TW201243496A - Membrane-forming composition containing silicon for multilayered resist process and pattern formation method - Google Patents

Abstract

The invention is a film-forming composition containing silicon for a multilayered resist process containing [A] a polysiloxane and [B] an electron receptor. The electron receptor [B] is preferably at least one type of compound selected from the group consisting of quinone compounds, quinodimethane compounds, dibenzofuran compounds, and compounds represented by the following formulas (1-1) and (1-2). Polysiloxane [A] is a product of the hydrolysis and condensation of a compound comprising the silane compound represented by the following formula (2).

Description

201243496 VI. Description of the Invention: [Technical Field] The present invention relates to a method for forming a composition comprising a ruthenium film for a multilayer photoresist process and a pattern for using the composition. [Prior Art] Conventionally, a process of a semiconductor device such as 1C or LSI is microfabricated by using a lithography of a photoresist composition. In recent years, with the high integration of integrated circuits, it has been required to form ultra-fine patterns in the sub-micron range or the quarter-micron range. Therefore, the exposure wavelength can also be seen to change from the g-line to the i-line, the KrF quasi-component, the sub-laser beam, and the short-wavelength of the ArF excimer laser light. For example, the liquid immersion exposure method using the ArF excimer laser light refining technique can form a refinement of 50 nm or less (see Patent Document 1). However, it is expected that a more detailed refinement technique of 30 nrn or less will be required in the future.

For the refinement technique of ArF excimer laser light, for example, EUV lithography (hereinafter also referred to as "EUVL") which uses lithography such as electron beams and X-rays and deep ultraviolet rays having a wavelength of 13.5 nm or less is used as a light source. By using EUVL, a fine pattern of 20 nm hp (half pitch) can be performed. However, with the thinning of the photoresist which is miniaturized, it is expected that it is difficult to obtain sufficient workability in the conventional single layer process (photoresist film + antireflection film + substrate). [Advanced Technical Literature] [Patent Literature]

S-5-201243496 [Patent Document 1] International Publication No. 04/068242 [Draft of the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a pattern collapseable The photoresist pattern excellent in the resistance, the resolution, and the rectangular shape of the pattern shape is particularly a ruthenium-containing film-forming composition for a multilayer photoresist process excellent in the processing property of the multilayer photoresist process. [Means for Solving the Problem] The invention completed to solve the above problems is a ruthenium-containing film-forming composition for a multilayer photoresist process comprising [A] polyoxane and [B] electron acceptor. Since the ruthenium-containing film-forming composition for a multilayer photoresist process of the present invention contains [A] polyoxane and [B] electron acceptor, the photoresist formed on the ruthenium-containing film formed thereby can be improved. The lithography performance of the pattern type collapse resistance, the resolution, and the rectangular shape of the pattern shape. Moreover, such an excellent photoresist pattern can improve the processing performance of the multilayer photoresist process. [B] The electron accepting system has a function of accepting electrons generated by the radiation function in the vicinity of the interface between the formed ruthenium-containing film and the photoresist film. Thereby, the amount of electrons participating in the decomposition of the acid generator or the like in the photoresist composition can be controlled in the vicinity of the interface between the ruthenium-containing film and the photoresist film. As a result, in the vicinity of the interface between the ruthenium-containing film and the photoresist film, the shape of the bottom of the photoresist pattern can be controlled by suppressing the excessive deprotection reaction of the polymer having an acid-dissociable group in the photoresist composition, thereby improving the pattern. The lithography performance of collapse resistance, resolution, and rectangular shape of the shape. By forming such a photoresist pattern having excellent performance in 201243496, in the multilayer photoresist process using the composition, the processing performance in the dry etching of the ruthenium-containing film or the substrate can be improved. Therefore, when a composition is formed by using a ruthenium-containing film in a multilayer photoresist process, excellent processing performance can be exhibited based on a multilayer photoresist process to form a good pattern. The [B] electron acceptor is preferably at least one selected from the group consisting of an anthracene compound, a quinodimethane compound, a dibenzofuran compound, and a compound represented by the following formulas (1-1) and (I-2), respectively. compound of.

(In the formulae (1-1) and (1-2), R1 to R5 are each independently a hydrogen atom, an alkyl group alkoxy group, a hydroxyl group or a halogen atom. The Z· and Q· systems are each independently OH—, Ra-co〇-, ra_so3- or Ra-N_-S02-Rb, RA is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, but some or all of the hydrogen atoms possessed by RA may be substituted. RB is an alkyl group or an aralkyl group, but some or all of the hydrogen atoms of Rb may be substituted by a fluorine atom). According to the bismuth-containing film forming composition for the multilayer photoresist process, the [B] electron acceptor can be appropriately controlled as the specific compound, and the pattern of the formed photoresist pattern can be collapsed. The resolution and the 201243496 pattern shape are more excellent in the shape of the rectangle, which improves the processing performance. [A] Polyoxane is preferably a hydrolysis condensate of a compound containing a decane compound represented by the following formula (2) (hereinafter also referred to as "decane compound (2)"). [Chem. 2] R6aSiX4-a (2) (In the formula (2), 'R6 is a hydrogen atom, a fluorine atom, an alkyl group of a carbon number of 5, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group, an aryl group or an aralkyl group. Substituted by a fluorine atom, an aryl group and an aralkyl group may be substituted. An X-based halogen atom or -OR7. R7 is a monovalent organic group. a is an integer of 0 to 3. However, when R6 and X are plural, respectively, 'R6 of a plural number And X may be the same or different.) When the composition is formed by using the ruthenium-containing film by the multilayer photoresist process, the yttrium-containing film is formed by using the above-mentioned specific structure of [A] polysiloxane to form a salt-blocking photoresist pattern. The rectangular shape of the pattern collapse resistance, the resolution, and the shape of the pattern is more excellent, and the processing performance can be further improved. The ruthenium-containing film-forming composition for the multilayer photoresist process has the above-described characteristics. Therefore, it can be applied to deep ultraviolet ray, X-ray or electron beam exposure. The method for forming the pattern of the present invention (hereinafter also referred to as "formation of the pattern" The method I") has the following steps: (1-1) using a ruthenium-containing film-forming composition for a multilayer photoresist process containing [A] polyoxane and [B] electron acceptor, on the substrate to be processed a step of forming a ruthenium-containing film on the side, (1-2) a step of forming a photoresist film on the ruthenium-containing film using a photoresist composition, -8 - 201243496 (1-3) radiation irradiation between the reticle, a step of exposing the photoresist film, (1-4) developing the exposed photoresist film to form a photoresist pattern, and (1-5) using the photoresist pattern as a mask The step of dry etching the above-mentioned ruthenium-containing film and the substrate to be processed is sequentially performed. According to the formation method I of the pattern, since the composition is formed by using the ruthenium-containing film for the multilayer photoresist process, a photoresist pattern excellent in pattern collapse resistance, resolution, and pattern shape can be formed. This gives excellent processing performance and can form a good pattern on the substrate to be processed. The radiation of the above step (1-3) is preferably deep ultraviolet rays, X-rays or electron rays. In the method of forming the pattern I, the composition for forming a multilayer film for a photoresist having the above properties is used. Therefore, when such radiation is used, the effect is more effective and a more favorable pattern is formed. Further, a method of forming another pattern of the present invention (hereinafter also referred to as "formation method II") has the following steps: (Π-1) using a multilayer photoresist containing [A] polyoxyalkylene oxide a step of forming a composition containing a ruthenium film in the process, forming a ruthenium-containing film on the upper surface side of the substrate to be processed, and (II-2) using a photoresist composition to form a photoresist film on the ruthenium-containing film, (Π- 3) a step of exposing the photoresist film to a deep ultraviolet ray or an electron beam, and exposing the photoresist film to the exposed photoresist film to form a photoresist pattern, and -9- 201243496 (II-5) The step of dry etching the above-mentioned ruthenium-containing film and substrate to be processed is carried out using the above-mentioned photoresist pattern as a mask. According to the formation method II of the pattern, a composition for forming a ruthenium-containing film for a multilayer photoresist process containing [Α] polysiloxane is used, and by using the above specific radiation, a pattern collapse can be formed by a multilayer photoresist process. A photoresist pattern excellent in resistance and resolution makes it possible to exhibit excellent processing properties and form a good pattern on the substrate to be processed. The term "organic group" means a group containing at least one carbon atom. [Effect of the Invention] As described above, according to the method for forming a ruthenium-containing film-forming composition and a pattern for a multilayer photoresist process of the present invention, pattern collapse resistance, resolution, and rectangular shape of a pattern can be formed. The photoresist pattern with excellent lithography performance, with such excellent photoresist pattern, can exhibit excellent processing performance, and can form a good pattern on the substrate to be processed. Therefore, the present invention is very suitable for the process of semiconductor devices which are increasingly miniaturized in the future, and is also very suitable for a multilayer photoresist process which is finer than 50 nm. [Mode for Carrying Out the Invention] <The ruthenium-containing film-forming composition for a multilayer photoresist process> The ruthenium-containing film-forming composition for a multilayer photoresist process contains [A] polysiloxane and [B] electron acceptor. Further, the ruthenium-containing film-forming composition for a multilayer photoresist process may contain a solvent [C] as an appropriate component, and may contain other optional components within a range that does not impair the effects of the present invention. Each component is described below. -10-201243496 &lt;[A] Polyoxane&gt; [A] Polyoxane is not particularly limited in structure, but is preferably a hydrolysis condensation of a compound containing a decane compound represented by the above formula (2). Things. By using such [A] polyoxyalkylene, the pattern collapse resistance, the resolution, and the rectangular shape of the pattern shape can be improved. In the above formula (2), the R6 hydrogen atom and the fluorine atom are used. An alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group, an alkenyl group, an aryl group or an aralkyl group. This alkyl group may be substituted by a fluorine atom, and an aryl group and an aralkyl group may be substituted. X is a halogen atom or -OR7. R7 is a monovalent organic group. a is an integer from 0 to 3. However, when R6 and X are complex numbers, respectively, R6 and X of the plural numbers may be the same or different. The alkyl group having 1 to 5 carbon atoms represented by the above R6, for example, a linear alkyl group such as a methyl group, an ethyl group, a η-propyl group, an n-butyl group or a η-pentyl group; an isopropyl group or a different group; a branched alkyl group such as a butyl group, a sec-butyl group, a t-butyl group or an isopentyl group. The fluorenyl group having 1 to 5 carbon atoms which is substituted by a fluorine atom represented by the above R6, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, Gas ethyl, peroxy η-propyl, hexaoxyisopropyl, perfluorobutyl, and the like. The cyanoalkyl group represented by the above R6 may, for example, be a cyanoethyl group, a propylidene group or the like. The alkylcarbonyloxy group represented by the above R6 may, for example, be a methyl methoxy group, an ethyl carbonyloxy group, a propylcarbonyloxy group or a butylcarbonyloxy group.

C 201243496 is a group represented by the following formula (i-1), for example, a rare group which is represented by the above R6. CH2 = CH-(CH2)n.* (i-1) In the above formula (i-1), η is an integer of 0 to 4. * indicates a bond β. The above η is preferably 〇 or 1', more preferably 〇 (vinyl). The aryl group represented by the above R6 may, for example, be a phenyl 'naphthyl group, a methylphenyl group or an ethylphenyl group. The aralkyl group represented by the above R6 may, for example, be a benzyl group, a phenylethyl group, a phenylpropyl group or a naphthylmethyl group. The substituent of the above aryl group and aralkyl group is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro 'alkoxy group, an aryloxy group or an anthracene group. A group, an amine group, a substituted amine group, and the like. The halogen atom represented by the above X may, for example, be a fluorine atom, a chlorine atom or the like. The monovalent organic group represented by R7 in the above -OR7, for example, a carbon number such as a methyl group, an ethyl group, an η-propyl group, an isopropyl group, an η-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group or the like 1 to 4 alkyl groups, etc. The above a is preferably an integer of 〇~2. Specific examples of the decane compound (2) are phenyltrimethoxydecane 'benzyltrimethoxydecane, phenethyltrimethoxylate, 4-methylphenyltrimethoxyanthracene, 4-ethylphenyl Trimethoxydecane, 4-methoxyphenyltrimethoxydecane, 4-phenoxyphenyltrimethoxylate, 4-hydroxyphenyltrimethoxylate, 4-aminophenyltrimethoxy Decane, 4-dimethylaminophenyltrimethoxydecane, 4-ethoxymethylamino-12-201243496 phenyltrimethoxydecane, 3-methylphenyltrimethoxydecane, 3-ethylbenzene Trimethoxy decane, 3-methoxyphenyl trimethoxy decane, 3-phenoxyphenyl trimethoxy decane, 3-hydroxyphenyl trimethoxy decane, 3-aminophenyl trimethoxy decane , 3-dimethylaminophenyltrimethoxydecane, 3-ethenylaminophenyltrimethoxydecane, 2-methylphenyltrimethoxydecane, 2-ethylphenyltrimethoxydecane , 2-methoxyphenyl trimethoxy decane, 2-phenoxyphenyl trimethoxy decane, 2-hydroxyphenyl trimethoxy decane, 2-aminophenyl trimethoxy decane, 2-dimethyl Amino group Trimethoxy decane, 2-ethenylaminophenyl trimethoxy decane, 2,4,6-trimethylphenyltrimethoxydecane, 4-methylbenzyltrimethoxydecane, 4-B Benzyltrimethoxydecane, 4-methoxybenzyltrimethoxydecane, 4-phenoxybenzyltrimethoxydecane, 4-hydroxybenzyltrimethoxydecane, 4-aminobenzyltrimethoxy An aromatic ring-containing trialkoxy decane such as decane, 4-dimethylaminobenzyltrimethoxydecane, 4-ethlylaminobenzyltrimethoxydecane, etc.; Methyl triethoxylate, methyl tri-n-propoxydecane, methyl tri-i-propoxydecane, methyl tri-n-butoxydecane, methyl tri-sec-butoxy Decane, methyltri-t-butylidene decane, methyldiphenoxylate, methyltriethoxylate, methyltrichloromethane, methyltriisopropenyloxydecane, methyl Ginseng (dimethyl decyloxy) decane, methyl ginseng (methoxyethoxy) decane, methyl gin (methyl ethyl ketoxime) decane, methyl ginseng (trimethyl decyloxy) decane, Methyl decane., ethyl trimethoxy samarium , ethyl triethoxy cerium, ethyl tri-n-propoxy sulphate, ethyl-1-propoxy cerium, ethyl di-n-butoxy sand, ethyl three _sec_ Butoxy decane, ethyl tri-t-butoxy decane, ethyl triphenoxy decane,

C -13- 201243496 Ethyl double ginseng (trimethyldecyloxy) decane, ethyl dichlorodecane, ethyl triethoxy decane, ethyl trichloro decane, η-propyl trimethoxy decane, n -propyltriethoxydecane, η-propyltri-n-propoxydecane, η-propyltri-i-propoxydecane' η-propyltris-n-butoxydecane, η- Propyltris-sec-butoxydecane, η-propyltri-t-butoxydecane, η-propyltriphenoxydecane, η-propyltriethoxydecane, η-propyltri Chlorodecane, i-propyltrimethoxydecane, i-propyltriethoxydecane, i-propyltri-n-propoxydecane, i-propyltri-i-propoxydecane, i- Propyltri-n-butoxydecane, i-propyl tris-sec-butoxydecane, i-propyltri-t-butoxydecane, i-propyltriphenoxydecane, η-butyl Trimethoxy decane, η-butyl triethoxy decane, η-butyl tri-η-propoxy decane, η-butyl tris-propoxy decane, η-butyl tri-n-butoxy Baseline, η-butyltris-sec-butoxydecane, η-butyltri-t-butoxydecane, η-butyltriphenoxydecane, η-butyltrichlorodecane' 2- Propyltrimethoxydecane '2-methylpropyltriethoxydecane, 2-methylpropyldi-n-propoxylate' 2- 2 -methylpropyltri-i-propoxylate Alkane, 2-methylpropyltri-n-butoxydecane, 2-methylpropyltris-sec-butoxydecane'2-methylpropyltri-t-butoxydecane, 2-methyl Propyltriphenoxydecane, 1-methylpropyltrimethoxydecane, 1-methylpropyltriethoxydecane, 1-methylpropioniumtris-n-propoxydecane, 1-methyl Propyltri-i-propoxydecane, 1-methylpropyltris-n-butoxydecane, 1-methylpropyltris-butoxybutane, 1-methylpropyltri-- T-butoxydecane, 1-methylpropyltriphenoxydecane, t-butyltrimethoxydecane, t-butyltriethoxydecane, t-butyltris-n-propoxydecane , t-butyltri-i-propoxydecane, t-butyldi-n-butoxylate, t-butyltris-sec-butoxy fluorene, t- -14- 201243496 butyl Alkylenetrialkyloxydecanes such as tris-t-butoxydecane, t-butyltriphenoxydecane, t-butyltrichlorodecane, t-butyldichlorodecane; vinyltrimethoxy Decane, ethylene Triethoxy decane, vinyl tri- η-propoxy decane, vinyl tri-i-propoxy decane, vinyl tri-n-butoxy decane, vinyl tri-sec-butoxy decane, Vinyl tri-t-butoxydecane, vinyltriphenoxydecane, allyltrimethoxydecane, allyltriethoxydecane,allyltri-n-propoxydecane, allyl Tris-i-propoxydecane, allyl tri-n-butoxydecane, allyl tri- sec-butoxydecane, allyl tri-t-butoxydecane, allyl tri Alkenyl trialkoxy decanes such as phenoxydecane; tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy a tetraalkoxy decane such as decane, tetra-sec-butoxy decane or tetra-tert-butoxy decane; tetraphenoxynonane, tetrachlorodecane or the like. Among them, from the viewpoints of reactivity and ease of use of the substance, phenyltrimethoxydecane, 4-methylphenyltrimethoxydecane, 4-methoxyphenyltrimethoxydecane, 4-methyl are preferable. Benzyltrimethoxydecanemethyltrimethoxydecane, methyltrimethoxydecane, methyltriethoxydecane,methyltri-n-propoxydecane,methyltri-i-propoxydecane 'Methyl tri-n-butoxy decane, methyl tri-sec-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl tri- η-propoxy decane, ethyl Tri-i-propoxydecane, ethyltri-n-butoxydecane, ethyltris-sec-butoxydecane, η-propyltrimethoxydecane, n-propyltriethoxydecane, N_propyltris-n-propoxydecane, η-propyltri-i-propoxydecane, η-propyltris-n-butoxy-15- 201243496 矽 、, η-propyl tri Sec_butoxylate, Ethylene trimethoxy sand, vinyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, more preferably phenyl trimethoxy Decane. Further, from the viewpoint of obtaining a pattern excellent in dry etching resistance, tetramethoxynonane or tetraethoxysilane is more preferable, and tetramethoxynonane is more preferable. The decane compound for [A] polyoxyalkylene is obtained, and if necessary, in addition to the compound (2), for example, other decane compounds such as hexamethoxydisceane, hexaethoxydioxane or hexaphenoxy are available. Decane, 1,1,1,2,2-pentamethoxy-2.methyldioxane, i,l,l,2,2-pentaethoxy-2-methyldioxane, 1,1, 1,2,2-pentaphenoxy-2-methyldioxane, 1,1,1,2,2-pentamethoxy-2-ethyl dioxane, 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, M,l,2,2-pentaphenoxy-2-phenyldioxane, 1, 1,2,2-tetramethoxy-1,2-dimethyldioxane, 1,1,2,2-tetraethoxy-1,2-dimethyldioxane, M, 2,2- Tetraphenoxy-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 -diphenyldioxane, i,l,2,2-four Oxy-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-triphenyloxy-1,2,2-tri Methyldioxane, 1,1,2-trimethoxy-1,2,2-triethyldioxane, 1,1,2-triethoxy-1,2,2 • triethyldioxane, 1,1,2-triphenoxy-1,2,2-triethyldi-16- 201243496 decane, 1,1,2-trimethoxy-1,2,2-triphenyldioxane, 1 1,2-triethoxy-1,2,2-triphenyldioxane, 1,1,2-triphenoxy-1,2,2-triphenyldioxane, 1,2-di Methoxy-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-1,1,2,2- 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(tri-i- Propoxydecylalkyl)methane, bis(tris-η-butoxydecylalkyl)methane, bis(tri-sec-butoxydecyl)methane, bis(tri-t-butoxydecyl)methane, 1,2-bis(trimethoxydecyl)ethane, 1,2-bis(triethoxydecyl)ethane, 1,2-bis(tri-n-propoxydecyl)ethane, 1,2-bis(tri-i-propoxydecyl)ethane, 1,2-bis(tris-n-butoxydecyl)ethane, 1,2-bis(tri-sec-butoxy) Base alkyl)ethane, 1,2-bis(tris-t-butoxydecyl)ethane, 1-(dimethoxymethyldecyl)-1-(trimethoxydecyl)methane, 1-(Diethoxymethyldecyl)-1-(triethoxydecyl)methane, 1-(di-η-propoxymethylindolyl)-1-(tri-n-propoxy) Base alkyl)methane, 1-(di-i-propoxymethyl decyl)-1-(tri-i-propoxydecyl)methane, 1-(di-n-butoxymethyl decane Base)-1-(three-η- Butoxyalkyl)methane, 1-(di-sec-butoxymethyldecyl)-1-(tris-butoxybutanyl)methane, 1-(di-t-butoxymethyl) Base alkyl)-1-(tri-t-butoxydecane)methane, 1-(dimethoxymethyl)

C -17- 201243496 矽alkyl)-2-(trimethoxydecyl)ethane, 1-(diethoxymethyldecyl)-2-(triethoxydecyl)ethane, 1- (di-η-propoxymethyl fluorenyl)-2-(tri-n-propoxydecyl)ethane, 1-(di-i-propoxymethyl fluorenyl)-2-(three -i-propoxydecylalkyl)ethane, 1-(di-η-butoxymethyldecyl)-2-(tri-n-butoxydecyl)ethane, 1-(di-sec -butoxymethyl decyl)-2-(tri-sec-butoxy decyl)ethane, 1-(di-t-butoxymethyl decyl)-2-(tri-t-butyl) Oxidylalkyl)ethane; bis(dimethoxymethyldecyl)methane, bis(diethoxymethyldecyl)methane, bis(di-n-propoxymethyldecyl)methane, Bis(di-i-propoxymethyldecyl)methane, bis(di-n-butoxymethyldecyl)methane, bis(di-sec-butoxymethyldecyl)methane, bis ( Di-t-butoxymethyl decyl)methane, 1,2-bis(dimethoxymethyl decyl)ethane, 1,2-bis(diethoxymethyl decyl)ethane, 1,2-bis(di-η-propoxy) Methyl decyl) ethane, 1,2-bis(di-i-propoxymethyl decyl)ethane, 1,2-bis(di-n-butoxymethyl decyl)ethane, 1,2-bis(di-sec-butoxymethyldecyl)ethane, 1,2-bis(di-t-butoxymethyldecyl)ethane, bis(dimethylmethoxy) Base alkyl)methane, bis(dimethylethoxydecyl)methane, bis(dimethyl-η-propoxydecylalkyl)methane, bis(dimethyl-i-propoxydecylalkyl)methane , bis(dimethyl-η-butoxydecyl)methane, bis(dimethyl-sec-butoxydecyl)methane, bis(dimethyl, yl-t-butoxydecyl)methane, 1,2-bis(dimethylmethoxydecyl)ethane, 1,2-bis(dimethylethoxydecyl)ethane, 1,2-bis(dimethyl-η-propoxy) Base alkyl) ethane, 1,2-bis(dimethyl-i-propoxydecyl)ethane, 1,2-bis(dimethyl-η-butoxydecyl)ethane, 1 , 2-bis(dimethyl-sec-butoxydecane-18-201243496)ethane, 1,2-bis(dimethyl-t-butoxydecyl)ethane; 1-(dimethyl oxygen Methyl decyl)-1-(trimethyldecyl)methane, 1-(diethoxymethyldecyl)-1-(trimethyldecyl)methane, 1-(di-η-propoxy) Methyl decyl)-1-(trimethyldecyl)methane, 1-(di-i-propoxymethyl decyl)-1-(trimethyldecyl)methane, 1-(di- η-Butoxymethyl decyl)-1-(trimethyldecyl)methane, 1-(di-sec-butoxymethylalkyl)-1-(trimethyldecyl)methane, 1 -(Di-t-butoxymethyldecyl)-1-(trimethyldecyl)methane,! -(dimethoxymethyldecyl)-2-(trimethyldecyl)ethane, 1-(diethoxymethyldecyl)-2-(trimethyldecyl)ethane, 1 -(di-η-propoxymethyl fluorenyl)-2-(trimethyldecyl)ethane, 1-(dipropylpropoxymethyl decyl)-2-(trimethyl.nonanyl) Ethyl, 1-(di-η-butoxymethyldecyl)-2-(trimethyldecyl)ethane, 1-(di-sec-butoxymethyldecyl)-2- a decane containing a didecyl group such as (trimethyldecyl)ethane or 1-(di-t-butoxymethylalkyl)-2-(trimethyldecyl)ethane; - bis(trimethoxydecyl)benzene, 1,2-bis(triethoxydecyl)benzene, 1,2-bis(tris-n-propoxydecyl)benzene, 1,2-double ( Tri-i-propoxydecylalkyl)benzene, 1,2-bis(tris-n-butoxydecyl)benzene, 1,2-bis(tris-butoxybutanyl)benzene, 1, 2-bis(tri-t-butoxydecyl)benzene, 1,3-bis(trimethoxydecyl)benzene, 1,3-bis(triethoxydecyl)benzene, 1,3-double (tri-n-propoxydecyl)benzene, 1,3-bis(tri-i-propoxy) Alkyl)benzene, 1,3-bis(tris-η-butoxydecyl)benzene, 1,3-bis(tri-sec-butoxydecyl)benzene, 1,3-bis(tri-t) -butoxyalkylene)benzene, 1,4-bis(trimethoxydecyl)benzene, 1,4-bis(triethoxydecyl)benzene, 1,4-bis(tri-η-propoxy) c -19- 201243496 矽alkyl)benzene, 1,4-bis(tri-i-propoxydecyl)benzene, 1,4-bis(tri-n-butoxydecyl)benzene, 1,4 a dioxane such as bis(tri-sec.butoxyalkyl)benzene or 1,4-bis(tri-t-butoxydecyl)benzene: polydimethoxymethylcarbane, polydi Polycarbane such as ethoxymethylcarbon decane. These decane compounds may be used alone or in combination of two or more. [A] Polyoxyalkylene may be contained in one or more than two types of the ruthenium-containing film-forming composition for the multilayer photoresist process. The polystyrene-equivalent weight average molecular weight (Mw) of [A] polyoxyalkylene gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, still more preferably 2,000 to 30,000. , especially good for 2,000 ~ 10,000. In addition, in the Mw system of [A] polyoxane in this specification, GPC column made by Tosoh (2 pieces of "G2000HXL", 1 piece of "G 3 Ο Ο Ο HX L", and "G4 0 0 0HXL" 1 are used. Support, and the flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C under the analytical strip, monodisperse polystyrene as the standard, measured by GP C. decane compound ( 2) A method of hydrolyzing and condensing other decane compound used as necessary, for example, a known method of hydrolytic condensation can be used. [A] The content of polysiloxane is based on the ruthenium-containing film-forming composition for the multilayer photoresist process. The total solid content is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more. &lt;[B] Electron acceptor&gt; [B] The electron accepting system has an function of accepting electrons. [B] The electron acceptor is not particularly limited as long as it has the above properties. [B] Electron accepting -20-201243496 The form of the body may be in the form of a compound as described later, for example, [A] polydecane Or other polymer having a form containing a group that accepts electrons, or may be [B] The electron-receiving system is irradiated with a deep ultraviolet ray such as EUV, etc. X-rays such as synchrotron radiation, and various kinds of radiation such as charged particle lines such as electron beams have an interface between the ruthenium-containing film and the photoresist film. The function of the electrons generated in the vicinity, thereby controlling the amount of electrons which are involved in the decomposition of the acid generator (P) in the photoresist composition described later in the vicinity of the interface between the ruthenium film and the photoresist film. In the vicinity of the interface between the film and the photoresist film, the excess deprotection reaction of the polymer having an acid dissociable group in the photoresist composition can be controlled to control the bottom shape of the photoresist pattern, thereby improving the pattern collapse resistance and solution. The lithographic properties of the image, the rectangular shape of the pattern, etc. [B] The electron acceptor is preferably selected from the group consisting of an anthracene compound, a quinodimethane compound, a dibenzofuran compound, and the above formulas (1_1) and (1_2), respectively. The compound represented by the following formula (3-1) to the following formula (3_5), etc., is a compound represented by the following formula (3-1) to the dibenzofuran compound. 3

f ° y 6

&lt;3·1) {3-2) (3-3) Y

-21 - 201243496 The γ-forms in the above formulae (3-1) to (3-5) are each independently a hydrogen atom, a hydroxyl group, a halogen atom or a cyano group. RXQ is independently a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or a cyano group. However, at least one of the compounds is a cyano group. The halogen atom represented by the above Y may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The above Y is preferably a halogen atom or a cyano group from the viewpoint of electronic controllability of the [B] electron acceptor. More preferably, it is a fluorine atom, a chlorine atom or a cyano group, and more preferably a cyano group. The compound represented by the above formula (3-1) to (3-5) may, for example, be a compound represented by the following formula. 【化4】

Ο

The lithographic performance is preferably 'the compound represented by the above formula (3-1) to (3-4), more preferably the compound represented by the above formula (3-3), and the formula (3 - 4) - 22- 201243496, more preferably 2,3,5,6-tetrachloro-1,4-benzoquinone, 7,7,8,8-tetracyanoquinodimethane, particularly preferably 7,7,8, 8-tetracyanoquinodimethane. Next, the compounds represented by the above formula (1-1) and formula (1-2) will be described. In the above formula (1-1) and formula (1-2), R1 to R5 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom. The Z· and Q· systems are independently OH., RA-CO〇-, Ra-S03- or RA-N, and S02-RB. RA is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. However, part or all of the hydrogen atoms possessed by RA may be substituted. RB is an alkyl or aralkyl group. However, one or all of the hydrogen atoms of the RB may be substituted by fluorine atoms. The alkyl group represented by R1 to R5 may, for example, be a methyl group, an ethyl group, an n-propyl group, a propyl group, an η-butyl group, an i-butyl group, a sec-butyl group or a t-butyl group. Alkoxy groups represented by R1 to R5, for example, methoxy, ethoxy, n-propoxy, i-propoxy, η-butoxy, i-butoxy, sec-butoxy, t _ Butoxy and the like. The halogen atom represented by R1 to R5 may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group represented by the above-mentioned shakuhachi and RB has, for example, the same groups as those exemplified above. The cycloalkyl group represented by the above RA may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a decyl group, a ruthenium group or the like. Examples of the aryl group represented by ra include a phenyl group, a tolyl group, a xylene group, a trimethylphenyl group, a cyclohexylphenyl group, a naphthyl group, and the like. The above octagonal and aralkyl represented by rb include, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a decylmethyl group and the like. RA may have a substituent 'for example, a fluorine atom, a chlorine atom, a bromine 23-201243496, a halogen atom such as an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxycarbonyl group, or an alkane group. Oxycarbonyloxy, thiol and the like. In the above, from the viewpoint of electron acceptability of the [B] electron acceptor, a halogen atom, a hydroxyl group, a cyano group, a nitro group, more preferably a fluorine atom, a chlorine atom, a hydroxyl group, a cyano group or a nitro group are preferable. Preferably, it is a fluorine atom or a hydroxyl group. The compound represented by the formula (1-1) and (1-2) is, for example, a compound represented by the following formula. 【化5】

-24- 201243496 In this case, considering the moderate improvement of the electronic controllability and the improvement of the lithographic performance of the obtained photoresist pattern, it is preferred that the compound represented by the above formula (1) (镝 salt) is more preferably contained in the electrons. The sulfonium salt of the anion of the aromatic ring of the attracting group is particularly preferably a mirror salt containing an anion of a benzene ring having a trifluoromethyl bond, particularly preferably diphenyl fluorene 2 - thiol-4 - dioxin Methyl benzoate, 4-cyclohexyl phenyl diphenyl sulfonium 2-hydroxy-4-trifluoromethyl benzoate, triphenyl sulfonium 2-hydroxy-4-trifluoromethyl benzoate . [B] The content of the electron acceptor is usually 0.1 parts by mass to 20 parts by mass, preferably 0.5 parts by mass to 15 parts by mass, based on 1 part by mass of the [A] polyoxyalkylene. Parts by mass to 10 parts by mass. [B] The content of the electron acceptor in the above range, using a pattern formed by a multilayer photoresist process which is finer than 50 nm, can be a lithographic property such as pattern collapse resistance, resolution, and rectangular shape of the pattern shape. More excellent. &lt;[C] Solvent&gt; The composition for forming a ruthenium-containing film for a multilayer photoresist process usually contains a [C] solvent. The solvent of [C] is not particularly limited as long as it can dissolve or disperse [a] polyoxalate, [b] electron acceptor, and any component described later. [C] The solvent may, for example, be an alcohol solvent, an ether solvent, a ketone solvent, an awakening solvent, an ester solvent or a hydrocarbon solvent. The alcohol solvent is, for example, methanol, ethanol, η-propanol, iso-propanol, n-butanol, iS0-butanol, sec. butanol, tert-butanol, n-pentanol, is〇-pentanol '2-methyl Butanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, - 25- 201243496 3-heptanol, η-octanol, 2-ethylhexanol, sec-octanol, η-nonanol ' 2,6-dimethyl-4-heptanol' η-nonanol, sec- ~{--yl alcohol, trimethyl sterol, sec-tetradecyl alcohol, sec. heptadecyl alcohol, mercapto alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-three Monool solvent such as methylcyclohexanol, benzyl alcohol or diacetone alcohol; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4·pentanediol, 2-methyl- 2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, a polyol solvent such as tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol Monophenyl ether, ethyl alcohol mono-2 Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethyl - unitary? Monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc. An alcohol partial ether solvent or the like. Examples of the ether solvent include aliphatic ether solvents such as diethyl ether, dipropyl ether, and dibutyl ether: aromatic cyclic ether solvents such as anisole and diphenyl ether; and tetrahydrofuran and dioxane. An ether solvent or the like. Ketone solvents, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone 'methyl-η-butyl ketone' diethyl ketone, methyl-is 〇 butyl ketone, methyl _ Η-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-is 〇 butyl -26- 201243496 ketone-methyl fluorenone, acetophenone and other chain ketone solvents '· A cyclic ketone solvent such as cyclopentanol, cyclohexyl copper, cycloheptanone, cyclooctanone or methylcyclohexanone; a diketone solvent such as 2'4·pentanone or acetonylacetone. The amine-based solvent is, for example, N-methylformamide 'N,N-dimethylformamide N,N-ethylformamide, acetamidine, oxime methylamine, N, a chain amide-based solvent such as N-dimethylacetamide or N-methylpropionamide; a cyclic guanamine such as N-methyl fluorenosterone or N,N,-dimethylimidazolidinone A solvent or the like. Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, is〇-butyl acetate, sec-butyl acetate, η-amyl acetate, and acetic acid sec. • Amyl ester, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate , n-decyl acetate, methyl acetate, ethyl acetate, ethylene glycol diacetate, methoxy diglycol acetate, ethyl propionate, propionic acid n-butyl vinegar, propionic acid iso -amyl ester, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, η-butyl lactate, η-amyl lactate, diethyl malonate, dimethyl phthalate a carboxylic acid ester solvent such as diethyl phthalate; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethyl Glycol monoethyl ether acetate, diethyl alcohol mono-η-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Ester, propylene glycol monobutyl a carboxylate solvent of a polyol partial ether such as ether acetate, dipropylene glycol monomethyl ether acetate or dipropylene glycol monoethyl-27-201243496 ether acetate; γ-butyrolactone, γ-pentane A lactone-based solvent such as an ester; a carbonate-based solvent such as diethyl carbonate or propyl carbonate; and the like. The hydrocarbon solvent is, for example, η-pentane, iso-pentane, η-hexane, iso-hexane, η-heptane, iso-heptane, 2,2,4-trimethylpentane, η-octane. An aliphatic hydrocarbon solvent such as an alkane, iso-octane, cyclohexane or methylcyclohexane; benzene, toluene, xylene, trimethylbenzene, ethylbenzene, trimethylbenzene, methylethylbenzene, η- An aromatic hydrocarbon solvent such as propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene or η-pentylnaphthalene. Among these, an alcohol solvent or an ester solvent is preferred, and a polyol partial solvent or a carboxylic acid ester solvent of a polyol partial ether is more preferred, and propylene glycol monomethyl ether and propylene glycol monoethyl ether are more preferred. , propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether acetate, particularly preferably propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate. &lt;Optional Component&gt; The ruthenium-containing film-forming composition for the multilayer photoresist process may further contain β-diketone, colloidal ruthenium oxide, colloidal shape in addition to [Α] polyoxane and [Β] electron acceptor. Any component such as alumina, an organic polymer, a surfactant, an acid generator, or a nitrogen-containing compound. &lt;Modulation method of ruthenium-containing film-forming composition for multilayer photoresist process&gt; The ruthenium-containing film-forming composition for the multilayer photoresist process is, for example, mixed [Α] -28- 201243496 polyoxyalkylene, [B] electron accepting Any component of the body, if necessary, then dispersed or dissolved in [C] solvent'. The solid content concentration of the composition containing the ruthenium-containing film in the multilayer photoresist process is usually from 0.5% by mass to 20% by mass, preferably 1% by mass. ~1 5 mass%, more preferably 〇. 5 mass%~2 · 0 mass%. &lt;Formation Method of Pattern&gt; [Formation Method I of Pattern] The method of forming the pattern of the present invention has the following steps: (1-1) using [A] polyoxane and [B] The electron-receptor multilayer photoresist process comprises a ruthenium-containing film-forming composition, a step of forming a ruthenium-containing film on the upper surface of the substrate to be processed, and 0-2) using a photoresist composition to form a photoresist film on the ruthenium-containing film. a step (1-3) a step of exposing the photoresist film to radiation exposure of the photomask, and (1-4) developing the exposed photoresist film to form a photoresist pattern Steps and (1-5) a step of dry etching the ruthenium-containing film and the substrate to be processed in sequence using the photoresist pattern as a mask. According to the formation method I of the pattern, since the composition is formed by using the ruthenium-containing film for the multilayer photoresist process, it is possible to form a photoresist pattern excellent in rectangularity of pattern collapse resistance, resolution, and pattern shape. A good stiffness is formed on the substrate to be processed. The steps are described below.

C -29- 201243496 [Step (1-1)] This step is a composition for forming a ruthenium-containing film for a multilayer photoresist process containing [A] polyoxane and [B] electron acceptor, in a substrate to be processed. A ruthenium-containing film is formed on the upper side. As the substrate to be processed, for example, a known wafer such as a tantalum wafer 'aluminum-coated wafer or the like can be used. On the substrate to be processed, another underlayer film (hereinafter also referred to as "other underlayer film") which is different from the ruthenium-containing film obtained by using the ruthenium-containing film-forming composition for the multi-layer photoresist process in advance can be formed. The other underlayer film is provided with a film having a reflection preventing function, flatness of a coating film, high etching resistance to a fluorine gas such as CF4, and the like. The other underlayer film can be formed, for example, by using a commercial product such as "NFC HM8005" (manufactured by JSR) or "NFC CT08" (manufactured by JSR). The film thickness of the other underlayer film is usually 1 〇 nm or more and 200 nm or less. In order to improve the patterning property and the processability, it is preferably 20 nm or more and 100 nm or less. The method for forming the other underlayer film is not particularly limited. For example, a coating film formed by forming a composition of another underlayer film by a known method such as a spin coating method on a substrate to be processed is exposed and/or It is formed by heating and hardening. A method for forming a ruthenium-containing film by using a ruthenium-containing film-forming composition for the multilayer photoresist process, for example, by coating a surface of a substrate to be processed or another underlayer film (including an anti-reflection film) formed on the substrate to be processed. Forming a coating film for forming a composition containing a ruthenium film for the multilayer photoresist process, wherein the coating film is subjected to heat treatment, or when the ruthenium-containing film-forming composition for the multilayer photoresist process contains a latent photoacid generator, The method of light irradiation and heat treatment to harden it is -30-201243496. The coating method is, for example, a known method, for example, a spin coating method, a roll coating method, a dipping method, or the like. After the above coating, the solvent in the coating film may be volatilized by baking (PB) as necessary. The PB temperature can be appropriately selected according to the compounding composition of the ruthenium-containing film-forming composition of the multilayer photoresist process, and is usually 50 ° C to 450 ° C, preferably 100 〇 C 3 300 〇 C 矽 formed yttrium film The film thickness is usually 5 nm or more and 200 nm or less. In order to improve the patterning property and the workability, it is preferably 5 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less, and more preferably 10 nm or more and 30 nm or less. [Step (1-2)] This step uses a photoresist composition to form a photoresist film on the above-mentioned ruthenium-containing film. The photoresist composition used in the step (1-2) is, for example, a positive or negative chemically amplified photoresist composition containing an acid generator, and an alkali-soluble resin and a quinonediazide-based sensitizer. A positive photoresist composition, a negative photoresist composition composed of an alkali-soluble resin and a crosslinking agent, and the like. The solid content concentration of the above photoresist composition is preferably from 0.1 to 50% by mass, more preferably from 5% to 30% by mass, still more preferably from 1% by mass to 15% by mass. The above photoresist composition is preferably filtered using a filter having a pore size of about 0.2 μη. In the method for forming a pattern of the present invention, the photoresist composition may be directly coated with a photoresist composition of a commercially available product, 201243496, and is not particularly limited. For example, a spin coating method or the like is used. Methods. When the photoresist composition is applied, the resulting photoresist film is formed to have a predetermined film thickness, and it is preferred to adjust the amount of the applied photoresist composition. The photoresist film is coated with the film formed of the photoresist composition, and the solvent in the coating film can be volatilized by baking (PB) or the like. The PB temperature can be appropriately adjusted depending on the type of the photoresist composition to be used, etc., preferably from 3 〇 t to 200. (:, more preferably 50 ° C to 150 ° C. The surface of the photoresist film may be provided with another film. The film thickness of the formed photoresist film is usually 10 nm or more and 20 nm or less, preferably 1 〇nm or more and 100 nm or less, more preferably 20 nm or more and 70 nm or less. [Step (1-3)] This step is a desired region of the photoresist film formed in the step (1-2), and is interposed between the mask having a specific pattern. The radiation is exposed to radiation, such as electromagnetic waves such as far ultraviolet rays, deep ultraviolet rays, X-rays, and gamma rays, electron beam lines such as electron lines, and alpha rays, etc. Among these, deep ultraviolet rays and X-ray 'electrons are preferable. The use of a ruthenium-containing film having a multi-layer photoresist process having the above properties forms a composition, so that when the radiation is deep ultraviolet rays, X-rays, and electron lines, the effect is more effective, and the formation method I of the pattern can be formed into a good shape. In the pattern, the exposure may be performed several times in succession, for example, the first exposure is performed on the desired region between the masks, and then the second exposure is performed in an interlaced manner for the exposure portions after the first exposure. When the primary exposure unit is interlaced with the second exposure unit, In the unexposed portion surrounded by the exposure portion, a true circular contact hole pattern is easily formed. For several exposures, different light sources can be used for exposure -32-201243496. For example, the first exposure uses an ArF excimer laser, and the second The secondary exposure uses EUV light, or vice versa. After exposure, post-exposure baking (PEB) is preferred. PEB can smoothly carry out the dissociation reaction of the acid dissociable group in the above photoresist composition. The PEB temperature is usually 30. °C~200°C, preferably 50°C~170°C. [Step (1-4)] This step is to use the developing solution for the photoresist film after the exposure of the step (1-3). The photoresist pattern can be appropriately selected depending on the type of the photoresist composition to be used. The photoresist composition is a positive chemically amplified photoresist composition or a positive light containing an alkali-soluble resin. When the composition is blocked, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, gas, ethylamine, η-propylamine, _diethylamine, di-η-propylamine, triethylamine can be used. 'Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (ΤΜΑΗ), tetraethyl Ammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4·3·0]-5- Further, the alkaline aqueous solution may contain an appropriate amount of a water-soluble organic solvent, such as an alcohol such as methanol or ethanol, etc. Further, an organic solvent containing an organic solvent as a main component may be used as the developing solution. A developing solution may be added with an appropriate amount of a surfactant. If necessary, for example, an ionic or nonionic fluorine-based and/or polyoxynoxy surfactant may be used as the surfactant. A method in which a substrate is immersed in a bath filled with a developing solution for a certain period of time (dipping method), and a developing solution is filled on a surface of the substrate -33-201243496 by surface tension and is imaged for a certain period of time and developed (liquid-covering method) a method of spraying a developing solution onto a surface of a substrate (spraying method), scanning a substrate at a constant speed, and scanning the developer liquid at a constant speed while ejecting the developing solution (dynamic coating method) Wait. After the above development, the photoresist can be washed with a washing liquid. The washing liquid is preferably water when the developing solution is an aqueous alkali solution, and is preferably a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent or a guanamine solvent when the developing solution is an organic solvent developing solution. Wait. Each component of the above washing liquid may be used singly or in combination of two or more. [Step (1-5)] In this step, the photoresist pattern formed in the step (1-4) is used as a mask, and the ruthenium-containing film and the substrate to be processed are sequentially dry-etched on the substrate to be processed. Form a pattern. The dry etching described above can be carried out using a conventional dry etching apparatus. Further, the source gas system during dry etching differs depending on the elemental composition of the etching material, and a gas containing an oxygen atom such as 〇2'CO or CO2; an inert gas such as He'N2 or Ar: a chlorine-based gas such as Cl2 or BC14; H2, NH3 gas, etc. Also, these gases can be used in combination. [Formation Method II of Pattern] The method of forming the pattern of the present invention has the following steps: (π-1) forming a composition using a ruthenium-containing film for a multilayer photoresist process containing [A] polysiloxane a step of forming a ruthenium-containing film on the upper surface side of the substrate to be processed, -34-201243496 (Π-2) using a photoresist composition, and forming a photoresist film on the ruthenium-containing film, (ΙΙ-3) between the light a step of exposing the photoresist to the deep ultraviolet ray or the electron beam, exposing the photoresist film, and ΙΙ-4) developing the exposed photoresist film to form a photoresist pattern, and (II-5) The step of dry etching the ruthenium-containing film and the substrate to be processed is sequentially performed using the photoresist pattern as a mask. According to the formation method II of the pattern, the composition for forming a ruthenium-containing film for a multilayer photoresist process containing [Α] polysiloxane is used as a deep ultraviolet ray or an electron line, and in the multilayer photoresist process, even light The resistance pattern is a film, and a good pattern can be formed on the substrate to be processed. [Step (ΙΙ-1)] This step is to form a ruthenium-containing film on the upper surface side of the substrate to be processed using a ruthenium-containing film-forming composition for a multilayer photoresist process containing [Α] polyoxyalkylene. The substrate to be processed is, for example, the same as the method of forming the above-described pattern I. The method for forming the ruthenium-containing film is, for example, the same method as the step (1-1) of the method of forming the pattern I described above. [Step (ΙΙ-2)] This step is to form a photoresist film using a photoresist composition on the ruthenium-containing film formed by the above step (II-1). The method of forming the above-mentioned photoresist film is, for example, the same method as the step (1-2) of the above-described pattern forming method I. -35- 201243496 [Step (Π-3)] This step exposes the photoresist film formed by the above procedure (ΙΙ_2) with a ray mask irradiated with deep ultraviolet rays or electron beams. In the above exposure method, in addition to the use of deep ultraviolet rays for radiation, for example, there are the same methods as those of the step (1-3) of the formation method j of the above-described pattern. [Step (11 - 4)] In this step, the photoresist film exposed by the above step (11_3) is developed to form a photoresist pattern. The method of developing the above is, for example, the same method as the step (1-4) of the method of forming the above-described pattern I. [Step (ΙΙ-5)] In this step, the ruthenium-containing film and the substrate to be processed are sequentially dry-etched by using the photoresist pattern formed in the above step (II-4) as a mask. The above-described method of dry hunging has, for example, the same method as the step (1_5) of the method of forming the above-described pattern I. &lt;Photoresist composition&gt; A photoresist composition for forming a pattern of the pattern is preferably a positive type chemically amplified photoresist composition containing a radiation-sensitive acid generator. The chemically amplified photoresist includes, for example, a polymer containing a structural unit having an acid-dissociable group (hereinafter also referred to as "polymer (I)"), a radiation-sensitive acid generator, and a solvent. It may contain an acid diffusion controlling agent or the like. -36- 201243496 [Polymer (1)] The above polymer (I) contains a structural unit having an acid-dissociable group. The structural unit having an acid-dissociable group is, for example, a structural unit (7) which will be described later in the structural unit represented by the following formula (4) (hereinafter also referred to as "structural unit (1)").

In the above formula (4), R8 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group. R9 is a divalent substituted or unsubstituted alicyclic hydrocarbon group. R| 〇 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms. The carbon number of the divalent alicyclic hydrocarbon group represented by R9 is not particularly limited, and is preferably 5 to 25, more preferably 5 to 2 Å, still more preferably 5 to 15. The above-mentioned divalent alicyclic hydrocarbon group represented by R9 is preferably a group having a monocyclic structure, a bicyclic structure, a tricyclic structure or a tetracyclic structure. A specific example of the above-mentioned divalent alicyclic hydrocarbon group represented by R9, wherein a group having a monocyclic structure is, for example, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, or a cyclooctanediyl group. a group, a cyclodecanediyl group, a cyclododecanediyl group or the like; a group having a bicyclic structure 'for example, a norbornanediyl group, a decahydronaphthalenyl group, a cedar enol group or the like: a group having a bicyclic structure 'For example, tricyclodecanediyl, adamantane

C-37-201243496 Diyl, noradamantandiyl, etc.; a group having a tetracyclic structure, for example, a tetracyclododecanediyl group or the like. In these, 'preferably a group having a monocyclic structure, a group having a bicyclic structure, a group having a bicyclic structure, more preferably a group having a monocyclic structure having a carbon number of 5 to 15, and having a bicyclic structure. a group having a tricyclic structure, more preferably a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, a cyclodecanediyl group, a cyclododecanedi group Base, adamantanediyl, decahydronaphthalenediyl, norbornanediyl. The above alicyclic hydrocarbon group may have a substituent such as a halogen atom such as a group such as a methyl group, an ethyl group or a propyl group, a hydroxyl group, a carboxyl group, a fluorine atom or a bromine atom, a methoxy group, an ethoxy group or a propoxy group. An alkoxy group such as a group or a butoxy group, an alkoxycarbonyl group such as a methylcarbonyl group or an ethoxycarbonyl group, or the like. The aryl group having 6 to 2 carbon atoms represented by the above R1Q is, for example, a group derived from the structure represented by the following formula (x-1) to (x-3). When R1Q is a group derived from a structure represented by the following formula (X-2) (ie, a naphthyl group), the bonding position 'bonded to R9 in the above formula (4)' may be either one or two . When R1G is a group derived from a structure represented by the following formula (x-3) (ie, a fluorenyl group), the bonding position of R9 bonded to the above formula (4) may be 1 position, 2 positions, and 9 positions. Ren-. [化7] (x-2)

The substituent which the aryl group represented by the above R1Q may have is the same as those exemplified as the substituent which the alicyclic hydrocarbon group represented by the above R9-38-201243496 may have. In addition to the structural unit (1), the polymer (I) may contain a structural unit represented by the following formula (5) (hereinafter also referred to as "structural unit (2)"), and a structure represented by the following formula (6) The unit (hereinafter also referred to as "structural unit (3)"), the structural unit represented by the following formula (7) (hereinafter also referred to as "structural unit (4)"), and the structural unit represented by the following formula (8) ( Hereinafter, it is also referred to as at least one of "structural unit (5)"). The polymer (I) may contain one or two or more kinds of each structural unit of each of the structural units (2) to (5). 【化8】

(5) In the above formula (5), R11 is a hydrogen atom or a methyl group. R] 2 is a monovalent organic group. i is an integer from 0 to 3. When the integer of j system 〇3 is 2 or more, the plural R12s may be the same or different. However, each of 0 Si+j is satisfied. 【化9】 R13

(6) £ -39- 201243496 In the above formula (6), R&gt;3 is a hydrogen atom or a methyl group. It is a monovalent organic group. k is an integer of 0 to 3 ^ m is an integer of 〇~3. When m is 2 or more, the plural R14s may be the same or different. But meet 〇Sk + m guest 5. [化1 〇] =0

(〇H^R16)p NH (7) In the above formula (7), R15 is a hydrogen atom or a methyl group. R16 is a monovalent organic group. η is an integer from 0 to 3. When p is an integer of ～3, when p is 2 or more, the plural R16s may be the same or different. But it satisfies OSn + pS 5. [1 1] R17

In the above formula (8), R17 is a hydrogen atom or a methyl group. R18 is a monovalent organic group. q is an integer of 〇~3. r is an integer from 0 to 3. When r is 2 or more, the plural R18s may be the same or different. The above-mentioned R12, R14, R16 and R18 represent a monovalent organic group, for example, -40-201243496 methyl, ethyl, η-propyl, iso-propyl, η-butyl, 2-methylpropyl, 1- a linear or branched alkyl group having a carbon number of 1 to 12, such as methyl propyl 'tert-butyl; methoxy, ethoxy, η-propoxy, iso-propoxy, η a linear or branched alkoxy group having 1 to 1 carbon atom such as a butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group or a tert-butoxy group; a cycloalkyl group such as a cyclohexyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclododecyl group; an adamantyl group, a norantayl group, a decahydronaphthyl group, a tricyclodecyl group, a tetracyclic ring Dodecyl, sulfhydryl, cedar enol, and the like. Among them, preferred are methyl, ethyl, η-butyl and tert-butyl. In the above formula (5), 'i is preferably 1 or 2, and" is preferably an integer of 〇~2 or 1. In the above formula (6), k is preferably! Or 2, m is preferably 〇 or b. In the above formula (7), η is preferably 1 or 2, p is preferably 〇 or b. In the above formula (8), q is preferably 1 or 2, and r is preferably. For 〇 or 1. 2, r is preferably

[1 2

C -41 - 201243496 【化1 3】r° 〇 Μ, -p6-c2^ :〇

OH (6-1) o

OH (6-2) The structural unit (4) is, for example, a structural unit represented by the following formula (7.n and (7_2), etc., ^h2, ten?-c10, H3? Η: ten c[ch ° h° NH Λ NH Λ V OH V OH (7-1) (7-2) The structural unit (5) is, for example, a structural list represented by the following formulas (8-1) and (8_2)

(8-1)

The polymer (I) may contain, in addition to the above structural units (1) to (5), a structural unit derived from -42 to 201243496 non-acid dissociable compound (hereinafter also referred to as "structural unit (6)"), derived from acid The structural unit of the dissociative compound (hereinafter also referred to as "structural unit (7)"). The polymer (I) may contain one type or two or more types of each of the structural units. The above non-acid dissociable compound is, for example, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, isodecyl acrylate, tricyclodecane a compound represented by the following formula (L-1) having a structure of a lactone, a compound represented by the following formula (S-1), a compound represented by the following formula (S-1): a (meth) acrylate, a tetracyclododeca (meth) acrylate, a compound having a lactone structure Wait. Among these, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene ' 3 -methylstyrene, tricyclodecyl acrylate, and the following formula ( A compound represented by L-1) or a compound represented by the following formula (S-1). [Chem. 1 6] RL1

V2 RL3 In the above formula (L-1), 'Rl1 is a hydrogen atom, a methyl group or a trifluoromethyl group. RL2 is a single bond or a divalent linkage. It is a monovalent organic group having a lactone structure.

C -43- 201243496 【化1 7】

(S-1) In the above formula (S-1), RS1 is a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may be substituted. RS2 is a hydrogen atom, a halogen atom, a cyano group or an alkyl group, a cycloalkyl group, an alkoxy group, a decyl group, a decyloxy group, an alkenyl group, an aryl group or an aralkyl group which may be substituted. RS3 to RS8 are each independently a hydrogen atom, a fluorine atom or an alkyl group which may be substituted. RS9 is a hydrogen atom, an alkyl group which may be substituted, a cycloalkyl group, a decyl group, an alkylsulfonyl group or an alkoxycarbonyl group. r is an integer of 5. s is an integer from 1 to 5. But satisfies r+s = 5. When RS2 to RS9 are plural, respectively, the complex RS2 to RS9 may be the same or different. However, at least one of rS2 to Rss is an alkyl group in which a fluorine atom or at least one hydrogen atom is replaced by a fluorine atom. The divalent linking group represented by the above is, for example, a linear or branched hydrocarbon group having a carbon number of 1 to 20 valence. The above RL3 represents a monovalent organic group having a lactone structure, and examples thereof include a group represented by the following formulas (L3-1) to (L3-6). -44- 201243496 【化1 8】

In the above formulae (L3-1) to (L3-6), Rlci is an oxygen atom or a methylene group. R is a hydrogen atom or a hospital with a carbon number of 1 to 4. The nLci system or the nLc2 system is an integer of 〇~3. * indicates a moiety β bonded to RL2 of the above formula (Ld). The group represented by the above formula (L3-1) to (L3-6) may have a substituent. The compound represented by the above formula (L-1) is, for example, a compound described in paragraph [〇〇43] of International Publication No. 2007/116664. The compound represented by the above formula (S-1) has, for example, a compound represented by the following formula (S-1-1), a compound represented by the formula (S - 2), and the like.

C -45- 201243496 【化1 9】r^S F3C—C—CF3 OH (S-1-1) F3C, hct :C^^^c/CF3

"c^0H (S-1-2) The above-mentioned acid-dissociable compound is, for example, a compound represented by the following formula: [Chemical 2 0]

In the above formulae (9-1) and (9-2), R19, r2q, r2 丨, r25, r26 and R27 each independently represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. The r22, r23, r24, r29, and R3Q are each independently a linear or branched group of carbon number 4, a monovalent alicyclic group of carbon 4 to 20, or a group thereof. Derived group. However, any two of R22, r23 and r24 or two of R28 'R29 and R3G are combined with each other to form a divalent fat having a carbon number of 4 to 20 together with the carbon atoms of the group -46 - 201243496 a group derived from a cyclic hydrocarbon group or the like. R19, R2Q and R21 of the above formula (9-1) and R and R27 of the formula (9-2) represent a linear or branched alkyl group having 1 to 4 carbon atoms, methyl, ethyl and η. -propyl 'i-propyl, n-butyl, 2-methylpropylmethylpropyl, t-butyl and the like. R19, R2Q and R21 of the above (9-1) and R25' R27 of the formula (9-2) represent a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, for example, a decane, a tricyclodecane, or a tetra a group of an alicyclic ring such as cyclodane, adamantane, cyclobutane, cyclohexane, cycloheptane or cyclooctane. The group derived from the above alicyclic hydrocarbon group may, for example, be a part or all of a hydrogen atom possessed by the upper alicyclic hydrocarbon group, by way of example, ethyl, η-propyl, i-propyl, η- a linear or branched alkyl group having 1 to 4 carbon atoms such as a butyl group, a 2-methylpropyl group, a propyl group or a t-butyl group, or a group having one or more substituents. The above alicyclic hydrocarbon group and the group derived therefrom, wherein the group consists of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, diamond, or cyclohexane A group in which a group consisting of such a lipid is substituted with the above alkyl group. Any two of R22, R23 and R24 or RH, R29 and any two of them may be bonded to each other by a carbon atom having 4 to 20 carbon atoms together with the carbon atom to which they are bonded, for example, a ring Dingyuan dipentanediyl, cyclohexanediyl, cyclooctanediyl and the like. Or the valence of a monovalent group such as a methyl 1-methyl group, which is formed by a group of 2, 5, and 2, for example, a group, a group of 1-.R26, and a cyclopentane, preferably formed in the cyclopentane ring group R30. Base, ring

S-47-201243496 A group derived from the above-described divalent alicyclic hydrocarbon group formed, for example, a part or all of a hydrogen atom of the above-mentioned divalent alicyclic hydrocarbon group, for example, a methyl group, an ethyl group, a linear or branched chain of 1-4 propyl, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, etc. having a carbon number of 1 to 4 One or more or one or more substituted groups. Among these, a cyclopentanediyl group, a cyclohexanediyl group, a group in which the group is substituted by the above alkyl group is preferable. The structural unit (7) is preferably a structural unit represented by the following formulas (9-1-1) to (9-1-7) and (9-2-1). [Chemical 2 1 c=o -R24

Handle I R22- R23 (9-1-1) η 2-C^· f21 -{-ch2-c-} i21 -f-CH2-C-4 ?=〇γ〇c=o A ? 〇I 0 C1 /-4-r24 R22_ —R24 R22 —R24 y 〇28_|_〇30 R29 (9-1-5) (9-1-6) (9-1-7) (9-2-1) In 9-1 1-7) and (9-2- 1), R21; 5 2 7 is independently a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R22 to R24 R28 to R3() are each a linear or branched alkane of a carbon number of 4 -48-201243496. The content ratio of the above structural unit (1) in the polymer (I) is relative to the composition. The total structural unit of the polymer (I) is from 5 mol% to 70 mol%, preferably from 5 mol% to 50 mol%. . When the content ratio is in the above range, the photoresist composition can be formed to have excellent nanoedge roughness. The total content of the structural units (2) to (5) is preferably 1 mol% or more, more preferably 5 mol% to 9.5 mol, based on the total structural unit constituting the polymer (I). % 'more preferably 5 mole % ~ 8 0 mole %. When the total amount exceeds 95 mol%, the nanoedge roughness of the photoresist composition may be deteriorated. The total content of the structural units (1) to (5) is preferably 10 mol% or more, and more preferably 40 mol% to 1 mol%, based on the total structural unit constituting the polymer (I). Ear %, more preferably 50 mole % ~ 100 moles. /〇. The total content of the content ratio is 10% by mole or more, and the photoresist composition can be formed to have excellent nano edge roughness. The content ratio of the above structural unit (6) is usually 80 mol% or less, preferably 0 mol% / 〇 to 60 mol%, more preferably 0% by mole based on the total structural unit constituting the polymer (I). 5 mole % ~ 30 mole %. Since the content ratio is 80 mol% or less, the photoresist composition can be excellent in the balance between the resolution of the resolution and the edge roughness of the nano edge. The content ratio of the above structural unit (7) is usually 60 mol% or less, preferably 〇 mol % to 50 mol%, more preferably 20 mol, based on the total structural unit constituting the polymer (I). %~50% by mole. Since the content ratio is 60% by mole or less, the photoresist composition can be excellent in the balance between the resolution of the resolution and the edge roughness of the nano edge. -49 - 201243496 The total content of the above structural units (6) and (7) is usually 90 mol% or less, preferably 〇 mol% to 80%, based on the total structural unit constituting the polymer (I). Moer%, more preferably 20 mol% ~ 70 mol%. This content ratio is 90 mol% or less, and the photoresist composition can be excellent in the balance between the resolution of the resolution and the edge roughness of the nano. The method for synthesizing the polymer (I) is not particularly limited, and examples thereof include a known method of radical polymerization or anionic polymerization. The polystyrene-reduced weight average molecular weight (hereinafter also referred to as "Mw") measured by gel permeation chromatography (GPC) of the polymer (I) is preferably 1,500 to 100,000 ', more preferably 1,500 to 40,000. More preferably, it is 2,000 to 25,000, and the best is 5,000 to 15,000. The ratio (Mw/Mn) of the Mw of the polymer (I) to the polystyrene-equivalent number average molecular weight (hereinafter also referred to as "Μη") measured by GPC is usually 1 to 5, more preferably 1 to 4, more preferably It is 1 to 3. [Thermionic acid generator] The radiation-sensitive acid generator (hereinafter also referred to as "acid generator (P)") is used in a lithography process to irradiate radiation or the like to light formed by the photoresist composition. When the film is blocked, an acid is generated in the photoresist film. The action of the acid generated by the acid generator (P), the acid dissociable group in the polymer (I), and the dissociation acid generator (P) are preferably selected from the viewpoints of good acid generation efficiency, heat resistance, and the like. At least one of a group consisting of a key salt, a medium nitrogen methane compound, and an N-sulfonoxy quinone imine compound. The acid generator (P) can be used alone or in combination of two or more types -50-201243496. The above key salt is preferably a compound represented by the following formula (b1). M + L' (bl) In the above formula (bl), M + is a monovalent gun cation. L_ is a monovalent anion 〇 The above sulfonium salt is, for example, an iodide salt, a phosphonium salt, a phosphonium salt, a diazo salt, a pyridine salt or the like. Among them, from the viewpoint of obtaining a more excellent sensitivity, a phosphonium cation (anthracene cation) containing a sulfur atom and a phosphonium cation (iodine cation) containing an iodine atom are preferable. The monovalent phosphonium cation represented by M + in the above formula (b1) is, for example, a cation represented by the following formula (bl-Μ-Ι), a cation represented by the following formula (bl-M-2), or the like. [Chem. 2 2] R32 R33—s+—R31 (b1-M-1) In the above formula (bl-Ml), R31, R32 and R33 are each independently a linear one having a carbon number of 1 to 10 which may be substituted or A branched alkyl group or an aryl group having 6 to 18 carbon atoms which may be substituted. However, any two of R31, R32 and R33 are bonded to each other to form a cyclic structure together with the sulfur atom to which they are combined, and the remaining one may be substituted with a linear or branched chain having a carbon number of 1 to 10. An alkyl group or an aryl group having 6 to 18 carbon atoms which may be substituted. -51 - 201243496 [Chem. 2 3] R35-J+-R34 (b1-M-2) In the above formula (bl-M-2), 'R34 and R35 are each independently a carbon number which can be substituted 1~1〇 A linear or branched alkyl group or an aryl group having 6 to 18 carbon atoms which may be substituted. However, R34 and R35 are bonded to each other to form a cyclic structure together with the iodine atoms to which they are combined. The linear or branched alkyl group having an unsubstituted carbon number of 1 to 1 in the above formula (bl-Μ-Ι) and the formula (bl-M-2), for example, a methyl group, an ethyl group, or a η -propyl, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, and the like. The alkyl group may have a substituent such as a halogen atom containing fluorine, chlorine, bromine, iodine or the like, a hydroxyl group, a thiol group, and a hetero atom (for example, a s-atom atom, an oxygen atom, a nitrogen atom, a sulfur atom 'a phosphorus atom) , anthracene atom, etc.). The non-substituted aryl group having 6 to 18 carbon atoms in the above formula (bl-Μ-Ι) and (bl-M-2) may, for example, be a phenyl group or a naphthyl group. The aryl group may have a substituent 'for example, a halogen atom containing fluorine, chlorine, bromine, iodine or the like, a hydroxyl group 'hydrothio group, an alkyl group and a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom) An organic group such as a phosphorus atom or a ruthenium atom. The monovalent gun cation represented by the above M + is preferably a phosphonium cation, more preferably a triarylsulfonium cation. More preferably, it is a triphenylphosphonium cation. The cation moiety of the valence gun represented by M + in the above formula (bl) is synthesized according to a known method described in, for example, Advances in Polymer Sciences, Vol. 62, p. 1-48 (1984). -52-201243496 The following formula: The monovalent anion represented by L_ in the above formula (b1) is, for example, an anion represented by (bl-L-Ι)~(bl-L-4). Among them, an anion represented by (bl-L-Ι) or (bl-L-2) is preferred. [化2 4] ro=s^oL N (b1-L-1)Io=s=o I R37 0R40—S1 o °=S=〇--C~ n I 〇=S=〇R39 (b1-L -2) R41CnF2nS03&quot; (b1-L-3) R42S03&quot; (b1-L-4) In the above formula (bl-L-1), 'R36 and R37 are each independently a fluorine having at least one fluorine atom. ~20 alkyl. However, r3&lt; combines to form a carbon number of 1 to 20 having at least one fluorine atom. In the above formula (bl-L-2), 'R38, R39 and R4 are each an alkyl group having at least one fluorine atom and having 1 to 20 carbon atoms. However, any two of R3 8 and R4Q are bonded to each other to form a cyclic structure having at least one fluorine number of 1 to 20, and the remaining one may be an alkyl group having at least one carbon number of 1 to 20. In the above formula (bl-L-3) and formula (bl-L-4), RW and r42 are a fluorine atom or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted. The integer. Atom or; and the ring of R37 is a carbon atom having R39 and a sub-generator, respectively, 1~1 0 -53- 201243496 having at least 1 in the above formulas (bl-Ll) and (bl-L-2) The alkyl group having 1 to 20 carbon atoms of a fluorine atom is, for example, methyl, ethyl, η-propyl, "propyl, η-butyl, 2-methylpropyl' 1-methylpropyl, t a group in which at least one hydrogen atom of an alkyl group such as a butyl group may be substituted by a fluorine atom, etc. Specific examples of the onium salt are triphenylsulfonium trifluoromethanesulfonate, triphenyl mirror, nonafluoro-η- Butane sulfonate, triphenylsulfonium benzene sulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium η-octane sulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate Acid salt, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2-(tetracyclic [4.4.0.12'5.17, 1Q]dodecane-8-yl)ethanesulfonate, triphenylsulfonium 1,1-difluoro-2-(bicyclo[2.2.1]heptan-2-yl)ethanesulfonate, three Phenylhydrazine 1,2-bis(cyclohexyloxycarbonyl)ethane-1-sulfonate, triphenylsulfonium 1,2-bis(norpodooxycarbonyl)ethane-1·sulfonate, three benzene 1,2-bis(tetrahydropyranyloxycarbonyl)ethane-1-sulfonate, triphenylsulfonium 1,2-bis(2.heptyloxycarbonyl)ethane-1-sulfonate; (4-t-butoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, (4_t-butoxyphenyl)diphenylphosphonium nonafluoro-η-butanesulfonate, (4-t -butoxyphenyl)diphenylphosphonium perfluoro-η-octanesulfonate, (4-t-butoxyphenyl)diphenylphosphonium 10-camphorsulfonate, (4-hydroxyphenyl) Diphenylphosphonium trifluoromethanesulfonate, (4-hydroxyphenyl)diphenylphosphonium hexafluoro-n-butane sulfonate, (4-hydroxyphenyl)diphenylphosphonium perfluoro-η-octyl Alkane sulfonate, (4-hydroxyphenyl)diphenylphosphonium 10-camphorsulfonate, (4-hydroxyphenyl)diphenylphosphonium octane sulfonate, ginseng (4-methoxybenzene) Base) 锍trifluoromethanesulfonate, ginseng (4-methoxyphenyl)phosphonium hexafluoro-η-butane sulfonate, ginseng (4-methoxyphenyl) fluorene-fluorine-xinxin Acid salt, ginseng (4-methoxyphenyl) 镝1〇_camphorsulfonate, (4-fluorobenzene-54-201243496-based) diphenylsulfonium trifluoromethanesulfonate, (4. fluorophenyl) Diphenylphosphonium hexafluoride _ η- Butane sulfonate, (4-fluorophenyl)diphenylphosphonium 10-camphorsulfonate: ginseng (4-fluorophenyl)phosphonium trifluoromethanesulfonate, ginseng (4-fluorophenyl) quinone Fluoro-η-butane sulfonate, ginseng (4-fluorophenyl) mirror 10-camphorsulfonate, ginseng (4-fluorophenyl) 锍ρ_toluenesulfonate, ginseng (4-trifluoromethyl) Phenyl) fluorinated trifluoromethanesulfonate&gt; 2,4,6-trimethylphenyldiphenylphosphonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylphosphonium 2 ,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenyl mirror 4-trifluoromethylbenzene-propionate; diphenyl-trifluoromethane compound, diphenyl Based on nonafluoro-n-butane sulfonate, diphenylphosphonium perfluoro-η-octane sulfonate, diphenyliodonium 10-camphorsulfonate, diphenyl η-octane sulfonate , bis(4-t-butylphenyl) chain trifluoromethanesulfonate, bis(4-t-butylphenyl)# quinodifluoro-n-butane sulfonate, double (4-1_ Butylphenyl) chain perfluoro-noctane sulfonate, bis(4-t-butylphenyl)iodo 10_camphorsulfonate, bis(4 + butylphenyl) Yao η-octyl sulphate Salt, (4-methoxyphenyl)phenyl iodide difluoromethanesulfonate Acid salt, (4-methoxyphenyl)phenyl iodide nonafluoro-η·butyl sulfonate, (4-methoxyphenyl)phenylhydrazine perfluoro-η-octane sulfonate, 4-fluorophenyl)phenylindole trifluoromethanesulfonate, (4-fluorophenyl)phenyl-n-nonafluoro-η-butanesulfonate '(4-fluorophenyl)phenylindole 1〇- Camphorsulfonate, • bis(4-fluorophenyl)phosphonium trifluoromethanesulfonate, bis(4-fluorophenyl) town, nonafluoro-n-butanesulfonate, bis(4-fluorophenyl) Town 1 〇- camphor salt; bis(4-chlorophenyl)iodotrifluoromethanesulfonate, bis(4-chlorophenyl)phosphonium hexafluoro-η-butane sulfonate, bis(4·chloro Phenyl) fluorene perfluorooctane salt, c -55 - 201243496 bis(4-chlorophenyl) η-laurylbenzenesulfonate, bis(4-chlorophenyl)iodo 10-camphorsulfonate , bis(4-chlorophenyl)鐄η-octane sulfonate, bis(4-chlorophenyl)phosphonium 4-trifluoromethylbenzenesulfonate, bis(4-chlorophenyl)iodoperfluorobenzene Sulfonic acid salt; bis(4-trifluoromethylphenyl)phosphonium trifluoromethanesulfonate, bis(4-trifluoromethylphenyl)phosphonium nonafluoro-n-butanesulfonate, double (4- Trifluoromethylphenyl)phosphonium perfluorene-η-octyl Sulfonate, bis(4-trifluoromethylphenyl)-locked η-laurylbenzenesulfonate, bis(4-trifluoromethylphenyl)-p-toluenesulfonate, bis(4-trifluoro) Methylphenyl)iodobenzenesulfonate, bis(4-trifluoromethylphenyl)indole 10-camphorsulfonate, bis(4-trifluoromethylphenyl)iodo-octanesulfonate, Bis(4-trifluoromethylphenyl)zhen 4-trifluoromethylbenzenesulfonate, bis(4-trifluoromethylphenyl) town perfluorobenzenesulfonate: the following formula (2χ-1) ~(2χ-43) indicates a compound or the like. -56- 201243496 【化2 5

S03 F3C (2x-1)

(2x-2)

S. -57- 201243496 【化2 6】

(2x-5)

C8F17SO3 (2x-6)

(2x-7)

(2X-8) -58- 201243496 [Chem. 2 7]

(2x-9)

(2x-10)

(2x-12) -59- 201243496 【化2 8】

(2x-13) (2X-14) (2x-15) [Chem. 2 9]

(2X-16)

(2x-17)

(2x-18) -60 - 201243496 【化3 0】

(2x-19)

(2x-20)

^ 〇wp ο,ρ F3〇_S—C 'S_CF3 〇—=〇 cf3 (2x-21)

S -61 - 201243496 【化3 2

〇2 /S_Cf2f3c-s - c; (2X-25) d^F2

Or

〇,, /? f202 /s-cf2 f3c-c-s -q pF2 cf2 (2X-26)

C2F5m°t° ‘〇T〇 C2F5 (2x-27)

【化3 3

CF3o=s=o I N— 〇=♦=〇 CF3 (2X-28)

?4f9o=s=o N-o=s=o C4F9 (2X-29)

-62- 201243496 【化3 4

S03

S’+ F3C-SO3

6) -3 (2X £ 63 201243496 [Chemical 3 5

Cf3 0=S=0 Ν' o=s two Ο CF3

(2X-39)

(2x-40>

O- among these key salts, preferred are triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-η-butanesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenyl 1,2-bis(cyclohexyloxycarbonyl)ethane-1-sulfonate, triphenylsulfonium 1,2-bis(norpodooxycarbonyl)ethane-1-sulfonate, triphenyl 1,2-bis(tetrahydropyranyloxycarbonyl)ethane-1-sulfonate, triphenylsulfonium 1,2-bis(2-heptyloxycarbonyl)ethane-bupropionate, 4-hydroxyphenyl)diphenylsulfonium trifluoromethanesulfonate-64- 201243496 acid salt, (4-hydroxyphenyl)diphenylphosphonium nonafluoro-n-butanesulfonate, ginseng (4-methoxyl) Phenyl) mirror trifluoromethanesulfonate, ginseng (4-methoxyphenyl)phosphonium nonafluoro-η-butanesulfonate, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonate , (4-fluorophenyl)diphenylphosphonium hexafluoro-η-butane sulfonate, 2,4,6-trimethylphenyldiphenylphosphonium trifluoromethanesulfonate, 2,4,6 -trimethylphenyldiphenylphosphonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylphosphonium 4-trifluoromethylbenzenesulfonate, diphenyl Locked trifluoromethanesulfonate, diphenyliodonium hexafluoro-η- Butane sulfonate, diphenyl hydride 10-camphor sulfonate, bis(4-t-butylphenyl) argon trifluoromethane sulfonate, bis(4-t-butylphenyl) town hexafluoro -η-butane sulfonate, bis(4-t-butylphenyl)indole 10-camphorsulfonate, (4-fluorophenyl)phenylphosphonium trifluoromethanesulfonate, (4-fluorobenzene) Phenyl quinone nonafluoro-η-butane sulfonate, (4-fluorophenyl)phenyl pin 10-camphorsulfonate, bis(4-fluorophenyl)-locked trifluoromethanesulfonate, double (4-fluorophenyl)phosphonium hexafluoro-η-butane sulfonate, bis(4-fluorophenyl)phosphonium 10-camphorsulfonate, ginseng (4-trifluoromethylphenyl) mirror trifluoromethane Sulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2-(tetracyclo[4·4·0·12, 5.17'Ι()]dodecane-8-yl)ethanesulfonate Acid salt, triphenylsulfonium 1,1-difluoro-2-(bicyclo[2.2.1]heptan-2-yl)ethanesulfonate; the above formula (2x-13) ' (2x-16) &gt ; (2x_17), (2x-18), (2x-19), (2x-20), (2x-27), (2x-28), (2x-29), (2x-31) ' (2x- 36), a compound represented by (2x-43), more preferably triphenylphosphonium 1,2-bis(cyclohexyloxycarbonyl)ethane-bupropionate, triphenylsulfonium 1,2- Bis(norpoxyloxycarbonyl)ethane-1-sulfonate, triphenylsulfonium 1,2-bis(tetrahydropyranyloxycarbonyl)ethane-1-sulfonate, triphenylsulfonium I, 2-bis(2-heptyloxycarbonyl)ethane-1-sulfonate. -65- 201243496 The above diazomethane compounds are, for example, bis(trifluoromethanesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(3,3-dimethyl-1,5- Dioxo[5.5]dodecane-8-sulfonyl)diazomethane, bis(1,4-dioxo[4.5]decane-7-sulfonyl)diazomethane, bis(t-butyl) Among these diazomethane compounds, bis(cyclohexylsulfonyl)diazomethane and bis(3,3-dimethyl-1,5-dioxospiro) are preferred. 5.5] Dodecane-8-sulfonyl)diazomethane, bis(1,4-dioxospiro[4.5]decane-7-sulfonyl)diazomethane. The aforementioned N-sulfodeoxyquinone imine compound, for example, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N- (Trifluoromethylsulfonyloxy)·7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(trifluoromethylsulfonyloxy)bicyclo[ 2.2.1] heptane-5,6-oxo-2,3-dicarboxyarminemine; N-(10-camphorsulfonyloxy) amber imine, N-(10-camphorsulfonyloxy) Phthaloin imine, N-(10-camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(10- Camphor sulfonate oxy)bicyclo[2_2.1]heptane-5,6-oxo-2,3-dicarboxy quinone imine, N-(10-camphorsulfonyloxy)naphthyl quinone imine, N- [(5-Methyl-5-carboxymethylbicyclo[2.2.1]heptan-2-yl)sulfonyloxy] succinimide; N-(n-octylsulfonyloxy)bicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, N-(n-octylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3- Dicarboxy quinone imine, N-(perfluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(perfluorophenyl sulfonate Base)-7 · -66- 201243496 oxa bicyclo [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(perfluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5 ,6-oxo-2,3-dicarboxy quinone imine 'N-(nonafluoro-η-butylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine, N-(nonafluoro-η-butylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N_(nonafluoro-η- Butylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyarliminide; Ν-(perfluoro-η-octylsulfonyloxy)bicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, fluorene-(perfluoro-η-octylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine, N-(perfluoro-η·octylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxy quinone imine, etc. . These bismuth-sulfonyloxy quinone imine compounds are preferably Ν-(trifluoromethylsulfonyloxy)bicyclo[2·2·1]hept-5-ene-2,3-dicarboxy quinone imine , Ν-(10-camphorsulfonyloxy) succinimide ' Ν-[(5-methyl-5-carboxymethylbicyclo[2.2.1]heptan-2-yl)sulfonyloxy]amber Yttrium. The content of the acid generator (Ρ) is preferably 0.1 part by mass to 5 parts by mass, more preferably 0.5 part by mass to 50 parts by mass, per part by mass of the polymer (Ϊ). When the content of the acid generator (Ρ) is less than 0.1 part by mass, the sensitivity and developability may be lowered. On the other hand, when the content exceeds 50 parts by mass, the transparency to the radiation, the shape of the pattern, the heat resistance, and the like may be lowered. [Acid Diffusion Control Agent] In addition to the above polymer (I) and the acid generator, the above-mentioned photoresist composition preferably further contains an acid diffusion controlling agent (hereinafter also referred to as an acid diffusion controlling agent (Q)). The acid diffusion controlling agent (Q) is controlled by exposure of an acid generator (Ρ) or the like by exposure.

C -67- 201243496 The diffusion phenomenon of the acid which is diffused into the photoresist film has a function of suppressing an undesirable chemical reaction in the unexposed portion. The acid diffusion controlling agent (Q) may, for example, be a nitrogen-containing organic compound or a photosensitive basic compound. The nitrogen-containing organic compound is, for example, a compound represented by the following formula (Q1) (hereinafter also referred to as "nitrogen-containing compound (i)"), and a compound containing two nitrogen atoms in the same molecule (hereinafter also referred to as "nitrogen-containing compound"). (ii)"), a polyamine compound or a polymer having three or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (iii)"), a compound containing a guanamine group, a urea compound, a nitrogen-containing heterocyclic ring Compounds, etc. [Chem. 3 6] R43 R44—N—R45 (Q1) In the above formula (Q1), R43, R44 and R45 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted. An aryl group which may be substituted or an aralkyl group which may be substituted. The nitrogen-containing compound (1) may, for example, be a mono(cyclo)alkylamine such as η-hexylamine, η-heptylamine, cardinamine, η-decylamine, η-decylamine or cyclohexylamine: di-n-butylamine, ~ η-pentylamine, di-η-hexylamine, di-η-heptylamine, di-η-octylamine 'di-dioxime, di-η-decylamine, cyclohexylmethylamine, dicyclohexylamine Equivalent di(cyclo)alkylamines; —Bene, di-η-propylamine, tri-η-butylamine, tri-η-pentylamine, tris-n-hexylamine, —η-heptylamine, tri-n Tris(cyclo)alkylamines such as octylamine, tri-n-decylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine Aniline, hydrazine-methylaniline, hydrazine, hydrazine-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenyl-68-201243496 amine, An aromatic amine such as diphenylamine, naphthylamine, 2,4,6-tris-461-butyl-]-methylaniline, N-phenyldiethanolamine or 2,6-diisopropylaniline. The above nitrogen-containing compound (ii) is, for example, ethylenediamine, ν, ν, ν'ν, -tetramethylethylenediamine, butanediamine, hexamethylenediamine, 4,4,-diaminodiphenylmethane, 4,4'--amino-mono-hydroxy ether, 4,4'-diaminobenzophenone, 4,4,-diaminodiphenylamine, 2,2-bis(4-aminophenyl) Propane, 2-(3-aminophenyl) 2_(4-aminophenyl)propene, 2-(4-aminophenyl)_2-(3-propionylphenyl)propyl, 2-(4) -aminophenyl)-2-(4-hydroxyphenyl)propane, anthracene, 4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, 1,3-bis[1] · (4. Aminophenyl)·ι·methylethyl]benzene, bis(2-dimethylaminoethyl)ether bis(2-diethylaminoethyl)ether, 1-( 2 -transethylidene)_2_imiprolinone, 2-quinoquinoxaline, N,N,N',N'-indole (2-hydroxypropyl)ethylenediamine, n,N,N, , N',, N,, -pentamethyldiethyltriamine, and the like. The nitrogen-containing compound (iii) may, for example, be a polymer of polyethyleneimine, polyallylamine or 2-dimethylaminoethyl acrylamide. The above-mentioned compound containing a guanamine group, for example, Nt-butoxycarbonyldi-η-octylamine, Nt-butoxycarbonyldi-n-decylamine, _N-t-butoxycarbonyldi-η- Mercaptoamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl- N-methyl-1-adamantylamine, (S)-(-)-l-(t-butoxycarbonyl)-2-pyrrolidinemethanol, (R)-( + )-l-(t- Butoxycarbonyl)-2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxydecylpiperazine, N,N - t· Butoxyl-l-Glycolylamine, N,N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butyl

C-69- 201243496 oxycarbonyl-4,4'-diaminodiphenylmethane, n,N'-di-t-butoxycarbonylhexamethylenediamine, N,N,N'N'-tetra- T-butoxycarbonylhexamethylenediamine, N,N'-di-t-butoxycarbonyl-1,7-diaminoheptane, hydrazine, Ν'·di-t-butoxycarbonyl-1, 8-Diaminooctane, N,N'-di-t-butoxycarbonyl-1,9-diaminodecane, anthracene, Ν'-di-t-butoxycarbonyl-1,10- Diamino decane, hydrazine, Ν'-di-t-butoxycarbonyl-1,12-diaminododecane, N,N'-di-t-butoxycarbonyl-4,4'- Containing diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, etc. In addition to the Nt-butoxycarbonylamino compound, for example, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-ethinyl-1-adamantylamine, trimeric isocyanate (2-hydroxyethyl) Ester). The above urea compound may, for example, be 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. The above nitrogen-containing heterocyclic compound is, for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole 'benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole 'Imidazoles such as benzyl-2-methyl-1H-imidazole; pyridine, 2 ·methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine '2-phenylpyridine, 4- Phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid 'nicotinic acid decylamine, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ' : 6 ', 2 ''-tetrapyridine and the like pyridines: piperazine, 1-(2-hydroxyethyl) piperazine and other piperazines, such as pyridoxine, pyrazole, pyridazine, quinazoline Porphyrin-70- 201243496 '嘌呤, pyrrolidine, piperidine, piperidine ethanol, 3-hexahydropyridine-1,2-propanediol, morphine, 4-methylmorphine, 1 -. (4 - morphinyl) Ethanol, 4-ethionylmorpholine, 3-(N-morpholino)-1,2-propanediol, 1,4-dimethylpiperazine, 1,4-dioxabicyclo[2.2.2]octane Wait. The photosensitive basic compound is a component which is partially decomposed by exposure and loses alkalinity, and the unexposed portion is not decomposed and remains directly. Such a photosensitive test compound can effectively utilize the acid generated in the exposed portion (exposure region) as compared with the non-photosensitive anthraquinone compound, so that the sensitivity can be further improved. The photosensitive basic compound is not particularly limited as long as it has the above properties. Specifically, for example, there are a compound represented by the following formula (Q2-1) or formula (Q2-2). [化3 7

R49

I+ G R50 (Q2-2) The above formula (Q2-1) and formula (Q2-2) are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a carbon number of a substituent, and may have a substituent. An alicyclic hydrocarbon group, -〇S〇2_Re group, or _s〇2_Rd group. R and Rd are each independently an alkyl group having 1 to 1 (1) carbon atoms which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.

S -71 - 201243496 Ε· is OH·, R51〇·, or R51COO·. R51 is a monovalent organic plug. R46 to R48 in the above formula (Q2-1) may be all the same or different. R49 and R5G in the above formula (Q2-2) may be the same or in the above-mentioned R46 to R5Q and R/ and Rd, and the carbon number is 1 to 10, such as methyl, ethyl, η-butyl, tert-butyl. 'Trifluoromethyl, the substituent of this alkyl group, for example, alkoxy group having a hydroxyl group, a carboxyl group, a fluorine atom, a halogen atom, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or the like, t-butyl The alkoxy group such as an oxycarbonylmethoxy group is the above R46 to R513 and 11. And an alicyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, adamantyl, tricyclodecyl, tetracyclododecyl or the like. The substituent of the cyclic hydrocarbon group is, for example, the same as those exemplified as the substituent of the alkyl group of the above R46 to R5. The halogen atom represented by the above R46 to R5Q may, for example, be a fluorine atom, a bromine atom or an iodine atom. Examples of the aryl group represented by the above formulas and Rd include a phenyl group, a methylphenyl group, a trimethylphenyl group, a naphthyl group, a methylnaphthyl group, a dimethylnaphthalene group, a methyl fluorenyl group, a dimethyl fluorenyl group and the like. The substitution for the aryl group is the same as that of the above-mentioned alkyl group having 1 to 1 ring of carbon represented by R46 to R5G. Among the above R46 to R5Q, a hydrogen atom and a t-butyl group are preferred. Among the above Re and Rd, a cyclohexyl group, a phenyl group, and a methyl group are preferable. The monovalent organic group represented by the above R51 may have, for example, a partial or all three. Alkyl, examples, etc. Instead of a bromine atom or the like, a t-butoxycarbonyl group or the like. , for example, having a fluorenyl group, a carbon number which is substituted for the bristles, a chlorophenyl group, a diyl group, a fluorenyl group, for example, a group of a substituent, a -34-201243496 alkyl group of a trifluoro substituent, which may have a substitution Base aryl and the like. The above L_ is preferably OH-, CH3COO, and an anion represented by the following formula (Q2_an~(Q2 a5). [Chem. 3 8] coo~

(Q2-a3)

COO

COO

F3C (Q2-a1)

OH COO (Q2-a4) (Q2-a2)

Specific examples of the photosensitive basic compound include a triphenylsulfonium compound (a compound represented by the above formula (Q2-1)). The anion portion (E) has, for example, 〇", CH3COCT, or the above formula (Q2-1) or Q2-3) indicates an anion or the like. The content of the acid diffusion controlling agent (Q) is preferably 30 parts by mass or less based on 100 parts by mass of the polymer (1), more preferably 0.001 parts by mass to 30 parts by mass, still more preferably 0.005 parts by mass to 15 parts by mass. Share. When the content of the acid diffusion controlling agent (Q) exceeds 30 parts by mass, the sensitivity of the formed photoresist film or the developability of the exposed portion may be lowered. On the other hand, when the content is less than 0.001 part by mass, the rectangularity or dimensional fidelity of the pattern shape of the formed resist pattern may be lowered depending on the process conditions. The acid diffusion controlling agent (Q) may be used singly or in combination of two or more.

C-73-201243496 [Solvent] The above-mentioned photoresist composition usually contains a solvent (hereinafter also referred to as "solvent (R)"). The solvent is not particularly limited as long as it can dissolve or disperse the polymer (1), the acid generator (P), the acid diffusion controlling agent (Q), and other components described later. The solvent (R) is, for example, the same solvent as that exemplified for the [C] solvent in the ruthenium-containing film-forming composition for a multilayer photoresist process. The solvent (R) is preferably an ester solvent or a ketone solvent, more preferably a carboxylate solvent, a polyol partial ether solvent, a carboxylic acid ester solvent of a polyol partial ether, a lactone solvent, or a chain. The ketone solvent and the cyclic ketone solvent are more preferably a carboxylic acid ester solvent or a carboxylic acid ester solvent of a polyol partial acid, particularly preferably propylene glycol monoalkyl ether acetate or lactate, and particularly preferably propylene glycol. Methyl ether acetate, ethyl lactate. [Other components] The photoresist composition may further contain a surfactant, a sensitizer, an aliphatic additive or the like as an additional component, if necessary. [Embodiment] [Examples] Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited to the examples. Further, in the present embodiment, the EB (electron line) is used for exposure of the photoresist film, but even if short-wavelength radiation such as EUV is used, the basic photoresist characteristics are similar and have a correlation with them. Various physical properties were determined according to the following methods. -74- 4 4201243496 [Mw and Μη] The Mw and Μ of the polymer were measured by the following conditions using a GPC column (G2000HXL 2, G3000HXL 1 , G4000HXL 1 , TOSOH).

Column temperature: 40 °C Solvent solvent: tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection amount: 1 〇〇μ L Detector: Differential refractometer standard Material: Monodisperse polystyrene PH-NMR analysis and 13C-NMR analysis] The structural analysis of the polymer was analyzed by 1H-NMR analysis and l3C-NMR analysis of a nuclear magnetic resonance apparatus (JNM-EX270, manufactured by JEOL Ltd.). [solid content concentration of polyoxyalkylene] The mass concentration of the polyaluminoxane solution was determined by calcining the polyaluminoxane solution 〇5g at 25 ° C for 30 minutes, and determining the solid concentration of the polyoxymethane solution (% by mass) ). &lt;[A] Synthesis of polyoxyalkylene&gt; [Synthesis Example 1] (Synthesis of polyoxyalkylene (A-1)) 1.28 g of oxalic acid was dissolved by heating in 12.85 g of water to prepare oxalic acid water.

C-75- 201243496 solution. Thereafter, a flask having 25.05 g of tetramethoxynonane, 3.63 g of phenyltrimethoxydecane, and 57.19 g of propylene glycol monoethyl ether was placed, and a cooling tube and a dropping funnel to which the above-prepared aqueous oxalic acid solution was added were placed. Subsequently, after heating to 60 ° C in an oil bath, the aqueous oxalic acid solution was gradually dropped, and the reaction was carried out at 60 ° C for 4 hours. After completion of the reaction, the flask to which the reaction solution was added was allowed to cool, and then placed in an evaporator to remove methanol formed by the reaction to obtain 97.3 g of a solution containing polyoxyalkylene (A-1). The solid content concentration in the obtained polyoxane-containing (A-1) solution was 18.0% by mass. Further, the obtained polyoxyalkylene (A-1) had a Mw of 2,000. &lt;Preparation of a ruthenium-containing film-forming composition for a multilayer photoresist process&gt; The [B] electron acceptor and [C] solvent for preparation of a ruthenium-containing film-forming composition for a multilayer photoresist process will be described below. [[B] electron acceptor] B-1 : 7,7,8,8-tetracyanoquinodimethane B·2 : triphenylsulfonium 2-hydroxy-4-trifluoromethylbenzoate (under Describe the compound represented by the mouth (B-2)) [Chem. 3 9]

(B-2) cf3 -76- 201243496 bl : Nt-pentyloxyalkyl-4-pyridylpiperidine b-2 : Nt-butoxycortyl-4-carbazide steep compound (b-Ι) And (b-2) is a substance which does not have an electron accepting function [[C] solvent] C-1: propylene glycol monomethyl ether acetate C-2: propylene glycol monoethyl ether [Example 1] (for multilayer photoresist process) Preparation of the ruthenium-containing film-forming composition (S-1)) A solution of (A-1) containing the [A] polyoxane obtained in the above Synthesis Example 4, 4_76 g, [B] electron acceptor (Bl) 0_043 g And [C] solvent (Cl) 29.23 g and (C-2) 69.3 7 g were mixed to prepare a ruthenium-containing film-forming composition (S-1) ° for the multilayer photoresist process [Examples 2 to 4 and Comparative Example 1 3] (Preparation of the sand-containing film-forming compositions (S-2) to (S-7) for the multilayer photoresist process) The same as in the first embodiment except that the components of the types and amounts shown in Table 1 below were used. The composition film (1_2)~(1_7) is formed by the ruthenium-containing film for modulating the multilayer photoresist process. -77- 1 201243496 r^ CO 卜cq CO CO 卜CO Bu CO amount (g&gt;〇&gt;ci&gt; d «0 ai &lt;〇a&gt;&lt;〇ai CD ai CO σί CO \ CO GO \ CO GO \ CO CO \ CO GO \ CO CD \ ς〇GO GO [C] Solvent\£&gt; CM 10 CM ui CM 10 CM ΧΩ IA CNI 1C&gt; CM CNJ | C4 | CM I CM 1 CM 1 CM 1 CM 1 骏 o V ovo Nv o V o \ a \ o , 1 \ r— 1 N yr— 1 , 1 &gt; 1 \ 1 , 1 oooooo 〇r·· gl S quantity (g) Ϊ.043 ).043 c&gt;c&gt; ) .043 ).043 1 ms S _1 pr dd Μ Ί 1 Type B-1 B_2 &gt; I JQ I 1 J3 CJ 1 1 1 QQ 1 ω sg Secret 11 3 &lt;D 4.76 CD CD g _ inch, xti &lt ;·Ν fritfrirtl r— I 1 1 1 r^· 1 ir— 1 1 w &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; πρ^ 8S§ S-1 S-2 S-3 S-4 ID 1 CO &lt;D 1 ¢0 S—7 ®5§ T- CJ CO inch r— CM CO Grip Grip ft ft ±2 -78- 201243496 &lt;Synthesis of Polymer (I)&gt; [ Synthesis Example 2] (Synthesis of Polymer (I_A)) 4.5 g of a monomer represented by the following formula (M-1) 35 mol%) and p-acetoxystyrene 5.5 g (65 mol%), 2,2'-azobis(isobutyronitrile) (AIBN) 0.4 g and t-lauryl mercaptan O. After lg was dissolved in propylene glycol monomethyl ether 10 g, the reaction vessel was stirred under nitrogen atmosphere while maintaining polymerization at 70 ° C for 16 hours. After the polymerization, the polymerization solution was dropped into 50 μg of n-hexane to solidify and purify the resulting polymer. Next, the obtained polymer was again dissolved in 7.5 g of propylene glycol monomethyl ether, and then 15 g of methanol, 4.0 g of triethylamine and 1.0 g of water were added, and the mixture was refluxed at the boiling point while the hydrolysis reaction was carried out for 8 hours. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the obtained polymer was dissolved in 10 g of acetone, and then added dropwise to 100 g of water to be solidified, and the resulting white powder was filtered and decompressed to 5 Torr. After drying overnight at ° C, a white powder of the polymer (Ι-A) was obtained (yield 68%). The polymer (Ι-A) had an Mw of 11, 〇〇〇' Mw/Mn of 2.3. Further, as a result of 13C-NMR analysis, the structural unit derived from the monomer (M-1) in the polymer (ΙΑ): the structural unit derived from P-hydroxyphenethyl group was 34.8: 65·2 (mole) %). [化4 0]

S-79-201243496 [Synthesis Example 3] (Synthesis of Polymer (Ι-B)) The monomer represented by the following formula (M-2): 4_66 g (35 mol%), p-ethyl oxy styrene 5.34g (65mol%), AIBN0.4g and t-lauryl mercaptan 〇.lg were dissolved in 10g of propylene glycol monomethyl ether, and the reaction pot was stirred under nitrogen atmosphere while maintaining 70 ° C, polymerization for 16 hours. After the polymerization, the polymerization solution was dropped into 500 g of n-hexane to solidify and purify the resulting polymer. Next, the obtained polymer was redissolved in 7.5 g of propylene glycol monomethyl ether, and then 15 g of methanol, 4·0 g of triethylamine and 1.0 g of water were added, and the mixture was refluxed at the boiling point while the hydrolysis reaction was carried out for 8 hours. After the reaction, the solvent and triethylamine were distilled off under reduced pressure. The obtained polymer was dissolved in 10 g of acetone, and then added dropwise to 100 g of water to be solidified. The resulting white powder was filtered, decompressed, and dried at 50 ° C. In the evening, a white powder of the polymer (IB) was obtained (yield 74.6%). This polymer (I-B) had an Mw of 9,600 and a Mw/Mn of 2.1. Further, as a result of 13C-NMR analysis, the structural unit derived from the monomer (M-2) in the polymer (IB): the content ratio of the structural unit derived from p-hydroxyphenethyl group was 35.2: 64.8 (mole. 4 1]

Ο (M-2)

-80-201243496 [Synthesis Example 4] (Synthesis of Polymer (I_C)) The monomer represented by the following formula (M-3) is represented by 5.29 g (30 mol%) and the following formula (M-4). 2.22 g (15 mol%) of monomer, 7.49 g (55 mol%) of p-acetoxystyrene, 0.83 g of AIBN and t-lauryl mercaptan, 3 g of 22.5 g of propylene glycol monomethyl ether Thereafter, the reaction vessel was stirred while maintaining a polymerization temperature of 70 ° C for 16 hours under a nitrogen atmosphere. After the polymerization, the polymerization solution was dropped into 75 g of η·hexane to solidify and purify the resulting polymer. Next, the obtained polymer is redissolved in propylene glycol monomethyl ether l〇.〇g, and then methanol 20 g, triethylamine 6 · 0 g, and water 1.5 g are added, and the mixture is refluxed at the boiling point, and the hydrolysis reaction is carried out. It takes 8 hours. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the obtained polymer was dissolved in 15 g of acetone, and then added dropwise to 150 g of water to be solidified, and the resulting white powder was filtered, decompressed, and dried at 50 ° C. In the evening, a white powder polymer (Ι-C) was obtained (yield 71.3%). This polymer (Ι-C) had an Mw of 7,800 and a Mw/Mn of 2.2. Further, the result of 13C-NMR analysis is 'structural unit derived from the monomer (.3) in the polymer (Ι-C): the structural unit derived from (M-4): each of the structural units derived from ρ-hydroxyphenethyl The ratio is 30.2 : 14.8 : 55.0 (mole [4 4]

S-81 - 201243496 [Synthesis Example 5] (Synthesis of Polymer (ID)) The monomer represented by the following formula (M-5): 6.21 g (30 mol%), and the monomer represented by the following formula (M_6) 3.99 g (15 mol %), p-acetoxystyrene 7.49 g (55 mol %), AIBN 0.83 g and t-lauryl mercaptan. 3 g dissolved in propylene glycol monomethyl ether 22.5 g 'nitrogen The reaction vessel was stirred while maintaining a temperature of 70 ° C for 16 hours. After the polymerization, the polymerization solution was dropped into 750 g of n-hexane to solidify and purify the resulting polymer. Next, the obtained polymer was redissolved in 1 〇〇g of propylene glycol monomethyl ether, and 20 g of methanol, 6.0 g of triethylamine, and 1.5 g of water were added, and the mixture was refluxed at the boiling point while the hydrolysis reaction was carried out for 8 hours. . After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the obtained polymer was dissolved in 15 g of acetone, and then dropped into water of i50 g to be solidified. The resulting white powder was filtered, decompressed, and dried at 50 ° C. Late, a white powdery polymer (Ι-D) was obtained (yield 69.3%). The polymer (Ι-D) had an Mw of 8,100 and a Mw/Mn of 2·2. Further, as a result of 丨3C-NMR analysis, the structural unit derived from the monomer (]^-5) in the polymer (Ι-D): the structural unit derived from (M-6): the structure derived from P-hydroxyphenethyl The ratio of each unit is 39·8: 20.4: 39.8 (% by mole). [化4 3]

-82-201243496 &lt;Preparation of Photoresist Composition&gt; An acid generator (p), an acid diffusion control agent (Q), and a solvent (R) for modulating a photoresist composition will be described below. [Acid generator (P)] P-ι: Triphenylsulfonium 1,2-bis(cyclohexyloxycarbonyl)ethane-1-sulfonate (compound represented by the following formula (P-1)) P -2: triphenylsulfonium 1&gt; 2_bis(norpodooxycarbonyl)ethane-hydrazine-sulfonate (compound represented by the following formula (P·2)) P-3: triphenylphosphonium-- Bis(tetrapyranyloxycarbonyl)ethane-b sulfonate (compound represented by the following formula (P-3)) &quot;•diphenylanthracene, 2_bis(2-heptyloxycarbonyl)B Alkyl-1-sulfonate (a compound represented by the following formula (P-4)) [Chemical 4 4]

C -83- 201243496 【化4 5】

(P-2)

-84- 201243496 【化4 7】

[Acid Diffusion Control Agent (Q)] Q-1: Triphenylsulfonium 2-hydroxy-4-trifluoromethylbenzoate (compound represented by the following formula (Q-1)) [Chem. 4 8]

(Q-1) [Solvent (R)] R-1: Propylene glycol monomethyl ether acetate R-2: Ethyl lactate [Preparation of preparation example 1 (photoresist composition U-1)) The above synthesis example 2 obtained polymer (I) (IA) 1.60g, acid yield -85-201243496 green agent (P) (Pl) 0.3 52g, acid diffusion inhibitor (q) (q_1) 〇〇 53〇g and The solvent (R) (Rl) 68.6 g and (R-2) 29.4 g were mixed. The prepared mixed solution was filtered using a filter having a pore size of 0·45 μm to obtain a photoresist composition (J-1). [Preparation Examples 2 to 8] (Modulation of Photoresist Compositions (J-2 to J-8)) A photoresist composition was obtained in the same manner as in Preparation Example 1 except that each component of the type and amount shown in Table 2 below was used. (J-2) ~ (J-8). -86- 201243496 3 σ&gt; 5 s 5 &lt;VJ CN Ol Μ Ol g 蘅CO GO CD CD CO CO &lt;0 cd CO &lt;D od &lt;D &lt;〇οϋ CD CO GD CD CD G0 CD cd cd CO . bond OJ I Ol 1 1 CM 1 Csl I 1 CM I 1/R-2 species Ct general TT 1 T 1 1 I 1 Q: Q: OC QL Ο: cr a: a: 1 m gH 4(g) 0.0508 0.0505 0,0507 0.0499 0.0507 0.0507 0,0507 0.3009 骏 t— r— wake up! 1 1 1 1 1 I 1 Zhao face o σ o σ σ oo σ S m quantity (g) 0,4178 0.4277 0.4195 0,4431 0.4195 0.4195 0.4195 0.3642 Species P-1 CM 1 €L P-4 Ρ-1 P-1 P-1 P-1 Amount (g) in 〇% GO σ&gt; o αο 〇&gt; GO σ&gt; GO O) 8 Rong &lt ;Π CO va * CM ID r OJ u*&gt; sr οι ΙΟ CM U) » CM U!) 4 CO CO *· Accounts &lt;&lt;&lt;&lt;&lt; ω 〇ao ilwri P 1 1 1 1 1 II 1 Photoresist composition t- CM CO inch ΙΟ CD Bu CO 1 1 1 1 -&gt; 1 I &quot;3 I l CM CO inch ΙΟ iO 卜 CO Cui Guo mm W1 m W1 turn m pin m wn pg n»3 Dirty i!m 鼷bjar im

V-87-201243496 &lt;Formation of ruthenium-containing film&gt; The ruthenium-containing film-forming composition for multilayer photoresist processes obtained in the above Examples 1 to 4 and Comparative Examples 1 to 3 was applied to ruthenium by spin coating method. On the wafer. For the spin coating, a coating/developing device (CLEAN TRACK ACT8, manufactured by Tokyo Denki Co., Ltd.) (the same as those described below) is used. With respect to the obtained coating film, PB was performed on a hot plate at 22 ° C for 1 minute to form a ruthenium-containing film. The film thickness of the obtained ruthenium-containing film was measured to be 15 nm using a film thickness measuring device (M-2000D, manufactured by J.A. Woollam). &lt;Evaluation&gt; Using the above-described ruthenium-containing film formed as described above, the composition of the sand-containing film for forming a multilayer photoresist process (s-1) to (S-7) and the photoresist composition obtained by the above preparation example (J) -1) ~ (J-8), various evaluations were performed according to the following methods. The evaluation results are shown in Table 3. [Oxygenation resistance] The ruthenium-containing film obtained above was subjected to eh treatment at 100 W for 120 seconds using an ashing apparatus (NA1300, manufactured by ULVAC), and the film thickness difference before and after the treatment was measured. When the difference between the two was less than 5 nm, the oxygen ashing resistance was evaluated as "good", and when it was 5 nm or more, it was evaluated as "B" (bad). [Micro-image evaluation] (Formation of photoresist pattern) [Example 5] -88 - 201243496 After the anti-reflection film forming material (manufactured by HM8006 or JSR) was spin-coated on an 8-inch wafer, it was carried out at 250 °C. Baking (PB) for 60 seconds, forming an anti-reflection film having a film thickness of 100 nm. The ruthenium-containing film-forming composition (S-1) was spin-coated on the anti-reflection film, baked at 220 ° C for 60 seconds, and then cooled at 23 ° C for 60 seconds to form a film thickness of 15 nm. Containing enamel film. Next, the photoresist composition (J-1) prepared above was spin-coated on a ruthenium-containing film, and after 60 seconds of PB at 130 ° C, it was cooled at 23 ° C for 30 seconds to form a photoresist film having a film thickness of 50 nm. . [Examples 6 to 14 and Comparative Examples 4 to 6] A photoresist film was formed in the same manner as in Example 5 except that the composition for forming a ruthenium-containing film for a multilayer photoresist process and the photoresist composition were as shown in Table 3 below. . [Comparative Example 7] The organic anti-reflection film forming composition (DUV42, manufactured by Nissan Chemical Co., Ltd.) was spin-coated on an 8-inch wafer, and then baked (PB) at 205 ° C for 60 seconds to form a film thickness of 60 nm. Anti-reflection film. Next, the above-prepared photoresist composition (J-1) was spin-coated on the anti-reflection film, baked at 130 ° C for 60 seconds, and then cooled at 23 ° C for 30 seconds to form a film having a film thickness of 50 nm. Resistor film [Comparative Example 8] After applying hexamethyldioxane to an 8 Å wafer, the above-prepared photoresist composition (J-1) was spin-coated on a wafer at 130 ° C. After baking-89-201243496 baking (PB) for 60 seconds, it was cooled at 23 ° C for 30 seconds to form a photoresist film having a film thickness of 50 nm. Each of the resist films formed as described above was irradiated with an electron beam using an electron beam drawing device (HL800D, manufactured by Hitachi, Ltd., output: 50 KeV, current density: 5.0 amp/cm 2 ). After the irradiation of the electron beam, PEB was carried out at 110 ° C for 60 seconds, followed by cooling at 23 t for 60 seconds, and then using a 2.38 mass % TMAH aqueous solution, and developing by puddle at 23 ° C for 60 seconds. Pure water is washed and dried to form a photoresist pattern. The photoresist pattern thus formed was evaluated by the following method. The evaluation results are shown in Table 3. (Evaluation) [Sensitivity] The amount of exposure was changed by the above-described electron beam drawing device, and the line width and pitch pattern were drawn, and a scanning electron microscope for semiconductors (high-decomposition energy FEB length measuring device S-9380, manufactured by Hitachi, Ltd.) was used. The line between the line and the line is wide (the width is wide). The line width of the line is 90 nm. The line between the line and the adjacent line is 9 Onm. The 1 line and the pitch form an optimum exposure of 1:1 line width as the sensitivity (pC). /cm2). (minimum collapsed size) The exposure amount is changed by the above-described electron beam drawing device, and the 9Onm line and pitch pattern is drawn, and the groove width (width is wide) between the lines and the lines is measured by using the above-described semiconductor scanning electron microscope. The width is wider and wider, and the final pattern produces line corruption. The maximum exposure of this photoresist pattern is not confirmed. -90- 201243496 The pitch width is defined as the minimum breakdown size (nm). The larger the value, the better the resistance of the pattern is. [Resolution] 1 : In the 1 line and pitch pattern, the minimum line width of the line pattern with the best exposure amount is taken as the resolution. [Rectangle of the shape of the figure The cross-sectional shape of the 9 Onm line and the pitch pattern of the photoresist film obtained by the evaluation of the above-mentioned "sensitivity" was observed using a scanning electron microscope (S_4800, manufactured by Hitachi High-Tech Co., Ltd.), and the lower portion of the resist pattern shown in Fig. 1 was measured. The line width Lb and the line width Lu of the upper layer of the photoresist pattern. The rectangular shape of the pattern shape is evaluated as "A" for the cross-sectional shape when the enthalpy calculated by Lu/Lb is 0.8$Lu/LbS1.2. (good), evaluated outside this range as B"(bad). 201243496 Pattern shape &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt;&lt;&lt;&lt;&gt;&lt;&lt;CD&gt; CD CD CQ Resolution (nm) 3 s 〇3 Minimum Destruction Size (nm) 119 118 119 123 113 116 .115 116 125 110 110 108 113 102 Sensitivity i (//C/cm2) 45.0 I_ 45.0 45.5 45.0 47.0 45.5 45.5 50.0 49.0 44.0 45.5 45.5 45.0 45.0 45.0 Oxygen ashing resistance &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;卜1 J-1 J J1 J-1 J-1 i J-1 HP趁m I S-1 I S-2 S-3 S-4 S-2 CM 1 CO S-2 S-2 S-2 CM 1 CO S-5 S-6 S-7 if H delamination film) Example 5 Example 6 Example 7 Example &amp; Example 9 Example ΊΟ Example ” Example 12 Example 13 Example 14 Comparison Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example &amp;-92-201243496 [Example 15] A coating/developing device (CLEAN TRACK ACT12, using a coating film of a 300 mm oxide film on a 12-inch wafer) Tokyo Electric Co., Ltd.) Rotary coating anti-reflection film forming material (HM8006, J) After the SR system, PB was formed at 250 ° C for 60 seconds to form an anti-reflection film having a film thickness of 10 nm. This anti-reflection film was spin-coated with a ruthenium-containing film-forming composition (S-5) for a multilayer photoresist process, and after PB was performed at 220 ° C for 60 seconds, it was cooled at 23 ° C for 60 seconds to form a ruthenium having a film thickness of 15 nm. membrane. Next, the prepared photoresist composition was spin-coated on the ruthenium-containing film, and after 1 P (TC, 60 seconds, PB, and then cooled at 23 ° C for 30 seconds to form a film thickness of 5 〇. Nm photoresist film. Then, using EUV exposure device (SFET, Canon, lighting conditions; ΝΑ0.30σ 0·70/0·30) 'The reticle pattern is used to expose the photoresist film. Then, after exposure The photoresist film was crucible at 1 l ° C for 60 seconds, and then cooled at 23 ° C for 60 seconds. Then, using a 2.38% by mass aqueous solution of TMAH, it was developed by a stirring method of 23.8% by mass. The pattern is cleaned and dried with pure water to obtain a photoresist pattern. The photoresist pattern thus formed is evaluated according to the following method. The results are shown in Table 4. (Evaluation) [Minimum Spoilage Method] by the above-mentioned electron line The same method as the minimum size of the photoresist pattern formed by exposure is measured. At this time, the exposure amount (pC/cm2) when forming a photoresist pattern of L/S = 1/1 with a line width of 40 nm is used as the optimum exposure. The amount of this optimum exposure is used as the sensitivity. The line width and the line-to-line distance are measured using the £-93 - 201243496 scanning electron microscope (CG-4100, [High-tech system] [Resolution] For the line and pitch pattern of L/S = 1/1, the minimum line width of the line pattern with the best exposure amount is taken as the resolution. [Processing performance evaluation] The 4 〇 nm line and the pitch pattern of the photoresist film obtained by the evaluation of the minimum smear method are used as a mask, and the processing performance is evaluated using an etching apparatus (Telius SCCM, manufactured by Tokyo Electric Co., Ltd.). First, the ruthenium containing film is performed using CF4 gas. Processing: The processed ruthenium-containing film is used as a mask, and the underlayer film is processed by 〇2/N2 gas. Then, the processed film is used as a mask using CHF3/Ar/02 gas, and the substrate processing with the oxide film is performed. When the oxide film is processed at a depth of 50 nm or more, the film under the mask of the oxide film is not bent or twisted. [Table 4] Oxidation of a photoresist composition containing a ruthenium-containing film for a multilayer photoresist process Resistance to massiness (mJ/cm2) Minimum reversal size (nm) Resolution (nm) Example 15 S-5 J-1 A 12.0 35 35 From the results of Table 3, the multilayer photoresist process of the embodiment was used. When a ruthenium-containing film is formed by forming a composition containing a ruthenium film, it can be maintained The higher oxygen ashing resistance of the ruthenium-containing film is superior to the pattern of the photoresist pattern formed by the collapse resistance, the resolution, and the shape of the pattern. According to the method for forming a composition comprising a ruthenium film for a multilayer photoresist process according to the embodiment and using the pattern of the composition of the composition of -94-201243496, it is formed on the organic-based anti-reflection film or directly above the substrate. In the case of the formed photoresist pattern, the shape of the pattern is excellent in squareness and resolution. Further, as is clear from the results of Table 4, when the composition for forming a multilayer film/resistance process according to the embodiment includes a dicing film, the ruthenium-containing film or the substrate can be formed with excellent workability. [Industrial Applicability] According to the method for forming a ruthenium-containing film-forming composition and a pattern for a multilayer photoresist process of the present invention, light having excellent pattern resilience, resolution, and pattern shape is formed. The resistance pattern, by forming this photoresist pattern, can exhibit excellent processing performance and form a pattern suitable for the substrate to be processed. Therefore, the present invention is very suitable for the process of semiconductor devices which are increasingly miniaturized in the future, and the like, and is particularly suitable for a multilayer photoresist process which is finer than 5 Onm. [Simple description of the drawing] [Fig. 1] A pattern diagram of a photoresist pattern section formed by a multilayer photoresist process. [Explanation of main component symbols] 1 : Photoresist pattern 2 : Antimony film 3: Substrate to be processed Lu: Line width of the upper layer of the photoresist pattern

Lb : line width of the layer below the photoresist pattern £ -95-

Claims (1)

201243496 VII. Application for Patent Park: 1. A ruthenium-containing film-forming composition for a multilayer photoresist process characterized by [A] polyoxane and [B] electron acceptor. 2. The ruthenium-containing film-forming composition for a multilayer photoresist process according to claim 1, wherein the [B] electron acceptor is selected from the group consisting of a ruthenium compound, a quinodimethane compound, a dibenzofuran compound, and the following formula ( 1-1) and (1-2) compounds of at least one compound grouped as a compound, respectively. (Formula 〇-1) and (1-2), RLR5 is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom, and the Z· and Q· systems are independently oh-, RA_CO〇- , rA-S〇3• or RA-N_-S〇2-RB, RA is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, but some or all of the hydrogen atoms of RA may be substituted RBS alkyl or aralkyl, but part or all of one of the hydrogen atoms of RB may be substituted by a fluorine atom). 3. The film-forming composition containing 矽-96-201243496 in the multilayer photoresist process of claim 1 or 2 wherein [A] polyoxymethane is a compound containing a decane compound represented by the following formula (2) Hydrolyzed condensate, R6aSiX4-a (2) (In the formula (2), 'R6 is a hydrogen atom, a fluorine atom, an alkyl group having a carbon number of 1 to 5', a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group. Alkyl, aryl or aralkyl, which may be substituted by a fluorine atom. 'Aryl and aralkyl may be substituted, X-based halogen atom or -OR7, R7 is a monovalent organic group, a system 〇~ An integer of 3, but when R6 and X are plural, respectively, the plural R6 and X may be the same or different, respectively. 4. The ruthenium-containing film-forming composition for a multilayer photoresist process according to claim 1 or 2, For deep ultraviolet, X-ray or electron beam exposure. 5. A method for forming a pattern, characterized by the following steps: (1-1) using [A] polyoxane and [B] electron accepting a multilayered photoresist process comprising a ruthenium-containing film forming composition, a step of forming a ruthenium-containing film on the upper surface side of the substrate to be processed, and (I. 2) using a photoresist composition, a step of forming a photoresist film on the ruthenium film, (1-3) a step of exposing the photoresist film by radiation irradiation of the intervening mask, and (1-4) displaying the exposed photoresist film For example, a step of forming a photoresist pattern, and (1-5) a step of dry etching the sand-containing film and the substrate to be processed by using the photoresist pattern as a mask. A method for forming a pattern of five items, wherein the radiation of step (97) of step-97-201243496 is deep ultraviolet light, X-ray or electron beam. 7. The method for forming a pattern has the following steps (II-1) A step of forming a ruthenium-containing film on the upper side of a substrate to be processed using a ruthenium-containing film-forming composition for a multilayer photoresist process containing [A] polyoxyalkylene, (II-2) using a photoresist a step of forming a photoresist film on the ruthenium-containing film, (II-3) a step of exposing the photoresist film by irradiating a deep ultraviolet ray or an electron beam with an intervening mask, and (II-4) a step of developing the exposed photoresist film to form a photoresist pattern, and (II-5) using the photoresist pattern as a mask. Sequence of the above silicon-containing film and the substrate to be processed by dry etching steps -98 -