer film formed was measured using an optical film thickness meter (UV-1280SE, manufactured by KLA TENCOL), and the average value was determined as the initial film thickness (T0). In addition, each of the photoresist underlayer films was formed in the same manner as described above, and the film thickness was measured in the same manner as described above, and the average value was determined as the film thickness after storage (T). . Next, the difference (T-T0) between the initial film thickness T0 and the film thickness T after storage is obtained, and the ratio [(T-T0)/T0] of the difference magnitude to the initial film thickness T0 is calculated as the film thickness change rate. When the value is 5% or less, the evaluation is "○", and when the value is more than 5%, the evaluation is "△", and when it is more than 8%, the evaluation is "X".

[Evaluation of Storage Stability (2)] (Time-dependent coating defect inhibition)

Each of the photoresist underlayer film forming compositions was applied onto the surface of the tantalum wafer at a number of revolutions of 2,000 rpm for 20 seconds using a spin coater, followed by drying at 250 ° C for 60 seconds on a hot plate, thereby forming Each photoresist underlayer film. The number of coating defects of each of the photoresist underlayer films formed was measured by a surface defect observation apparatus (KLA-2800), and this was used as the initial coating defect number (D0). Further, a composition for forming a lower layer film of each of the photoresists after heating at 40 ° C for one week was used, and a photoresist underlayer film was formed in the same manner as above, and the number of coating defects was measured, and this was used as a post-storage coating. Number of cloth defects (D). Next, the difference (D-D0) between the initial coating defect number D0 and the number of coating defects D after storage is calculated as the number of coating defects increase, and when the value is 100 or less, it is evaluated as "◎", and 101 or more and 200 or less. The time is evaluated as "○", and when it is more than 200, it is evaluated as "X".

[adhesiveness]

Another underlayer film forming material ("NFC HM8005", manufactured by JSR) was applied onto a tantalum wafer by a spin coater, and dried on a hot plate at 250 ° C for 60 seconds, thereby forming another lower layer having a film thickness of 300 nm. membrane. Each of the resist underlayer film forming compositions prepared in the above Examples and Comparative Examples was applied onto the surface of the other underlayer film by a spin coater, and baked at 250 ° C for 60 seconds on a hot plate at 250 ° C to form a film. The underlayer film of each photoresist having a film thickness of 30 nm. Next, a photoresist composition ("ARX2014J", manufactured by JSR) was applied onto each of the photoresist underlayer films, and dried at 90 ° C for 60 seconds to form a photoresist film having a thickness of 100 nm. Next, a liquid immersion upper film forming material ("NFC TCX091-7", manufactured by JSR) was applied onto the formed photoresist film, and dried at 90 ° C for 60 seconds to form a liquid immersion upper film having a film thickness of 30 nm. Subsequently, the substrate was heated at 115 ° C for 60 seconds using an ArF excimer laser irradiation apparatus ("S610C", manufactured by NIKON) under the conditions of 16 mJ/cm ² . Subsequently, it was subjected to development treatment with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to form a line pattern of a line width of 50 nm and a pattern of a spacer pattern. The photoresist pattern formed on the substrate was observed by a scanning electron microscope (SEM). The photo-resist pattern was evaluated as "○" when no image peeling occurred, and the image peeling was evaluated as "×". .

As is understood from the results of Table 3, it is understood that the composition for forming a photoresist underlayer film of the present invention can reduce the number of defects generated when the coating film is formed. Further, the number of defects of the composition for forming a photoresist underlayer film of the present invention is less increased with time, and the film thickness of the underlying photoresist film formed is less with time, so that it is found that the storage stability is excellent. In addition, it is understood that the photoresist underlayer film forming composition of the present invention can form a photoresist underlayer film excellent in adhesion to the photoresist film.

[Industrial availability]

According to the composition for forming a photoresist underlayer film and the pattern forming method of the present invention, a photoresist underlayer film excellent in coating defect suppressing property and storage stability can be formed. Accordingly, the composition for forming a photoresist underlayer film can be preferably applied to a lithography step requiring finer refinement.

Claims (10)

A composition for forming a photoresist underlayer film, comprising [A] polyoxoxane and [B] solvent, and [B] solvent comprising [B1] an organic solvent having a normal boiling point of 150.0 ° C or more, and [B2] water [B1] The content of the organic solvent is 1% by mass or more and 50% by mass or less based on the total amount of the solvent of [B], and the content of water of [B2] is 1% by mass or more based on the total amount of the solvent of [B]. Below mass%. The composition for forming a photoresist underlayer film of claim 1, wherein the [B1] organic solvent has a normal boiling point of 180 ° C or higher. The composition for forming a photoresist underlayer film according to claim 1 or 2, wherein the [B1] organic solvent is at least one selected from the group consisting of esters, alcohols, and ethers. The composition for forming a photoresist underlayer film according to claim 1 or 2, wherein the [B1] organic solvent is at least selected from the group consisting of lactones, carbonates, and compounds represented by the following formula (B-1). One kind, (In the formula (B-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a mercapto group having 1 to 4 carbon atoms; R ³ is a hydrogen atom or a methyl group, and n is 1 An integer of ~4, when R ³ is a complex number, the plural R ^{3 's} may be the same or different). The composition for forming a photoresist underlayer film according to any one of claims 1 to 4, wherein the specific dielectric ratio of the [B1] organic solvent is 13 or more and 200 or less. The composition for forming a photoresist underlayer film according to any one of claims 1 to 5, wherein the [B] solvent further contains [B3] an alcohol other than [B1]. The composition for forming a photoresist underlayer film according to any one of claims 1 to 6, which further comprises a [C] acid diffusion controller. The composition for forming a photoresist underlayer film according to any one of claims 1 to 7, wherein [A] polyoxymethane is a hydrolysis condensate of a compound containing a hydrolyzable decane compound represented by the following formula (i), [ 2]R ^A _a SiX _4-a (1) (In the formula (i), R ^A is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a carbon number of 6 An aryl group or a cyano group of ~20, wherein one or all of the hydrogen atoms of the above alkyl group may be substituted with an epoxy group, an epoxy group, an acid anhydride group or a cyano group, and the hydrogen atom of the above aryl group Some or all of them may be substituted by a hydroxyl group, X is a halogen atom or -OR ^B , but R ^B is a monovalent organic group, a is an integer of 0 to 3, and when R ^A and X are each plural, plural R ^A and X Can be the same or different). The composition for forming a photoresist underlayer film according to any one of claims 1 to 8, which is used in a multilayer photoresist process. A pattern forming method comprising the steps of forming a photoresist underlayer film on a substrate to be processed, using a photoresist underlayer film forming composition according to any one of claims 1 to 9, using a photoresist composition a step of forming a photoresist film on the underlying photoresist film, and irradiating the radiation through the mask to expose the photoresist film to expose the exposed photoresist film to form a photoresist pattern And the step of sequentially etching the photoresist underlayer film and the substrate to be processed by using the photoresist pattern as a mask.