TW200920791A - Silicon-containing film-forming composition, silicon-containing film, silicon-containing film-bearing substrate, and patterning method - Google Patents

Abstract

A silicon-containing film is formed from a heat curable composition comprising (A-1) a silicon-containing compound obtained through hydrolytic condensation of a hydrolyzable silicon compound in the presence of an acid catalyst, (A-2) a silicon-containing compound obtained through hydrolytic condensation of a hydrolyzable silicon compound in the presence of a base catalyst, (B) a hydroxide or organic acid salt of Li, Na, K, Rb or Ce, or a sulfonium, iodonium or ammonium compound, (C) an organic acid, (D) a cyclic ether-substituted alcohol, and (E) an organic solvent. The silicon-containing film ensures effective pattern formation, effective transfer of a photoresist pattern, and accurate processing of a substrate.

Description

200920791 IX. Description of the Invention [Technical Field] The present invention relates to a ruthenium-containing film for use as an intermediate layer in a multilayer photoresist method used in microfabrication in the process of manufacturing a semiconductor element or the like, and is particularly suitable for use in a slewing process. A method of forming an intermediate layer to form a film composition containing ruthenium, a film containing ruthenium formed thereon, a substrate formed of a film containing ruthenium, and a method of forming a pattern using the same. [Prior Art] With the high integration and high speed of LSI, the size of the pattern is rapidly reduced. In order to cope with the miniaturization, the lithography technique achieves a fine pattern by shortening the wavelength of the light source and appropriately selecting a photoresist composition corresponding thereto. The center is a positive photoresist composition for use in a single layer. The single-layer positive-type photoresist composition is a resistive resin which has a corrosion-resistant skeleton with respect to dry uranium using a chlorine-based or fluorine-based gas, and is dissolved and exposed by a photoresist mechanism that dissolves the exposed portion. After the pattern is formed, the remaining photoresist pattern is used as an etching mask to dry-etch the material of the substrate on which the photoresist composition is applied, but the film thickness of the photoresist film used is directly reduced, that is, When the width of the pattern is reduced, the resolution of the photoresist film is lowered, and when the pattern of the photoresist film is used to develop the pattern of the photoresist film, the so-called aspect ratio is excessively increased, causing the pattern to collapse. Therefore, as the miniaturization is required, the thickness of the photoresist film is made thin. In addition, the processing method used for the substrate to be processed is generally that the patterned photoresist film is used as an etching mask, and the substrate is processed by dry etching. However, the dry etching method cannot make the photoresist film on the actual -6 - 200920791. The complete etching selectivity is obtained between the substrate and the substrate to be processed, and the photoresist film is damaged during the processing of the substrate, causing the photoresist film to collapse during the processing of the substrate. Therefore, the photoresist pattern cannot be accurately reproduced on the substrate to be processed. Therefore, with the miniaturization of the pattern, the photoresist composition is required to have higher dry etching resistance. Further, in order to shorten the wavelength of the exposure wavelength, the resin used in the photoresist composition is required to be a resin having a weak absorption of light at an exposure wavelength, and therefore, the novolac is used instead of the i-line, KrF, or ArF. Resin, polyhydroxystyrene, and a resin having an aliphatic polycyclic skeleton. However, in actuality, the etching rate of the dry etching condition is very fast, so that the corrosion resistance of the photoresist composition having the recent high resolution is lowered. Since it is necessary to dry-etch the substrate to be processed with a thinner and less resistant photoresist film, it is imperative to ensure the materials and steps of the process. One of the ways to solve this type of problem is the multilayer photoresist method. In the method, a photoresist film is interposed between the photoresist upper layer film and the substrate to be processed, and an etching film having an etching selectivity different from that of the photoresist upper layer film is obtained, and after the photoresist upper layer film is patterned, the upper layer photoresist pattern is obtained. The type is a dry etching mask, the pattern is copied to the intermediate film by dry etching, and the intermediate film is used as a dry etching mask, and the pattern is copied to the substrate to be processed by dry etching. A two-layer photoresist method which is one of the multilayer photoresist methods, for example, a resin containing ruthenium for the upper photoresist composition and a novolak resin for the intermediate film (for example, Patent Document 1: JP-A-6-9 5 3 8 5) ). Tantalum resin has good uranium resistance relative to reactive dry uranium using oxygen plasma, but is easily removed using a fluorine-based gas excimer. Further, the novolac resin is easily removed by reactive dry etching using an oxygen gas or the like, but has good uranium resistance with respect to dry etching using a fluorine-based gas ion or a chlorine-based gas. Therefore, the novolac resin is formed into a photoresist intermediate film on the substrate to be processed, and a photoresist upper layer film is formed thereon by using a resin containing ruthenium. Secondly, the ray-containing photoresist film is irradiated with energy lines and developed, and then formed into a pattern, which is used as a dry etch mask by reactive dry etching using oxygen plasma, and dry etching removes the removed photoresist pattern. Part of the novolak resin and copying the pattern onto the novolac film'. Then the pattern copied to the novolak film is a dry etching mask, and then etching by using a fluorine-based gas plasma and a chlorine-based gas plasma. The pattern is copied to the substrate to be processed. In the method of copying the pattern by dry etching, when the corrosion resistance of the etching mask is sufficient, a replica pattern having a good shape can be obtained, so that the pattern collapse is caused by the friction of the developing liquid when the photoresist is not easily generated. The problem is that the pattern with higher length and width can be obtained. For example, when a photoresist film for an interlayer film using a novolak resin has a film thickness, it can be used as a fine pattern which cannot be directly formed due to collapse of a pattern due to an aspect ratio problem or the like. The double-layer resist method is obtained by the double-layer resist method, and has a pattern of a novolak resin which is sufficient as a thickness of the dry etching mask of the substrate to be processed. Further, the multilayer photoresist method may be a 3-layer photoresist method using a general photoresist composition used in a single-layer photoresist method. For example, after an organic film for a photoresist underlayer film is formed on a substrate to be processed by using a novolac or the like, a film containing a ruthenium film for the photoresist intermediate film is formed thereon, and a photoresist upper layer film is formed thereon. Generally organic photoresist film. Compared with the dry etching using a fluorine-based gas plasma, the organic photoresist upper film has a good etching selectivity to the yttrium-containing photoresist intermediate film, so that dry etching using a fluorine-based gas plasma can be used. The photoresist pattern is replicated in a photoresist film containing tantalum. The method can also copy the pattern to the ruthenium containing the photoresist composition having a sufficient film thickness for forming the substrate to be processed directly, and the photoresist composition having insufficient dry etching resistance for the processed substrate. The film of the furfural varnish film having sufficient dry etching resistance when processed by the double-layer photoresist method. The ruthenium-containing photoresist intermediate film used in the above-described three-layer photoresist method may be a ruthenium-containing inorganic film derived from CVD, for example, a SiO 2 film (for example, Patent Document 2: JP-A-7-183 1 94). A SiON film (for example, Patent Document 3: JP-A-H07-186), or a film obtained by spin coating, for example, an S Ο G (cyclotron) film (for example, Patent Document 4: Special Opening) 5 -29 1 208, etc., Non-Patent Document 1: Appl. Polym. Sci., Vol. 8 8, 63 6-64 0 (2 00 3 )) and a crosslinkable sesquiterpene oxide film (for example, a patent) Document 5: JP-A-2005-5203, etc., or the like, or a polydecane film (for example, Patent Document 6: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. Among them, the S i Ο 2 film and the SiON film have a high performance when used as a dry etching mask for the dry etching of the underlying organic film, but a special device is required for film formation. On the other hand, the S Ο G film, the crosslinkable sesquioxane film, and the polydecane film can be formed by spin coating and heating, and it is estimated that the production efficiency is high. The application of the multilayer photoresist method is not limited to increasing the resolution limit of the photoresist film. As in the fast-rotation method of one of the substrate processing methods, when the processing intermediate substrate has a large drop, forming a pattern with a single photoresist film causes a large deviation in the thickness of the photoresist film, so that it is impossible to expose the photoresist. Correctly match the focus and other issues. At this time, after the flattening of the embedding film is used to flatten the film, the photoresist film is formed on the upper surface of the film -9 - 200920791 to form a photoresist pattern, but the above-described multilayer photoresist method can be used (for example, Patent Document 7: Special opening 2 0 0 4 - 3 4 9 5 7 2, etc.). There have been several problems with the ruthenium-containing film previously used in the multilayer photoresist method. For example, when a photoresist pattern is formed by photolithography, it is known that the incident light is disturbed by the substrate reflecting the light source, and a so-called constant wave problem is generated. In order to obtain a fine pattern in which the photoresist film does not contain edge roughness, The antireflection film is used as an intermediate film. In particular, the control of reflection under the high-nano exposure conditions of the most advanced is a necessary condition. In order to control the reflection, in the multilayer photoresist method, particularly in the step of forming a film containing ruthenium for the intermediate layer from C V D , an organic anti-reflection film is interposed between the photoresist upper film and the ruthenium-containing intermediate film. However, when the organic anti-reflection film is placed, the organic anti-reflection film is patterned by using the photoresist upper layer film as a dry etching mask, and the anti-reflection film is dry-etched by the photoresist upper layer film as a pattern mask during dry etching. The intermediate layer containing ruthenium is then transferred. Therefore, it is possible to increase the dry uranium load by processing only the upper layer of the anti-reflection film. In particular, the thin film of the most advanced photoresist film is less able to escape the dry etching load. Therefore, the three-layer photoresist method in which the film of the light absorbing ytterbium containing no etching load as the intermediate film is used as the intermediate film is attracting attention. Such a light-absorbing ytterbium-containing intermediate film is known as an 'intermediate film of a light-absorbing ytterbium containing a spin coating type. For example, a method of using an aromatic structure as a light absorbing structure has been disclosed (Patent Document 8: JP-A No. 2 005 - 1 5 7 79). However, when the aromatic ring structure which can effectively absorb light is dry-etched by using a fluorine-based gas plasma, the dry etching rate is lowered, which is disadvantageous for the dry etching of the interlayer film under no load of the photoresist film. Therefore, it is not advisable to add a large number of such light-absorbing substituents, and -10-200920791 should be suppressed to the minimum introduction amount. In addition, when the interlayer film is processed by the interlayer film as a dry etching mask, the dry etching rate with respect to the reactive dry etching using oxygen plasma is generally small in order to increase the uranium engraving selection ratio of the interlayer film and the underlying film. Preferably, it is expected to increase the amount of ruthenium having a higher reactivity of the interlayer film with respect to the fluorine-based etching gas. In order to meet the processing conditions of any of the above-mentioned upper photoresist film and the underlying organic film, the intermediate film preferably contains a ruthenium containing a component having a higher reactivity with respect to fluorine gas. However, in actuality, in the composition for forming a ruthenium-containing intermediate film by a spin coating type, the ruthenium-containing compound contains an organic substituent which is soluble in an organic solvent. A composition for forming an SOG film in a currently known ruthenium containing interlayer film is disclosed in Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)) using KrF excimer laser light. The lithography etching object. However, since the composition does not have a description of the light absorbing group, it is presumed that the film containing ruthenium obtained from the composition does not have an antireflection function. Therefore, it is impossible to avoid light reflection at the time of exposure with respect to the lithography etching using the most advanced high-NA exposure machine, and a high-definition pattern shape cannot be obtained. In addition to the requirements for dry etching characteristics and antireflection effects, the formation of an intermediate film composition having a high enthalpy content is particularly problematic in terms of the preservation stability of the composition. The preservation stability at this time means a case where the molecular weight of the composition is changed when the stanol group of the ruthenium-containing compound contained in the condensed composition is contained. Thus, variations in film thickness and changes in lithographic etching performance were observed. In particular, the lithographic etching variation is very sensitive, so that even when the sulfohydrin group in the molecule is condensed, the film thickness rise and the molecular weight change cannot be observed, and the shape change of the high-definition pattern can be observed from -11 to 200920791. Previously, such a highly reactive stanol group was relatively stable when stored in an acidic state, for example, Non-Patent Document 2 (CJ Brinker and G_W. Scherer, Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing), Academic Press, San Diego (1 990)), etc. Non-Patent Document 1: (J. Appl. Polym. Sci., Vol. 88, 63 6-640 (2003)), Patent Document 9 (Special Open 2004) Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2 0 0 4 - 1 9 1 3 8 6 discloses that water is added to improve storage stability. However, the method disclosed in the patent document is disclosed. The produced ruthenium-containing compound can not completely prevent the condensation reaction of the stanol group by using this means, and will slowly change the ruthenium-containing compound in the composition over time, thereby changing the composition resulting from the change. It has the properties of a ruthenium film. Therefore, it should be stored in a refrigerated or frozen state before use, and it should be used as soon as possible after returning to the use temperature (usually 23 ° C). [Patent Document 1] JP-A-6-95 3 8 5 Patent Document 2] Unexamined Patent Publication No. 7_1 8 3 1 94 [Patent Document [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei No. 2005-520354 (Patent Document 6) Japanese Laid-Open Patent Publication No. 2004-349572 (Patent Document No. JP-A-2005-277749) [Non-Patent Document 11] J. Appl. Polym. Sci., Vol. 88, 636-640 (2003) [Non-Patent Document 12] CJ Brinker and GW Scherer, ^Sol-Gel SUMMARY OF THE INVENTION Problem to be Solved by the Invention An object of the present invention is to provide (1) a film formed on an organic film. When a photoresist film is formed on a film containing germanium, when a photoresist pattern is formed, since the film containing germanium has light absorption properties, a good pattern can be formed even under high NA exposure conditions, and (2) The photoresist layer on the upper layer of the film and the organic film on the bottom layer form a good dry etching mask with a film containing ruthenium, (3) good preservation stability A composition for forming a film containing ruthenium, a film containing ruthenium obtained from the composition, a substrate formed of a film containing ruthenium, and a method of forming a pattern. In order to solve the problem, the present inventors have focused on the lithographic characteristics and stability of the composition for forming an intermediate film containing ruthenium, and have found that the following (Β) component, (C) component, and (D) component are obtained. And the (Ε) component is added, and the hydrazine-containing compound obtained by hydrolyzing and condensing the hydrolyzable hydrazine compound with an acid as a catalyst, and the hydrazine-containing compound obtained by hydrolyzing and condensing the hydrolyzable hydrazine compound with a base as a catalyst may be used. (1) By introducing a light-absorbing substituent described later, the film containing yttrium can be suppressed even under any exposure conditions of dry or liquid immersion, and (2) when used as a dry etching mask The uranium engraving is selected to be larger than the film containing ruthenium, and the present invention has been completed by forming a film composition containing ruthenium without a change in properties of the lithographic etching property for a long period of time. In other words, the present invention provides a composition for forming a film containing ruthenium containing a thermosetting property, which comprises (A-1) a ruthenium-containing compound obtained by hydrolyzing and condensing a hydrolyzable ruthenium compound with an acid as a catalyst, (A) - 2) a hydrazine-containing compound obtained by hydrolyzing and condensing a hydrolyzable hydrazine compound with a base as a catalyst, and (B) one or more of the compounds represented by the following general formula (1) or (2),

LaHbX (1) (wherein L is lithium, sodium, potassium, riveted or planed, X is a hydroxyl group, or a monovalent or divalent or higher organic acid group having a carbon number of 1 to 30, a is an integer of 1 or more, and b is An integer of 0 or more, a + b is the valence of a hydroxyl group or an organic acid group)

MaHbA (2) (wherein, hydrazine, iron iodide or ammonium 'A is the above X or non-nucleophilic counter ion, a, b are the same as above, a + b is a trans group, an organic acid group or a non-parent (C) a valence of 1 to 30 or more of an organic acid, (D) a monovalent or divalent or higher alcohol having a substituent of a cyclic ether-14- 200920791 (E) Organic solvent. (Applicant's patent scope 1). The hydrolyzable hydrazine compound (hereinafter referred to as a monomer) is hydrolyzed by a hydrolyzable substituent bonded to a hydrazine atom by an action of water under an acid catalyst to form a stanol group. The stanol group is then subjected to a condensation reaction with other stanol groups or unreacted hydrolyzable groups to form a decane linkage. The reaction is repeated to form the desired oligomer, polymer, or yttrium-containing compound as the case may be. In this case, the sterol group derived from the monomer, the oligomer, the polymer, and the like which are formed by the hydrolysis reaction is subjected to a condensation reaction in the order of the most reactive substance to consume a monomer, an oligomer, a polymer, or the like. The stanol group forms a ruthenium containing compound. Since the condensation reaction proceeds without limitation, it is finally possible to gel the ruthenium-containing compound. However, it is known from Non-Patent Document 2 (CJ Brinker and GW Scherer, ''Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)) that a specific pH can suppress the condensation. The reaction, in particular, Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 8 8, 6 3 6 - 6 4 0 (2 0 0 3 )) has described pH 1.5 (hereinafter referred to as stable pH). Settled. The present inventors have found that the use of the component (C) to control the stability of the pH can improve the preservation stability. Further, it is known that a monomer which is different from an acid catalyst by an action of water under an alkaline catalyst can obtain a ruthenium-containing compound (A-2) having a high condensation and a small stanol group (Non-Patent Document 2: (C) J_ Brinker and G. W. Scherer,, Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing -15- 200920791 ", Academic Press, San Diego (1990)). Since the sterol group at the end of the mouth (A-2) is small, even if the film containing ruthenium is formed only from the ruthenium-containing compound (A-2), the bond between the ruthenium-containing compound (A-2) can be reduced. The film having a lower density is obtained. Therefore, the present inventors have found that 'from the mixed sand; the cerium-containing compound (A-1) having a large amount of alcohol groups and the sand-containing compound (A-2) having a small stanol group. When the composition forms a film containing ruthenium, the ruthenium-containing compound (A-2) having a small stanol group is biased on the surface of the film, so that the surface sterol can be formed without adding the ruthenium-containing compound (A-2). A film containing less ruthenium. Since the influence of the unavoidable stanol group remaining in the ruthenium-containing film can be minimized, a well-shaped photoresist pattern can be formed. Further, it is found that when the sterol group remaining in the ruthenium-containing compound is suppressed from being near the room temperature, it is found that when a monovalent or divalent or higher alcohol having a substituent of a cyclic alcohol is added as a stabilizer The condensation can be suppressed in the vicinity of room temperature, and the stability of the composition can be improved by the flying type. Previously, the cerium-containing compound was hardened by using a high temperature of TC or higher and an acid catalyst by a thermal acid generator. The invention is characterized in that, after heat-hardening after coating the composition, the pH of the sulfanol group is changed from a stable pH to an unstable pH by using a thermal crosslinking promoting action of the added component (B) (such as a non-patent Document 2 (CJ Brinker and GW Scherer, 'Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990))), so that the film can be hardened more effectively. It can provide a fine film which is crosslinked faster than the previous cured film when heat-hardened under the same conditions as the previous temperature conditions. Therefore, it is possible to suppress the transfer of the active component in the photoresist to the film containing ruthenium, and it is obtained from -16 to 200920791. The same lithographic etching characteristics of the organic anti-reflection film. The yttrium-containing compound (A-2) having less stanol groups is biased on the surface at the beginning as described above, and ρ Η is changed during hardening to effectively promote condensation between stanol groups. The reaction is carried out, so that a film containing a very small amount of ruthenium alcohol group can be obtained. Since the surface of the film is almost free of stanol groups, the effective components in the photoresist film are not adsorbed, and the lithographic etching characteristics equivalent to those of the general organic antireflection film can be obtained. In addition, the combination of pH control, stabilizer addition and cross-linking catalyst technology can provide a composition that is stable at room temperature and hardened at the time of hardening, so that it can be obtained with the same stability as the previous organic anti-reflection film. Anti-reflective film composition. The present invention provides a composition for forming a film containing ruthenium containing a ruthenium according to the first aspect of the patent application, wherein the ruthenium-containing compound (A-1) is contained in the inorganic acid and the sulfonic acid derivative. One or more selected compounds are ruthenium-containing compounds obtained by subjecting an acid catalyst to hydrolysis-condensation of a hydrolyzable ruthenium compound to substantially remove the above-mentioned acid catalyst in a ruthenium-containing reaction mixture (Application No. 2). The ruthenium-containing compound produced by the prior art is used for forming a coating film composition under the use of an acid catalyst which is not substantially removed by hydrolysis. Therefore, the condensation reaction catalyst remains in the composition, so that the composition controlled at a stable pH cannot inhibit the condensation of stanol, and only a composition having poor stability can be stored. In addition, a composition for forming a coating film which is obtained by using an acidic substance which has a decyl alcohol as a stable pH as a hydrolysis condensation catalyst, does not sufficiently carry out a condensation reaction of a stanol group, and a large amount of stanol groups remain, so that The group -17-200920791 maintains a stable pH and will only retain a less stable composition due to the excess amount of stanol. In the present invention, the bismuth-containing compound obtained by using the optimum acid catalyst for hydrolytic condensation substantially removes the acid catalyst, and then the components (C) and (D) are used to improve the storage stability. The present invention provides a composition for forming a film containing ruthenium containing a ruthenium according to the first or second aspect of the patent application, wherein the ruthenium-containing compound (A-2) is contained, and hydrolyzability can be obtained by using a base as a catalyst. A ruthenium-containing compound obtained by the step of substantially removing the base catalyst in the ruthenium-containing reaction mixture obtained by hydrolytic condensation of a ruthenium compound (Patent No. 3 of the patent application). In general, the stability region of stanol is an acidic side, so when the composition is added without the (A-2) removal of the base catalyst used in the production of (A-2), the pH balance in the composition is disintegrated and the composition is lowered. The stability of things. Therefore, after removing the alkaline catalyst for the manufacture of (A - 2), the addition of the components (C) and (D) can improve the stability. The present invention provides the heat of any one of the claims 1 to 3 of the patent application. The composition of the film containing ruthenium is formed by a hardening property, wherein the enthalpy of the general formula (2) is a three-stage sulphur gun, a second-stage iodine oxime or a quaternary ammonium (application patent item 4). When the compound represented by the general formula (2) is a (ruthenium) component and a thermal crosslinking accelerator is used as a composition to form a cured film, a fine film obtained by crosslinking can be provided. Therefore, it is possible to suppress the transfer of the active component in the photoresist film to the film containing ruthenium, which is equivalent to the lithographic etching property of the general organic anti-reflection film. The present invention provides a thermosetting composition for forming a film containing ruthenium according to any one of claims 1 to 4, wherein 一般 -18- 200920791 of the general formula (2) is photodegradable (patent pending) Item 5). When the component (B) cannot be completely volatilized during heat curing, the component (B) may remain in the film containing ruthenium. This component may deteriorate the shape of the photoresist pattern. Further, when a compound which can decompose the cationic portion of the component (B) during exposure is used, it is possible to prevent deterioration of the shape of the resist pattern during exposure. Namely, it is possible to provide a hardened film containing ruthenium which can improve the hardenability of the ruthenium-containing compound while obtaining a good lithographic etching shape. The present invention provides a composition for thermosetting a sand-containing film according to any one of claims 1 to 5, wherein the mass in the composition is (Α-1)>(Α-2) ( Apply for patent scope item 6). When the composition contains a majority of the cerium-containing compound (A_2) having a small stanol group, the fineness of the film containing the sand after hardening is lowered. As a result, the effective component in the photoresist film is transferred to the film containing germanium, and the shape of the photoresist pattern after the photolithography is deteriorated. In order to prevent this result, it is necessary to contain a sufficiently crosslinkable chopping compound (A-1). When the ruthenium-containing compound (A_;[) has a higher mass than the ruthenium-containing compound (A-2), it can have sufficient cross-linking reactivity to form a fine film, so that a photoresist pattern after lithography etching can be obtained. A film containing ruthenium that has no adverse effect on the shape. The present invention provides a composition for forming a film containing ruthenium containing a thermosetting property according to any one of claims 1 to 6, which further contains a photoacid generator (Application No. 7). The component (B) cannot be completely volatilized during heat hardening and exposure, and the (B) component remaining in the film containing ruthenium may affect the shape of the pattern. In order to prevent this result from occurring in the formation of a photoresist pattern, an acid may be generated in the film containing ruthenium to prevent deterioration of the shape of the photoresist pattern. -19-200920791 The present invention provides a composition for forming a sand-containing film of a thermosetting type according to any one of claims 1 to 7, which further contains water (Application No. 8 of the patent application). The addition of water activates the stanol group in the ruthenium-containing compound, and a finer film can be obtained by a heat hardening reaction. The use of such a fine film allows the lithographic etching performance of the upper photoresist layer to be equal to or higher than that of the general organic antireflection film. The present invention further provides the following ruthenium-containing film, substrate, and pattern forming method, a ruthenium-containing film formed from the composition of any one of claims 1 to 8, which is processed After forming an organic film on the substrate, a film containing ruthenium is formed thereon, and a photoresist film is formed thereon by using a chemically-reinforced photoresist composition containing no ruthenium. After the photoresist film pattern is processed, the light is used. The pattern of the ruthenium-containing film is patterned, and the pattern of the film containing ruthenium is processed by the uranium engraved mask to pattern the underlying organic film, and then the processed organic film is used as an etch mask. A film containing ruthenium used for processing a substrate for etching by a multilayer photoresist method (Patent No. 9 of the patent application). A film comprising ruthenium formed by the composition of any one of claims 1 to 8 which is in the step of a multilayer photoresist of the ninth application of the patent application, in the step of chemically reinforced photoresist A film containing ruthenium used in a multilayer photoresist method in which an organic anti-reflection film is interposed between a photoresist film of a composition and a film containing ruthenium (Patent No. 1 of the patent application). A substrate characterized by sequentially forming an organic film on a film comprising ruthenium formed from a composition according to any one of claims 1 to 8 above, and a photoresist film thereon (patent pending) Scope item 1). -20- 200920791 A substrate characterized by sequentially forming an organic film, and a film containing ruthenium formed on the organic film by the composition of any one of claims 1 to 8, and an organic anti-reflection Membrane, and the photoresist film above it (Patent No. 12 of the patent application). The substrate according to claim 11 or 12, wherein the organic film is a film having an aromatic skeleton (No. 13 of the patent application). A method for forming a pattern, characterized in that, in a method of forming a pattern on a substrate, preparing a substrate as in claim 1 of the patent application, exposing the field of the photoresist circuit of the photoresist film of the substrate to Forming a photoresist pattern on the photoresist film like liquid imaging, and using the photoresist pattern forming the photoresist pattern as an etching mask to dry-etch the film containing germanium to form a patterned film containing germanium Etching the organic film for etching the mask, and etching the substrate by using the organic film forming the pattern as a mask to form a pattern on the substrate (Patent No. 14 of the patent application) 〇 a method of forming a pattern, The method of forming a pattern on a substrate, preparing a substrate as in the second aspect of the patent application, exposing the pattern loop region of the photoresist film of the substrate, and developing the image with a developing solution A photoresist pattern is formed on the resist film, and the photoresist film forming the photoresist pattern is used as an uranium engraved mask to dry-etch the organic anti-reflection film and the antimony-containing film to form a patterned crucible film. Etching the mask to etch the organic film, and then forming the pattern of the organic film as a picture The substrate is etched to form a pattern (patent the range 1 5) on the substrate. A method of forming a pattern of the first or fourth aspect of the patent application, wherein the organic film is a film having an aromatic skeleton (Application No. 16-21-200920791). For example, the method for forming a pattern of the patent application No. 14, 4, or 16 is used in the formation of a photoresist pattern, and the photolithography method using a light having a wavelength of 3 〇〇 nm or less (application patent scope) 1 7 items). When the intermediate film and the substrate of the present invention are used to form a pattern on the substrate by lithography, a fine pattern can be formed on the substrate with high precision. In this case, an organic film having an aromatic skeleton is used, and in addition to the antireflection effect of the microphotographing step, it can be an organic film having sufficient corrosion resistance during substrate etching, so that it can be processed by uranium engraving. Further, when the substrate of the present invention is used to form a pattern on the substrate by lithography, a fine pattern can be formed on the substrate with high precision. The present invention forms a pattern by using light having a wavelength of 300 nm or less, particularly a lithography of an ArF excimer laser, so that a fine pattern can be formed with high precision. EFFECT OF THE INVENTION The use of the interlayer film containing ruthenium formed by the composition for forming a film containing ruthenium according to the present invention allows a light-shielding film formed thereon to form a good pattern. Further, since the etching selectivity is high with the organic material, the formed photo resist pattern can be sequentially copied to the ruthenium containing intermediate film and the organic underlayer film by the dry uranium step. Finally, the organic underlayer film is used as an etch mask to process the substrate with high precision. Further, it is possible to provide a material which suppresses generation of defects after patterning by lithography and which has excellent preservation stability. -22-200920791 BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting composition of the present invention forms a composition for a film containing ruthenium, and the ruthenium-containing compound used in the present invention is a monomer (hydrolyzable sand compound) under an acid catalyst. Hydrolyzed and condensed. Preferably, the method for producing a ruthenium-containing compound is as follows, but is not limited thereto. The monomer of the starting material can be represented by the following general formula (3). R m 丨 R m 2 R m 3 S i ( 0 R ) ( 4 - m 1 - m 2 - m 3 ) ( 3 )

(R is an alkyl group having 1 to 3 carbon atoms, and Ri, r2, and R3 are each the same or different hydrogen atom' or a monovalent organic group having 1 to 30 carbon atoms, and ml, m2, and m3 are 0 or 1. ml. +m2 + m3 is 〇 to 3, particularly preferably 〇 or 1) Q, which is obtained by hydrolyzing and condensing a selected one or a mixture of two or more of the monomers represented by the general formula (3). The organic group means a group containing carbon, and additionally contains hydrogen, or may contain nitrogen, oxygen, sulfur, and the like. The organic group of R1, R2, and R3 is, for example, a linear, branched, cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group or the like, and an unsubstituted monovalent hydrocarbon group' a group in which one or more hydrogen atoms are substituted by an epoxy group, an alkoxy group, a hydroxyl group or the like, and a group in which c0_, _〇C〇-, -coo-, and -ocoo- are substituted, and the like is expressed by a general formula (4) described later. The base, and the organic group containing a 矽-矽 bond. In the monomer represented by the general formula (3), Ri, R2, and R3 are preferably, for example, a hydrogen atom, a methyl group, an ethyl group, an η-propyl group, an is〇-propyl group, an n-butyl group, an is〇·butyl group, or the like. Sec-butyl, butyl, n-pentyl, 2-ethylbutyl, 3-ethylbutyl, -23- 200920791 2,2-diethylpropyl, cyclopentyl, η-hexyl, cyclohexyl An alkynyl group such as an alkyl group, a vinyl group or an allyl group, or an alkynyl group such as an ethynyl group, or an aryl group such as a light-absorbing phenyl group or a tolyl group, an aryl group such as a benzyl group or a phenethyl group. Monomer such as ml = 0, m2 = 0, m3 = 0 tetraalkoxy decane, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetra-iso-prop Oxydecane. Preferably, it is a tetramethoxy decane, a tetraethoxy decane oxime, and another three-compartment oxygen sand court of ml = l, m2 = 0, and m3 = 0, for example, trimethoxy decane, triethoxy decane, Tri-n-propoxydecane, tri-i so-propoxydecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltri-iso - propoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl tri-n-propoxy decane, ethyl tri-iso-propoxy decane, vinyl trimethoxy decane, Vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl tri-iso-propoxy decane, η-propyl trimethoxy decane, η-propyl triethoxy sand, Η-propyltri-n-propoxylate, η-propyltri-iso-propoxy sand, i-propyltrimethoxydecane, i-propyltriethoxydecane, i-propyl Tris-n-propoxydecane, i-propyl tri-iso-propoxydecane, η-butyltrimethoxydecane, η-butyltriethoxydecane, η-butyltris-η- Propoxydecane, η-butyltri-iso-propoxydecane, sec-butyltrimethoxy Alkane, sec-butyl-i-triethoxydecane, sec-butyl-tri-n-propoxydecane, sec-butyl-tri-iso-propoxydecane, t-butyltrimethoxy Decane, t-butyltriethoxydecane, t-butyltri-n-propoxydecane, t-butyltri-iso-propoxydecane, cyclopropyltrimethoxydecane, cyclopropyltriethyl Oxydecane, cyclo-24- 200920791 propyl-tri-n-propoxydecane, cyclopropyl-tri-iso-propoxydecane, cyclobutyltrimethoxydecane, cyclobutyltriethoxydecane , cyclobutyl·tris-n-propoxydecane, cyclobutyl-tri-iso-propoxydecane, cyclopentyltrimethoxydecane, cyclopentyltriethoxydecane, cyclopentyl-tri- Η-propoxydecane, cyclopentyl·tri-iso-propoxydecane, cyclohexyltrimethoxydecane, cyclohexyltriethoxydecane, cyclohexyl-tri-n-propoxydecane, cyclohexyl- Tri-iso-propoxydecane, cyclohexenyltrimethoxydecane, cyclohexenyltriethoxydecane, cyclohexenyl-tri-n-propoxydecane, cyclohexenyl-tri-iS0 -propoxydecane, cyclohexenylethyltrimethoxydecane, cyclohexenylethyltriethoxy Decane, cyclohexenylethyl, tri-n-propoxydecane, cyclohexenylethyl-tri-iso-propoxydecane, cyclooctyltrimethoxydecane, cyclooctyltriethoxy Baseline, cyclooctyl-tris-n-propoxydecane, cyclooctyl-tri-iso-propoxydecane, cyclopentadienylpropyltrimethoxynonane, cyclopentadienylpropyl Triethoxydecane, cyclopentadienylpropyl-tri-n-propoxydecane, cyclopentadienylpropyl-tri-iso-propoxydecane, dicycloheptenyltrimethoxydecane, Dicycloheptenyltriethoxydecane, dicycloheptenyl-tri-n-propoxydecane, dicycloheptenyl-tri-iso-propoxydecane, dicycloheptyltrimethoxydecane, Dicycloheptyltriethoxydecane, dicycloheptyl-tri-n-propoxydecane, dicycloheptyl-tri-iso-propoxydecane, adamantyltrimethoxydecane, adamantyl Ethoxy decane, adamantyl-tri-n-propoxy decane, adamantyl-tri-iso-propoxy decane, and the like. Further light absorbing monomers such as phenyltrimethoxydecane, phenyltriethoxydecane, phenyltri-n-propoxydecane, phenyltri-iso-propoxydecane, benzyltrimethoxy Decane, benzyltriethoxydecane, benzyltri-n-propoxydecane-25- 200920791, benzyltri-iso-propoxydecane, tolyltrimethoxydecane, tolyltriethoxydecane , tolyltri-n-propoxydecane, tolyl tri-iso-propoxydecane, phenethyltrimethoxydecane, phenethyltriethoxydecane, phenethyltri-n-propoxy Decane, phenethyltri-iso-propoxydecane, naphthyltrimethoxydecane, naphthyltriethoxydecane,naphthyltri-n-propoxydecane,naphthyltri-iso-propoxydecane Wait. Preferred are methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, η- Propyltrimethoxydecane, ία-propyltriethoxydecane, iso-propyltrimethoxydecane, iso-propyltriethoxydecane, η-butyltrimethoxydecane, η-butyl III Ethoxy decane, iso-butyl trimethoxy decane, iso-butyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, cyclopentyl trimethoxy decane, ring Butyl triethoxy decane, cyclohexyl trimethoxy decane, cyclohexyl triethoxy decane, cyclohexenyl trimethoxy decane, cyclohexenyl triethoxy decane, phenyl trimethoxy decane, benzene Triethoxy decane, benzyl trimethoxy decane, benzyl triethoxy decane, phenethyl trimethoxy decane, phenethyl triethoxy decane. For example, m 1 = 1, m 2 = 1, m 3 = 0, which is, for example, dimethyldimethoxydecane, dimethyldiethoxydecane, methylethyl Methoxy decane, methyl ethyl diethoxy decane, dimethyl-di-n-propoxy decane, dimethyl-di-iso-propoxy decane, diethyl dimethoxy decane, Diethyldiethoxydecane, diethyl-di-n-propoxydecane, diethyl-di-iso-propoxydecane, di-n-propyldimethoxydecane, di- 26- 200920791 η-propyldiethoxydecane, di-η-propyl-di-η-propoxydecane, di-n-propyl-di-iso-propoxydecane, di-iso-propane Dimethoxy decane, di-iso-propyl diethoxy decane, di-iso-propyl-di-η-propoxy decane, di-iso-propyl-di-iso-propoxy decane , bis-η-butyldimethoxydecane, di-η-butyldiethoxydecane, di-η-butyldi-η-propoxydecane, di-η-butyldi-iso- Propoxy decane, di-sec-butyl dimethoxy decane, di-sec-butyl diethoxy decane, bis- sec-butyl-di-n-propoxy decane, di-sec-butyl Base-two -iso-propoxydecane, di-t-butyldimethoxydecane, di-t-butyldiethoxydecane, di-t-butyl-di-n-propoxydecane, di- T-butyl-di-iso-propoxydecane, di-cyclopropyldimethoxydecane, di-cyclopropyldiethoxydecane, di-cyclopropyl-di-n-propoxydecane , di-cyclopropyl-di-isopropoxydecane, dicyclobutyldimethoxydecane, di-cyclobutyldiethoxydecane, di-cyclobutyl-di-n-propoxy Decane, di-cyclobutyl-di-iso-propoxydecane, di-cyclopentyldimethoxydecane, di-cyclopentyldiethoxydecane, di-cyclopentyl-di-n-propyl Oxydecane, di-cyclopentyl-di-iso-propoxydecane, di-cyclohexyldimethoxydecane, di-cyclohexyldiethoxydecane, di-cyclohexyl-di-n-propoxy Basearane, di-cyclohexyl-di-iso-propoxydecane, di-cyclohexenyldimethoxydecane, di-cyclohexenyldiethoxydecane, di-cyclohexenyl-di- Η-propoxydecane, di-cyclohexenyl-di-iso-propoxydecane, di-cyclohexenylethyldimethoxydecane, di-cyclohexenylethyldiethoxy Baseline, di-cyclohexenylethyl-di-n-propoxydecane, di-cyclohexenylethyl-di-iso-propoxydecane, di-cyclooctyldimethoxydecane , di-cyclooctanediethoxy decane, di-cyclooctyl-di-n-propoxy hydrazine-27- 200920791 alkane, di-cyclooctyl-di-iso-propoxy decane, Di-cyclopentadienylpropyl dimethoxydecane, di-cyclopentadienylpropyl diethoxy decane, di-cyclopentadienylpropyl-di-n-propoxy decane, two -cyclopentadienylpropyl-di-iso-propoxydecane, bis-bicycloheptenyldimethoxydecane, bis-bicycloheptenyldiethoxydecane, bis-bicycloheptene -di-n-propoxydecane, bis-bicycloheptenyl-di-iso-propoxydecane, bis-dicycloheptyldimethoxydecane, bis-bicycloheptyldiethoxy Decane, bis-bicycloheptyl-di-η-propoxydecane, bis-bicycloheptyl-di-iso-propoxydecane, bis-adamantyl dimethoxydecane, bis-adamantyl Diethoxydecane, bis-adamantyl-di-η-propoxydecane, bis-adamantyl-di-iso-propoxydecane, and the like. Further light absorbing monomers such as diphenyldimethoxydecane, diphenyl-di-ethoxydecane, methylphenyldimethoxydecane, methylphenyldiethoxydecane, diphenyl Base-di-n-propoxydecane, diphenyl-di-iso-propoxydecane, and the like. Preferred is dimethyldimethoxydecane, dimethyldiethoxydecane, diethyldimethoxydecane, diethyldiethoxydecane, methylethyldimethoxydecane, Ethyl ethyl ethoxy decane, di-η-propyl-di-methoxy decane, di-η-butyl-di-methoxy decane, methyl phenyl dimethoxy decane, methyl benzene Diethoxy decane and the like. For example, m 1 = 1, m 2 = 1, m 3 = 1 one of the alcoxy sands, for example, trimethyl methoxy decane, trimethyl ethoxy decane, dimethyl ethyl methoxy Decane, dimethylethyl ethoxy decane, and the like. Further light absorbing monomers such as dimethylphenyl methoxy decane, dimethylphenyl ethoxy decane, dimethyl benzyl methoxy decane, dimethyl benzyl ethoxy decane, dimethyl Alkyl phenyl-28-200920791 methoxy methoxy decane, dimethyl phenethyl ethoxy decane, and the like. Preferred are trimethylmethoxydecane, dimethylethylmethoxydecane, dimethylphenylmethoxydecane, dimethylbenzylmethoxydecane, dimethylphenethylmethoxy Decane and so on. Other than the organic group represented by R1, R2 and R3, for example, an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, for example, it has an organic group having one or more selected from the group consisting of an epoxy group, an ester group, an alkoxy group, and a hydroxyl group. The organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (3) is, for example, a group represented by the following formula (4) (P-Ql-(Si) v1-q2 -) u- (t) v2-Q3_ (S2) V3-Q4- (4) (In the above formula, 'P is a hydrogen atom, a hydroxyl group, an epoxy ring [Chemical 1] (CH2CH-), a carbon number of 1 to 4) An alkoxy group, an alkylcarbenyloxy group having 1 to 6 carbon atoms, or an alkylcarbonyl group having 1 to 6 carbon atoms, Qi, q2, Q3 and Q4 are each independently -CqH(2q-p)Pp- (wherein , P is the same as above, p is an integer from 〇 to 3, q is an integer from 0 to 10 (but q = 0 is a single bond), u is an integer from 0 to 3, and 3, and s2 are each independently _〇_, _C0-, -〇c〇. '-COO - or - OCOO-.vl, V2, V3 are each independently 0 or 1. Further, T is a divalent group formed by an alicyclic or aromatic ring which may contain a hetero atom. The alicyclic or aromatic ring which may contain a hetero atom such as an oxygen atom is as follows. The bonding position of Q 2 and Q 3 in T is not particularly limited, and a commercially available reagent for reactivity and reaction from a stereoscopic factor may be considered. Appropriate choices such as acquisition). -29- 200920791 【化2】

ν π 〇 Q Q JQ ^ Q Ο O °Q. 〇

The organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (3) is preferably as follows. Further, in the following formula (Si), the bonding position with Si is described. -30- 200920791 【化3】

-31 - 200920791 【化4】

OH

OH

OH OCH3 OH OH OH OCH3 〇- (Si), ^^〇c〇CH3 (Si), (Si) 【化5】

(Si)

.OCOCH 1 3 (Si)

OH

OCOCH 3

OH

(Si) (Si)

Further, as the organic group of R1, R2 or R3, for example, an organic group containing a fluorene bond may be used, and specific examples thereof include the following. -32 - 200920791 [Chemical 6] CH3 H C Hs!>;Si-Si-Si?c4 h3c j ch3 fSi-Si-Si-Cft JL CH3 ,c,S\

HaC.^CI H3C., ch3 (Si) ch3 ch3 H3C~Si—Si—CH3 ^ CH3 (Si) 9H3 ch3 ch3 (Si) (Si) "(Si) CH3 CH39H3CH3 Si—*Si—Si—Si- Qi-jj )CH3CH3CH3 ~Si—Sf—*ΌΗ3 I 1 _ J ch3 ch3 CH3CH3 9H3

H3C—Si——Si—Si—GH3 H3C J CH3 y (Si) (Si) H3C-^CH3 H^?>Si-Si-Si-cH^3 H<3C^j-ciH3 (Si) h3c ch3 Η^ς CH3 H3〇Si/, Si-CH3 / \ 0 HsC-Si, /Si-CH3 h3c ch3 (CH3 H3C-S1 gj-CH; H3C Si^ 'CH3 |'ch3 (sir (Si)" One or two or more kinds of monomers may be selected, and a ruthenium-containing compound may be used as a reaction raw material before or during the reaction. The ruthenium-containing compound may be, preferably, an inorganic acid, an aliphatic sulfonic acid or an aromatic sulfonic acid. One or more kinds of compounds are selected as acid catalysts, and the monomers are hydrolyzed and condensed. The acid catalyst used at this time is, for example, hydrofluoric acid, hydrochloric acid, hydrogen bromide, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, Methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, difluoromethyl sulfonic acid, etc. The amount of catalyst used is from 10.6 to 10 moles, preferably from 10 to 5 moles per mole of sand monomer. More preferably, the molar amount is from 1 to 4 to 1 mol. When the monomer is hydrolyzed and condensed to obtain a ruthenium-containing compound, the amount of water added is relative to the hydrolyzable substituent bonded to the monomer. Good for 〇〇ι to 1〇〇莫耳' is preferably 0.05 to 50 moles. It is better to 〇” to 3〇-33- 200920791 Moer. When the amount exceeds 丨〇〇莫耳, the reaction device will be too large and uneconomical. The operation method such as 'adding monomer to the aqueous solution of the catalyst to start hydrolysis and condensation In this case, the organic solvent may be added to the aqueous solution of the catalyst, or the monomer may be diluted with the organic solvent or both. The reaction temperature is from 〇 to l〇〇t, preferably from 5 to 8 (rc. preferably drops The monomer is kept at a temperature of 5 to 8 ° C, and then matured at 20 to 8 Torr. The organic solvent in which the aqueous solution of the catalyst or the diluent is added is preferably methanol, ethanol, or 1-propyl. Alcohol '2-propanol, 丨-butanol, 2-butanol, 2-methyl-b propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2- N-amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol-ethyl ether, ethylene glycol monoethyl ether, Propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate vinegar, ethyl pyruvate, Butyl acrylate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-Urt-butyl ether acetate, 7- Butyl lactone and mixtures of these, etc.. Solvents are preferred among these solvents. For example, methanol 'ethanol, 1 -propanol, 2-propanol and other alcohols, ethylene glycol, propylene glycol, etc. Valence alcohol, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol A polyvalent alcohol condensate derivative such as monopropyl ether, propylene glycol monopropyl ether or ethylene glycol monopropyl ether; acetone, acetonitrile, tetrahydrofuran or the like. Among them, it is particularly preferred to be a boiling point of less than 100 °C. The use amount of the organic solvent is preferably from 〇 to 1,000 ml, particularly preferably from 〇 to 500 ml, based on the monomer 1 molar. When the amount of organic solvent used is too large, the reaction vessel will be too large and uneconomical. Thereafter, a catalyst neutralization reaction may be carried out as necessary, and the alcohol formed by the hydrolysis condensation reaction may be removed under reduced pressure to obtain an aqueous solution of the reaction mixture. The amount of the basic substance which can be used for neutralization at this time is preferably from 1 to 2 equivalents based on the acid used for the catalyst. The alkaline substance may be alkaline in water and may be any substance. The alcohol formed by the hydrolysis condensation reaction is then removed from the reaction mixture. The heating temperature of the reaction mixture at this time depends on the organic solvent to be added and the type of alcohol produced by the reaction, but is preferably from 10 to TC, preferably from 10 to 9 〇 ° C, more preferably from 15 to 5. 80 ° C. At this time, the degree of decompression will vary depending on the organic solvent and alcohol type to be removed, the exhaust device, the condensation device, and the heating temperature, but it is preferably below atmospheric pressure and below 8 OkP a absolute pressure. Preferably, it is preferably an absolute pressure of 5 OkP a or less. Although it is difficult to accurately know the amount of alcohol removed, it is desirable to remove 80% by mass of the alcohol formed. Secondly, the acid used for the hydrolysis condensation can be removed from the reaction mixture. Catalyst. The method of removing the acid catalyst, such as 'mixing water and containing cerium compound, and taking the cerium compound in an organic solvent. The organic solvent used at this time is preferably a solvent which can dissolve the cerium-containing compound. a two-layered separation, for example, methanol, ethanol, 1-propanol, 2-propanol, [-butanol, 2-butanol, 2-methyl-propylidene, acetone, tetrahydrofuran, toluene, hexane, Ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, butanediol - Ether, propylene glycol-methyl ether, ethyl alcohol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, B-35-200920791 diol monoethyl ether, butanediol monopropyl ether, Propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether 'diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, pyruvic acid Ester, butyl acetate 'methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate tert-butyl propionate, propylene glycol-tert-butyl ether acetate, T-butyl lactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof, etc. Further, a mixture of a water-soluble organic solvent and a water-insoluble organic solvent may be used. Preferably, methanol + ethyl acetate , ethanol + ethyl acetate, 1-propanol + ethyl acetate, 2-propanol + ethyl acetate, butanediol monomethyl ether + ethyl acetate, propylene glycol monomethyl ether + ethyl acetate, ethylene glycol Monomethyl ether, butanediol monoethyl ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate, ethylene glycol monoethyl ether + ethyl acetate, butanediol monopropyl +ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl ether + ethyl acetate, methanol + methyl isobutyl ketone, ethanol + methyl isobutyl ketone, 1-propanol + Methyl isobutyl ketone, 2-propanol + methyl isobutyl ketone, propylene glycol monomethyl ether + methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monoethyl ether + methyl isobutyl Base, ethylene glycol monoethyl ether + methyl isobutyl ketone, propylene glycol monopropyl ether + methyl isobutyl ketone, ethylene glycol monopropyl ether + methyl isobutyl ketone, methanol + cyclopentyl Methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + cyclopentyl methyl ether, 2-propanol + cyclopentyl methyl ether, propylene glycol monomethyl ether + cyclopentyl methyl ether, B Glycol monomethyl ether + cyclopentyl methyl ether, propylene glycol ~ ethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentane Methyl ether, ethylene glycol monopropyl ether + cyclopentyl methyl ether, methanol + C-36- 200920791 diol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, 丨_propanol + propylene glycol methyl ether acetate ' 2 -propanol + propylene glycol methyl ether acetate , propylene glycol monomethyl ether + propylene glycol methyl ether acetate, ethylene glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate 'ethyl alcohol monoethyl ether a composition such as ether + propylene glycol methyl ether acetate, propylene glycol monopropyl ether + propylene glycol methyl ether acetate, ethylene glycol - propyl ether + propylene glycol methyl ether acetate, but is not limited to such compositions . The mixing ratio of the water-soluble organic solvent to the water-insoluble organic solvent can be appropriately selected, and the water-soluble organic solvent may be 0.1 to 1 , 〇〇〇 by mass, preferably 1 to 5, with respect to 1 part by mass of the water-insoluble organic solvent. 00 parts by mass, more preferably 2 to 1 part by mass. Then wash with neutral water. The water used may be generally referred to as deionized water and ultrapure water. The amount of water is 0.01 to 100 L, preferably 0.05 to 50 L, more preferably 0.1 to 5 L, relative to 1 L of the cerium-containing compound solution. The washing method may be such that the separated water is allowed to stand after mixing both sides in the same container. The number of times of washing may be one or more, and since only a washing effect is obtained even if it is washed one or more times, it is preferably from 1 to 5 times. Other methods for removing the acid catalyst include, for example, a method using an ion exchange resin, or a method of neutralizing and then removing an epoxy compound such as ethylene oxide or propylene oxide. These methods can be appropriately selected in accordance with the acid catalyst used for the reaction. In the above-described operation of removing the catalyst, the substantial removal of the acid catalyst means that the amount of the catalyst to be added added to the reaction of the ruthenium-containing compound is allowed to remain at 10% by mass or less, preferably 5% by mass or less. At this time, the washing operation will cause some of the cerium-containing compound to escape into the water layer' and -37-200920791 is equivalent to the effect of the substantial division operation'. Therefore, the number of washing times and the amount of washing water can be appropriately determined after the catalyst removal effect and the division effect are identified. select. Regardless of the ruthenium-containing compound containing the residual acid catalyst or the ruthenium-containing compound from which the acid catalyst is removed, the ruthenium-containing compound solution can be obtained by adding a solvent to the final solvent and then performing solvent exchange under reduced pressure. The solvent exchange temperature at this time depends on the type of the reaction solvent to be removed and the extraction solvent, but is preferably 〇 to 10 (TC, preferably 10 to 90 ° C, more preferably 15 to 8 0 ° C. Further, the degree of decompression at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but it is preferably at most atmospheric pressure and preferably at an absolute pressure of 80 kPa or less. More preferably, the absolute pressure is 50 kPa or less. At this time, changing the solvent causes the ruthenium-containing compound to be unstable. Because the final solvent and the ruthenium-containing compound are phase-sensitive, in order to prevent the addition of the stabilizer, the component (C) described later may be added. The amount is from 〇 to 25 parts by mass, preferably from 0 to 15 parts by mass, more preferably from 〇 to 5 parts by mass, based on 100 parts by mass of the cerium-containing compound in the solution before solvent exchange, but it is preferably added in an amount of 0.5 parts by mass or more. If necessary, the solution before the solvent exchange may be added with the component (C) for solvent exchange operation. When the ruthenium-containing compound is concentrated to a certain concentration or more and then subjected to a condensation reaction, it may be changed to a state in which it is no longer dissolved with respect to the organic solvent. Moderate concentration In the case of a solution, the concentration is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less. The final solvent to which the cerium-containing compound solution is added is preferably an alcohol-based solvent. An alkyl ether such as an alkyl ether such as an alcohol, diethylene glycol or triethylene glycol, or a propylene glycol or dipropylene glycol. The specific example is preferably butanediol monomethyl ether-38 - 200920791, propylene glycol monomethyl Ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol Further, other reaction operations such as 'water or aqueous organic solvent are added to the organic solvent of the monomer or monomer to start the hydrolysis reaction. At this time, the catalyst can be added to the organic solvent of the monomer or monomer' Or adding water or an organic solvent containing water. The reaction temperature is 〇 to 10 ° C, preferably 10 to 8 (TC. It is heated to 1 〇 to 50 ° C when dripping water, and then 20 to The method of ripening of 80 is preferred. It is preferably water-soluble when using an organic solvent, for example, methanol, ethanol, 1 -propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol' acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, B Glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether a polyvalent alcohol condensate derivative such as propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate 'propylene glycol monoethyl ether acetate' propylene glycol monopropyl ether, and the like The organic solvent can be used in the same amount as described above. The resulting reaction mixture can be treated as described above to obtain a ruthenium-containing compound. The molecular weight of the obtained ruthenium-containing compound can be controlled by polymerization. The reaction conditions are adjusted, but when a weight average molecular weight of more than 100,0 0 is used, a foreign matter and a coating spot may be generated depending on the case, and therefore it is preferably used in an amount of 100,000 or less, more preferably 200 to 50,000, particularly preferably 300 to 30,000 things. The data on the above-mentioned weight average molecular weight is represented by a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC) using an RI detector and polystyrene as a standard substance, using -39-200920791. The composition for forming a film containing ruthenium according to the present invention may be a product produced under acidic conditions, or may contain two or more kinds of ruthenium-containing compounds having different compositions and/or reaction conditions. Next, the other ruthenium-containing compound (A-2) used in the present invention is obtained by subjecting a monomer to hydrolysis and condensation by a basic catalyst. Preferably, the method for producing a ruthenium-containing compound is as follows, but is not limited thereto. The monomer of the starting material to be used may be the one represented by the above general formula (3), specifically, for example, the above. The ruthenium-containing compound can be obtained by hydrolyzing and condensing a monomer in the presence of a basic catalyst. The basic catalyst used at this time is, for example, methylamine, ethylamine, propylamine, butylamine, ethylidene diamine, hexamethylenediamine, dimethylamine, diethylamine, Ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, monomethylethanolamine, monomethyl Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine , ν, Ν-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, four Butyl ammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like. The amount of the catalyst used is 丨〇-6 to 10 mols, preferably ΗΓ5 to 5 mols, more preferably 1〇·4 to 1 mol-40-200920791 by hydrolysis. The amount of water obtained by condensing the monomer-containing hydrazine-containing compound is preferably 0.01 to 100 moles per mole of the hydrolyzable substituent bonded to the monomer, and preferably 0.05 to 50 moles. S to 30 moles. More than 100 moles will make the reaction device economical. For example, the monomer is added to the aqueous solution of the catalyst to start the reaction. At this time, an organic solvent may be added to the aqueous solution of the catalyst, the solvent may be diluted, or both may be simultaneously performed. The reaction temperature is 0, preferably 5 to 80 °c. Further, it is kept at 5 to 10 degrees when the monomer is dropped, and then 20 to 8 (the method of TC is preferred. It can be added to the aqueous solution of the catalyst or the organic solvent for diluting the monomer, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, ethyl diacid, cyclohexanone, methyl-2-n-amyl ketone, dibutyl Alcohol-propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl glycol dimethyl ether, propylene glycol one Ethyl acetate, propylene glycol acetate, ethyl pyruvate, butyl acetate, ethyl methoxypropionic acid ethoxypropionate, tert-butyl acetate, tert-butanol propionate-tert- Butyl ether acetate, 7-butyl lactone, and the like are preferably water-soluble, such as methanol, propanol, 2-propanol, alcohol, ethylene glycol, propylene glycol The multi-valent 'added ear is preferably ΐ preferably 0.1 large without hydrolysis condensation or organic to 1000 ° C 80 ° C temperature agent such as alcohol, 2-methylbenzene, ethyl methyl ether , ether, propyl ether, two Ethyl ethyl ether methyl ester, 3-ester, propylene diacetate, etc., ethanol, alcohol, butyl-41 - 200920791 alcohol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol a polyvalent alcohol condensate derivative such as ethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether 'butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, Acetonitrile, tetrahydrofuran, etc. Among them, particularly preferred is a boiling point of 100 ° C or less. The amount of the organic solvent used is preferably from 0 to 1,0 0 ml, particularly preferably from 〇 to 500 ml, relative to the monomer 1 molar. When the amount of use is too large, the reaction vessel may be too large and uneconomical. Thereafter, a catalyst neutralization reaction may be carried out if necessary, and the alcohol formed by the hydrolysis condensation reaction may be removed under reduced pressure to obtain an aqueous solution of the reaction mixture. The amount of the acidic substance added is preferably from 0.1 to 2 equivalents based on the base of the catalyst. The acidic substance may be an acidic substance in water, and may be any substance. The reaction mixture is then removed to remove the hydrolysis condensation reaction. Alcohol. The heating temperature of the reaction mixture is based on The organic solvent to be added and the type of alcohol produced by the reaction, but preferably from 0 to 10 (TC, preferably from 10 to 90 t, more preferably from 15 to 80 ° C. Also, at this time The degree of pressure reduction varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably at most atmospheric pressure, and preferably at an absolute pressure of 80 kPa or less, more preferably at an absolute pressure of 50 kPa. In this case, it is not easy to accurately understand the amount of alcohol to be removed, but it is preferable to remove 80% by mass or more of the produced alcohol. Next, in order to remove the catalyst for hydrolysis and condensation, the cerium-containing compound may be extracted by an organic solvent. The organic solvent to be used is preferably one which can dissolve the ruthenium-containing compound 'mixed water and can be separated in two layers. For example, methanol, ethanol, -42-200920791 1 -propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-; 1-propanol, acetone, tetrahydrofuran, toluene, hexane, Ethyl acetate, cyclohexanone, .methyl-2-n-pentyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether 'butanediol monoethyl ether' Propylene glycol monoethyl ether, ethylene glycol monoethyl ether 'butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert acetate -butyl ester, tert-butyl propionate, propylene glycol-tert-butyl ether acetate, τ-butyl lactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof, etc. A mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent can be used. Preferably, methanol + ethyl acetate, ethanol + ethyl acetate, 1-propanol + ethyl acetate, 2-propanol + ethyl acetate, butanediol monomethyl ether + ethyl acetate, propylene glycol monomethyl Ether + ethyl acetate, ethylene glycol monomethyl ether, butanediol monoethyl ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate 'ethylene glycol ethyl ether + ethyl acetate, dibutyl Alcohol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl ether + ethyl acetate, methanol + methyl isobutyl ketone, ethanol + methyl isobutyl ketone, 1-propanol + methyl isobutyl ketone, 2-propanol + methyl isobutyl ketone, propylene glycol monomethyl ether + methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monoethyl ether +Methyl isobutyl ketone, ethylene glycol monoethyl ether + methyl isobutyl ketone, propylene glycol monopropyl ether + methyl isobutyl ketone, ethylene glycol monopropyl ether + methyl isobutyl ketone , methanol + cyclopentyl methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + cyclopentyl methyl ether, 2-43 - 200920791 propanol + cyclopentyl methyl ether, propylene glycol one Ether ether + cyclopentyl methyl ether, ethylene glycol monomethyl ether + cyclopentyl Ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentyl methyl ether, ethylene glycol monopropyl Ether + cyclopentyl methyl ether, methanol + propylene glycol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, propanol + propylene glycol methyl ether acetate, 2-propanol + propylene glycol methyl ether Acetate, propylene glycol monomethyl ether + propylene glycol methyl ether acetate, ethylene glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate, ethylene Compositions such as alcohol monoethyl ether + propylene glycol methyl ether acetate, propylene glycol monopropyl ether + propylene glycol methyl ether acetate, ethylene glycol monopropyl ether + propylene glycol methyl ether acetate, but are not limited The composition. The mixing ratio of the water-soluble organic solvent to the water-insoluble organic solvent can be appropriately selected, but the water-soluble organic solvent may be 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, per 1 part by mass of the water-insoluble organic solvent. More preferably, it is 2 to 100 parts by mass. Then wash with neutral water. The water used may be generally referred to as deionized water and ultrapure water. The amount of the water is from 0.01 to 100 L, preferably from 0.05 to 50 L, more preferably from 0.1 to 5 L, based on 1 L of the cerium-containing compound solution. The washing method may be such that the water layer is left to stand after the two sides are mixed in the same container. The number of times of washing may be one or more. However, even if it is washed 10 times or more, only the washing effect is obtained, so it is preferably 1 to 5 times. Other methods for removing the alkaline catalyst are, for example, a method using an ion exchange resin. These methods can be suitably selected in conjunction with the basic catalyst for the reaction. In the present invention, the basic catalyst is substantially removed, and the alkaline catalyst for allowing the remaining ruthenium-containing compound -44 - 200920791 is 1% by mass or less, preferably 5% by mass or less. After removing the basic catalyst, the final solvent is added to the ruthenium-containing compound solution, and the solvent is exchanged under reduced pressure to obtain a ruthenium-containing compound solution. The solvent exchange temperature at this time depends on the type of the extraction solvent to be removed, but is preferably from 0 to 100 t, more preferably from 1 Torr to 90 ° C, still more preferably from 15 to 80 ° C. Further, the degree of decompression at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but it is preferably at most atmospheric pressure, and preferably at an absolute pressure of 80 kPa or less, more preferably absolute. The pressure is below 50 kPa. The final solvent to be added to the cerium-containing compound solution is preferably an alcohol-based solvent, preferably one of an alkyl ether such as ethylene glycol, diethylene glycol or triethylene glycol, or an alkyl ether such as propylene glycol or dipropylene glycol. Specific examples are preferably, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, Butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, and the like. Further, other reaction operations such as adding water or an aqueous organic solvent to the organic solvent of the monomer or monomer start the hydrolysis reaction. The catalyst may be added to the organic solvent of the monomer or monomer, or added to water or an aqueous organic solvent. The reaction temperature may be from 〇 to 100 ° c ', preferably from 10 to 8 ° C. Further, it is preferred to heat the mixture to ίο to 50 °c' while dripping in water, and then to raise the temperature to 20 to 80. When an organic solvent is used, it is preferably a water-soluble substance such as 'methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, Tetrahydrofuran, acetonitrile, butanol monomethyl ether, propylene glycol monomethyl-45- 200920791 ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol Monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate And a polyvalent alcohol condensate derivative such as propylene glycol monoethyl ether acetate or propylene glycol monopropyl ether, and the like, and the like. The organic solvent can be used in the same amount as described above. The obtained reaction mixture may be subjected to post-treatment in the same manner as described above to obtain a ruthenium-containing compound (A-2). The molecular weight of the ruthenium-containing compound (A-2) obtained may be controlled by polymerization in addition to monomer selection. Conditional adjustment 'But when using a weight average molecular weight of more than 10, 〇〇〇, 〇〇〇, depending on the situation, foreign matter and coating spots may be generated, so it is better to use less than 8,000,000', preferably 200 to 5,000,000, more preferably It is 300 to 3,000,000. The data on the above-mentioned weight average molecular weight is expressed by the polystyrene standard molecular weight measured by gel permeation chromatography (GPC) using an RI detector or a light scattering detector using polystyrene as a standard substance. The composition for forming a film containing ruthenium according to the present invention may be one which is produced under alkaline conditions, or may contain two or more kinds of ruthenium-containing compounds (A-2) having different compositions and/or reaction conditions. Further, the thermal crosslinking accelerator (B), the acid (c), the stabilizer (D), and the organic solvent (E) are added to the above-mentioned cerium-containing compound (Al) and (A-2) to form a film containing ruthenium. Use the composition. In this case, the ruthenium-containing compound (A-1) and the ruthenium-containing compound (A-2) are preferably 'the ratio of the former mass to the latter mass (i.e., '(eight-1"...-2)). -46 - 200920791. More preferably, the amount of (A_2) added to (A-1) 1 〇 0 parts by mass is 〇 < (A-2) S50 parts by mass 'preferably 〇 < (A_2) G3 〇 parts by mass, more preferably 〇 ((A-2) S 20 parts by mass. In order to further promote the crosslinking reaction in the formation of the ruthenium-containing film of the present invention, it is necessary to contain (B) component for thermal crosslinking promotion. The compound is, for example, a compound represented by the general formula (i) or (2).

LaHbX (1) (wherein, L is lithium, sodium, potassium, rubidium or planer, x is a hydroxyl group, or a monovalent or higher organic acid group having a carbon number of 丨 to 3〇, & an integer of 1 or more, b is 〇 or an integer of 1 or more, and a + b is the number of hydroxyl groups or organic acid groups).

MaHbA (2) (wherein 'Μ is sulphur, iodine or ammonium, preferably a three-stage sulphur gun, a second-stage iodine gun or a quaternary ammonium, especially a photodecomposable substance, ie a triphenyl sulphur gun Compound, diphenyl iodine gun compound. Α is the above X or non-nucleophilic counter ion, a, b is the same as above, a + b is the valence of hydroxyl group, organic acid group or non-nucleophilic counter ion). The compound represented by the general formula (1) is an alkali metal organic acid salt. For example, lithium, sodium, potassium, hydrazine, hydroxyacid, formate, acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, citrate , citrate, oleate, stearate, linoleate, linolenate, -47 - 200920791 benzoate, citrate, isophthalate, terephthalate, water a monovalent salt such as salicylate, trifluoroacetate, monochloroacetate, dichloroacetate or trichloroacetate, monovalent or divalent oxalate, malonate, methylmalonate, B Base malonate, propyl malonate, butyl malonate, dimethylmalonate, diethyl malonate, succinate, methyl succinate, glutarate , adipate, itaconate, maleate, fumarate, citrate, citrate, carbonate, and the like. Specifically, for example, lithium formate, lithium acetate, lithium propionate, lithium butyrate, lithium valerate, lithium hexanoate, lithium heptanoate, lithium octoate, lithium niobate, lithium niobate, lithium oleate, lithium stearate, sub Lithium oleate, lithium linolenate, lithium benzoate, lithium niobate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, Lithium dichloroacetate, lithium trichloroacetate, lithium hydroxide, lithium hydrogen oxalate, lithium hydrogen malonate, lithium hydrogen methacrylate, lithium hydrogen oxalate, lithium propyl propyl hydride, butyl Lithium hydrogen malonate, lithium dimethylmalonate, lithium diethyldihydrogenate, lithium hydrogen succinate, lithium methyl succinate, lithium hydrogen glutarate, lithium hydrogen adipate, Yikang Lithium hydrogen phosphate, lithium hydrogen maleate, lithium hydrogen fumarate, lithium hydrogen citrate, lithium hydrogen citrate, lithium hydrogencarbonate, lithium oxalate, lithium malonate, lithium methylmalonate, ethyl propylene Lithium acid, lithium propylmalonate, lithium butylmalonate, lithium dimethylmalonate, lithium diethylmalonate, lithium succinate, lithium methyl succinate, lithium glutarate, hexane Lithium acid, itaconic acid Lithium, lithium maleate, lithium fumarate, lithium citrate, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium valerate, sodium hexanoate, sodium heptanoate, octanoic acid Sodium, sodium citrate, sodium citrate, sodium oleate, sodium stearate, sodium linoleate, sodium linolenate, sodium benzoate, citric acid-48-200920791 sodium, sodium isophthalate, sodium terephthalate, Sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, sodium hydrogen oxalate, sodium hydrogen malonate, methyl propylene Sodium hydrogen hydride, sodium ethyl malonate, sodium propylmalonate, sodium butyl methacrylate, sodium dimethylmalonate, sodium diethylmalonate, sodium hydrogen succinate , methyl sodium benzoate, sodium hydrogen glutarate, sodium hydrogen adipate, sodium itaconate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium citrate, sodium hydrogen citrate, Sodium bicarbonate, sodium oxalate, sodium malonate, sodium methylmalonate, sodium ethylmalonate, sodium propylmalonate, sodium butylmalonate, sodium dimethylmalonate, diethyl Malonic acid 'Sodium succinate, sodium methyl succinate, sodium pentoxide, sodium adipate, sodium itaconate, sodium maleate, sodium fumarate, sodium citrate, sodium citrate, sodium carbonate, potassium formate , potassium acetate, potassium propionate, potassium butyrate, potassium pentanoate potassium, potassium heptate, potassium octoate, potassium citrate, potassium citrate, potassium oleate, potassium stearate, potassium linoleate, flax Potassium acid, potassium benzoate, potassium citrate, potassium isophthalate, potassium terephthalate, potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, Potassium trichloroacetate, potassium hydroxide, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen malonate, potassium hydrogen propyl malonate, potassium propyl malonate, potassium hydrogen butyl acrylate , potassium dimethylmalonate, potassium hydrogen dihydromalonate, potassium hydrogen succinate, potassium hydrogen methyl succinate, potassium hydrogen glutarate, potassium hydrogen sulphate, potassium itaconate, horse Potassium hydrogenate, potassium hydrogen fumarate, potassium hydrogen citrate, potassium hydrogen citrate, potassium hydrogencarbonate, potassium oxalate 'potassium malonate, potassium methylmalonate, potassium ethylmalonate, propyl Potassium malonate, butyl Potassium diacid, potassium dimethylmalonate, potassium diethylmalonate, potassium succinate, potassium methyl succinate, potassium pentoxide-49- 200920791, potassium adipate, potassium itaconate, horse Potassium acid, potassium fumarate, potassium citrate, potassium citrate, potassium carbonate, and the like. The compound represented by the general formula (2) is a sulfur gun compound, an iodine gun compound, or an ammonium compound represented by (Q·!), (Q_2), and (Q_3). [Ration 7] R204 r205 S® Q R206 A R204 r205 Θ A R207 p208 N ^r< .N© a R2〆, R209 A (QD (Q-2) (Q-3) (where r 2〇4, R2〇5 'r206 are each a linear chain of carbon numbers 1 to η,

Branched or cyclically substituted, alkenyl, carbonylalkyl or carbonylalkenyl, substituted or unsubstituted aryl of carbon 6 S 2 ' or aralkyl having 7 to 12 carbons or aryl &; 院基基's part or all of the hydrogen atoms of these groups may be taken by alkoxy groups, etc. ' π:. Further, R2 5 and r2G6 form a ring, and when the ring is formed, r2G5 and r206 are alkyl groups of from 1 to 6. A- is a non-nucleophilic counterion. R °7 '11208, R2Q9, R21 are the same as R204, R205, R206, but can be hydrogenogen =. Nw and r2G8, r2Q7 and r2Q8 and r2q9 form a ring, forming a ring h R °7 and R2G8, R2G7 and R2Q8 and R2Q9 are a C 3 to 1 Q alkyl group). The above R2. 4, R2 °5, R2 0 6 , R207, R2 0 8 , R2 0 9 , r21Q may be phased different each time 'specific hospital base such as 'methyl' ethyl, propyl, isopropyl, butyl Base, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, ττιη pentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl' ring P ? > methyl group, fatigue base, King Kong base, etc. The chain is suspected to be a base such as phenyl group -50.200920791, allyl, propenyl, butenyl, hexenyl, cyclohexenyl and the like. A carbonylalkyl group such as 2-carbonylcyclopentyl, 2-carbonylcyclohexyl or the like, or 2-carbonylpropyl, 2-cyclopentyl-2-carbonylethyl '2-cyclohexyl-2-carbonylethyl, 2 -(4-Methylcyclohexyl)-2-carbonylethyl and the like. Aryl such as 'phenyl, naphthyl, etc.' or p-methoxyphenyl, m-methoxyphenyl, fluorenyl-methoxyphenyl, ethoxyphenyl, p-tert-butoxybenzene Or an alkyloxy group such as m-tert-butoxyphenyl, or 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butyl Alkyl such as phenyl, 4-butylphenyl or _methylphenyl, alkylnaphthyl such as methylnaphthyl or ethylnaphthyl, methoxynaphthyl, ethoxynaphthyl and the like a dialkoxynaphthyl group such as a dialkylnaphthyl group such as an oxynaphthyl group, a dimethylnaphthyl group or a diethylnaphthyl group, a dimethoxynaphthyl group or a diethoxynaphthyl group, or the like, an aralkyl group such as Benzyl, phenylethyl, phenethyl and the like. An arylcarbonylalkyl group such as 2-phenyl-2-carbonylethyl, 2-(1-naphthyl)-2-carbonylethyl, 2-(2-naphthyl)-2-carbonylethyl, etc. 2- Aryl-2-carbonylethyl and the like. Non-nucleophilic counter-ions such as hydroxy ions, formic acid ions, acetate ions, propionic acid ions, butyric acid ions, valeric acid ions, hexanoic acid ions, heptanoic acid ions, octanoic acid ions, citrate ions, strontium ions Acid ion, oleic acid ion, stearic acid ion, linoleic acid ion, linolenic acid ion, benzoic acid ion, P-methylbenzoate ion, pt-butyl benzoate ion, citrate ion, isophthalic acid ion , terephthalic acid ion, salicylic acid ion, trifluoroacetic acid ion, monochloroacetic acid ion, dichloroacetic acid ion, trichloroacetic acid ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion , chlorate ion, perchlorate ion, bromate ion, iodate ion, oxalate ion, malonate ion, methylmalonate ion, ethylmalonic acid-51 - 200920791, propylmalonic acid Ionic, butylmalonate, dimethyl, diethylmalonic acid ion, succinic acid ion, methyl amber glutarate ion, adipic acid ion, itaconic acid ion, maleic acid horse acid ion , citraconic acid ion, citric acid Specific sulphur gun compounds such as ionic and carbonate ions, such as triphenyl sulfone formic acid, ethyl sulphur gun, triphenyl sulphide propionate, triphenyl sulfonium butyrate, iron valerate, triphenyl sulfonate caproate, Triphenylsulfate heptanoate, caprylic acid tris, triphenylsulfuric acid citrate, triphenylsulfuric acid citrate, triphenylsulfuric acid triphenyl stearate, triphenylsulfuric acid linoleum, flax Acid gun, benzoic acid triphenylsulfide gun, P-methylbenzoic acid triphenyl pt-butyl benzoic acid triphenylsulfide gun, triphenylsulfuric acid triphenylsulfuric acid triphenylsulfur gun, terephthalic acid Phenylsulfur gun, salicylic sulphur, triphenylsulfur trifluoromethanesulfonate, triphenylsulfate triphenylphosphoric acid triphenylsulfur gun, triphenylsulfonium dichloroacetate, triphenylsulfonium, Triphenylsulfide hydroxide, triphenylsulfonium triphenylsulfide oxalate, triphenylsulfuric acid methyl malonate, ethyl propylene disulfide gun, triphenylsulfide propyl malonate, butyl Triphenylsulfuric acid triphenyl dimethyl malonate, triphenyl sulfonate triethyl benzoate, triphenyl sulfonate methyl succinate, pentane sulphur gun Triphenyl adipate Sulfur gun, itaconic acid triphenylsulfur gun, phenyl sulfide gun, triphenylsulfide gun, citraconic acid triphenylsulfur gun triphenylsulfide gun, triphenylsulfide carbonate gun, triphenyl chloride Thiosulfate thiosulfur gun, triphenylsulfide iodide, triphenylsulfuric acid nitrate, base sulfur gun, triphenylsulfuric acid perchlorate, triphenylsulfuric acid bromine, malonic acid acid ion , ions, rich, etc. Triphenyltriphenylsulfanylthiothiosulfuric acid, triphenylsulfanylsulfuric iron, triphenylsulfuric acid, chloroacetic acid, triphenylmalonate Sulfur gun, triphenylmaleic acid trisuccinate, citric acid, triphenyl benzene oxybromide triphenyl-52- 200920791 base sulphur iron, oxalic acid bis triphenyl sulphur gun, malonic acid bis triphenyl Base sulphur gun, dimethyl succinic acid bis triphenyl sulphur gun, ethyl malonate bis triphenyl sulphur gun, propyl malonic acid bis triphenyl sulphur gun, butyl succinic acid bis triphenyl sulphide Gun, bis-trimethyl sulphate bistriphenyl sulphide, diethyl succinic acid bis triphenyl sulphide, bistriphenyl sulfonium succinate, methyl succinate bis triphenyl sulphur gun, pentane Acid bis triphenyl sulphide, bistriphenyl sulfonium adipate, bis(triphenyl thiosulfate) itaconate, bis-triphenyl sulphide maleate, bis-triphenyl sulfite citrate, citraconic acid Bis-triphenylsulfur gun, bis-triphenylsulfuric acid citrate, bis-triphenylsulfuric acid carbonate, and the like. Further, the specific iodine gun compound, such as diphenyl iodine gun for formic acid, diphenyl iodine gun for acetic acid, diphenyl iodine gun for propionate, diphenyl iodine gun for butyrate, diphenyl iodine valerate, caproic acid Phenyl iodide gun, heptanoic acid diphenyl iodine gun, octanoic acid diphenyl iodine gun, diphenyl iodine citrate, diphenyl iodine citrate, diphenyl iodine oleate, diphenyl stearyl Iodine gun, linoleic acid diphenyl iodine gun, linolenic acid diphenyl iodine gun, benzoic acid diphenyl iodine gun, P-methyl benzoic acid diphenyl iodine gun, pt-butyl benzoic acid diphenyl iodine Gun, diphenyl iodine citrate, diphenyl iodonium isophthalate, diphenyl iodonium terephthalate, diphenyl iodine salicylate, diphenyl iodine trifluoromethanesulfonate, Triphenyl iodine trifluoroacetate, diphenyl iodine gun for monochloroacetic acid, diphenyl iodine gun for dichloroacetic acid, diphenyl iodine gun for trichloroacetic acid, diphenyl iodine gun for hydrogen peroxide, diphenyl iodine gun for oxalic acid , malonate diphenyl iodine gun, methyl malonate diphenyl iodine gun, ethyl malonate diphenyl iodine iron, propyl malonic acid diphenyl iodine gun, butyl malonic acid diphenyl Base iodine gun, dimethyl propyl Acid diphenyl iodine gun, diethyl malonate diphenyl iodine gun, diphenyl iodine succinate, diphenyl iodine gun methyl succinate, diphenyl iodine glutaric acid, adipic acid Phenyl iodine gun, itaconic acid diphenyl iodine gun, Malay-53- 200920791 acid diphenyl iodine gun, diphenyl iodine gun fumarate, diphenyl iodine gun citrate, diphenyl citrate Iodine gun, diphenyl iodine gun, diphenyl iodine gun, diphenyl iodine gun, diphenyl iodide gun, diphenyl iodine gun, diphenyl iodine gun, high Diphenyl guanidine chlorate gun, diphenyl iodine bromine gun, diphenyl iodonium iodate, bis-diphenyl iodine gun oxalic acid bis-diphenyl iodine gun, methyl propylene dibenzoate Base iodine gun, ethyl malonate bisdiphenyl iodine gun, propyl malonic acid bisdiphenyl iodine gun, butyl malonic acid bisdiphenyl iodine gun, dimethylmalonate bisdiphenyl Iodine gun, diethyl malonate bisdiphenyl iodine gun, bis-diphenyl iodine succinate, bis-phenyl phenyl succinate, bis-diphenyl thionate, adipic acid Diphenyl iodine gun, itaconic acid bisdiphenyl iodine gun, maleic acid Diphenyliodonium gun, diphenyliodonium fumarate, bis gun, citraconic acid bis diphenyliodonium gun, guns diphenyliodonium bis citrate, diphenyliodonium carbonate, bis gun. In addition, specific ammonium compounds such as tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium valerate, tetramethylammonium hexanoate, heptanoic acid Tetramethylammonium, tetramethylammonium octoate, tetramethylammonium citrate, tetramethylammonium citrate, tetramethylammonium oleate, tetramethylammonium stearate, tetramethylammonium linoleate, linolenic acid Tetramethylammonium, tetramethylammonium benzoate, tetramethylammonium p-methylbenzoate, tetramethylammonium pt-butylbenzoate, tetramethylammonium citrate, tetramethylammonium isophthalate, Tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate , tetramethylammonium trichloroacetate, tetramethylammonium hydroxide, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium methylmalonate, tetramethylammonium ethylmalonate, C-54- 200920791 tetramethylammonium malonate, tetramethylammonium butylmalonate, tetramethylammonium dimethylmalonate, tetramethylammonium diethylmalonate, tetramethyl succinate Glutamate Tetramethylammonium citrate, tetramethylammonium glutarate, tetramethylammonium adipate, tetramethylammonium itaconate, tetramethylammonium maleate, tetramethylammonium fumarate, citraconic acid Tetramethylammonium, tetramethylammonium citrate, tetramethylammonium carbonate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethyl chlorate Ammonium, tetramethylammonium perchlorate, tetramethylammonium bromate, tetramethylammonium iodate, bistetramethylammonium oxalate, bistetramethylammonium malonate, bistetramethylammonium methylmalonate , bis-tetramethylammonium ethyl malonate, bis-tetramethylammonium propyl malonate, bis-tetramethylammonium butyl malonate, bis-tetramethylammonium dimethylmalonate, diethyl propyl Di-tetramethylammonium diamine, bistetramethylammonium succinate, bistetramethylammonium methyl succinate, bistetramethylammonium glutarate, bistetramethylammonium adipate, itaconic acid Base ammonium, bistetramethylammonium maleate, bistetramethylammonium fumarate, bistetramethylammonium citrate, bistetramethylammonium citrate, bistetramethylammonium carbonate, tetrapropylammonium formate , tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropyl butyrate Ammonium, tetrapropylammonium valerate, tetrapropylammonium hexanoate, tetrapropylammonium heptanoate, tetrapropylammonium octoate, tetrapropylammonium citrate, tetrapropylammonium citrate, tetrapropylammonium oleate, Tetrapropylammonium stearate, tetrapropylammonium linoleate, tetrapropylammonium linolenate, tetrapropylammonium benzoate, tetrapropylammonium P-methylbenzoate, tetrapropyl pt-butylbenzoate Ammonium, tetrapropylammonium citrate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate Ammonium, tetrapropylammonium monochloroacetate, tetrapropylammonium dichloroacetate, tetrapropylammonium trichloroacetate, tetrapropylammonium hydroxide, tetrapropylammonium oxalate, tetrapropylammonium malonate, methyl Malonic acid-55- 200920791 tetrapropylammonium, tetrapropylammonium ethylmalonate, tetrapropylammonium propylmalonate, tetrapropylammonium butylmalonate, tetrapropylammonium dimethylmalonate Ammonium, tetrapropylammonium diethyl malonate, tetrapropylammonium succinate, tetrapropylammonium methyl succinate, tetrapropylammonium glutarate, tetrapropylammonium adipate, itaconic acid Propyl ammonium, tetrapropylammonium maleate , tetrapropylammonium fumarate, tetrapropylammonium citrate, tetrapropylammonium citrate, tetrapropylammonium carbonate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide , tetrapropylammonium nitrate, tetrapropylammonium chlorate, tetrapropylammonium perchlorate, tetrapropylammonium bromide, tetrapropylammonium iodate, bistetrapropylammonium oxalate, bistetrapropyl malonate Ammonium, bistetrapropylammonium methylmalonate, bistetrapropylammonium ethylmalonate, bistetrapropylammonium propylmalonate, bistetrapropylammonium butylmalonate, dimethylpropane Bis-tetrapropylammonium diphosphate, bistetrapropylammonium diethylmalonate, bistetrapropylammonium succinate, bistetrapropylammonium methyl succinate, bistetrapropylammonium glutarate, adipic acid Bis-tetrapropylammonium, bis-tetrapropylammonium itaconate, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, bistetrapropylammonium citrate, bistetrapropylammonium citrate, Bis-tetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium valerate, tetrabutylammonium hexanoate, heptanoic acid Butylammonium, tetrabutylammonium octoate, tetrabutylammonium citrate, hydrazine Tetrabutylammonium, tetrabutylammonium oleate, tetrabutylammonium stearate, tetrabutylammonium linoleate, tetrabutylammonium linolenate, tetrabutylammonium benzoate, tetrabutyl P-methylbenzoate Ammonium, tetrabutylammonium pt-butylbenzoate, tetrabutylammonium citrate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate, trifluoromethane Tetrabutylammonium sulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutyl oxalate- 56- 200920791 Ammonium, tetrabutylammonium malonate, tetrabutylammonium methylmalonate, tetrabutylammonium ethylmalonate, tetrabutylammonium propylmalonate, butylmalonic acid Butyl ammonium, tetrabutylammonium dimethylmalonate, tetrabutylammonium diethylmalonate, tetrabutylammonium succinate, tetrabutylammonium methyl succinate, tetrabutylammonium glutarate, Tetrabutylammonium adipate, tetrabutylammonium itaconate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citrate, tetrabutylammonium citrate, tetrabutyl carbonate Base ammonium, tetrabutylammonium chloride, Tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium nitrate, tetrabutylammonium chlorate, tetrabutylammonium perchlorate, tetrabutylammonium bromide, tetrabutylammonium iodate, oxalic acid Bis-tetrabutylammonium, bis-tetrabutylammonium malonate, bis-tetrabutylammonium methylmalonate, bis-tetrabutylammonium propyl malonate, bis-tetrabutylammonium propyl malonate, butyl Bis-tetrabutylammonium malonate, bis-tetrabutylammonium dimethylmalonate, bis-tetrabutylammonium diethylmalonate, bis-tetrabutylammonium succinate, bis-tetrabutylammonium methyl succinate , bis-tetrabutylammonium glutarate, bis-tetrabutylammonium adipate, bis-tetrabutylammonium itaconate, bis-tetrabutylammonium maleate, bis-tetrabutylammonium fumarate, citraconic acid Tetrabutylammonium, bis-tetrabutylammonium citrate, bis-tetrabutylammonium carbonate, and the like. Further, the above-mentioned thermal crosslinking accelerator may be used singly or in combination of two or more kinds. The amount of the thermal crosslinking accelerator added is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 40 parts by mass, per 100 parts by mass of the base polymer (the cerium-containing compound obtained by the above method). In the thermosetting composition of the present invention, the composition for a film containing ruthenium is required to be added to the composition of the present invention in order to stabilize the yttrium-containing compound (A-1) having a composition of at least half of the composition (C). 30% or more organic acids. The acid added at this time is, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexa-57 - 200920791 acid, heptanoic acid, caprylic acid, citric acid, citric acid, oleic acid, stearic acid, linoleic acid, Linolenic acid, benzoic acid 'citric acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid , ethylmalonic acid, propyl malonic acid, butyl malonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methyl succinic acid, glutaric acid 'adipic acid, clothing Kang acid, maleic acid, fumaric acid, citraconic acid, citric acid, and the like. Preferred are oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like. Further, in order to maintain stability, two or more kinds of acids may be used in combination. The amount of addition may be 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, more preferably 0.1 to 5 parts by mass, per part by mass based on the total amount of the cerium-containing compounds (A-1) and (A-2). .

Further, it is preferred that the organic acid is converted to the pH of the composition, and is added to 〇 S pH S 7, preferably 0.3 彡 pH S 6_5, more preferably 0.5 S pH $6. Further, the addition of the stabilizer (D) to a monovalent or divalent or higher alcohol having a substituent of a cyclic ether, particularly an ether compound represented by the following structure, can improve the stability of the composition for forming a film containing ruthenium. Such compounds are as follows:

Ό· -58- 200920791

[chemical 9] v

-59- 200920791

Wherein R9Ga is a hydrogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, and R91〇-(CH2CH2〇)ni-(CH2)n2- (wherein 〇Snl$5 , 0Sn2S3, R91 is a hydrogen atom or a methyl group), or R9 2 0-[ CH(CH3)CH20 ] n3-(CH2)n4- (wherein n3S 5, OS n4S 3 'R92 is a hydrogen atom or a methyl group)' R9()b is a linear, branched or cyclic monovalent hydrocarbon group having a hydroxyl group of 1 to 1 Å having 1 or more hydroxyl groups, H0-(CH2CH20)n5-(CH2)n6 - (wherein 1$ n5S 5, IS n6S 3), or H0-[CH(CH3)CH20]n7-(CH2)n8- (wherein n7S 5, IS n8S 3) The above stabilizers may be used alone or in 2 The above combination is used. The amount of the stabilizer added is preferably 0.001 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of the base polymer (the cerium-containing compound obtained by the above method). Further, these stabilizers may be used singly or in combination of two or more kinds. Among them, a preferred structure is a compound having a cyclic ether derivative and a substituent in which the bridge position is a bicyclic ring of an oxygen atom. When the stabilizer is added, the charge of the acid can be made more stable, so that the stability of the sand-containing compound in the composition can be imparted. In the composition containing the cerium-containing compound of the present invention, the (E) component used may be the same as the organic solvent used in the preparation of the cleavage compound, preferably -60-200920791 is a water-soluble organic solvent, particularly preferably B. Alkyl ether such as diol, diethylene glycol ' η B, propylene glycol, dipropylene glycol, butanediol, pentanediol monoalkyl ether. Specifically, for example, butanediol monomethyl ether, propylene glycol to methyl, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl glycol monoethyl ether, butanediol monopropyl ether An organic solvent selected from the group consisting of propylene glycol monopropyl ether glycol monopropyl ether. Water can be added to the composition of the present invention. When water is added, the sand-containing material can be hydrated to enhance the lithographic etching characteristics. The water content of the solvent component of the composition is more than 5% by mass and less than 50% by mass, preferably 0.3 to 30% by mass, preferably 0.5 to 20% by mass. When the amount of each component is too large, the coating uniformity is deteriorated, and when it is the worst, it bounces off. In addition, when the amount added is too small, the etching performance is lowered. The total amount of the aqueous solvent to be used is preferably from 500 to 1,000,000 parts by mass, particularly preferably from 400 to 50,000, based on the base polymer. The photoacid generator and the photoacid used in the present invention can be used in the present invention. For example, (A-Ι) the following general formula (Pla-1), (Pla-2) or (Plb) gun salt, (A-II) the following general formula (P2) diazomethane derivative, (A-III) an ethylenediazine derivative of the following general formula (P3), (A-IV) a double maple derivative of the following general formula (P4), (AV) N- of the following general formula (P5) a hydroxy sulfoximine compound of a sulfonic acid sulfonate (A-VI) /3-ketosulfonic acid derivative, (A - V 11) a second-milling derivative, a glycol-based ether acid, a acetylation rate, and the like A low trace amount of the film occurs -61 - 200920791 (A-VIII) a nitrobenzyl sulfonate derivative (A-IX) sulfonate derivative or the like. [化1 0] R101b jjl01a_4+_Rl〇lc pl01a_j+_jjl〇lc

JC K (Pla-1) (Pla-2) (wherein R1 (na, R1Qlb, Ri(1) are each a linear, branched or cyclic alkyl, alkenyl or carbonyl alkane having 1 to 12 carbon atoms a group or a carbonyl alkenyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or an arylcarbonylalkyl group having 7 to 12 carbon atoms, or some or all of the hydrogen atoms of the group may be alkoxy Substituent substitution. Also 'foot 1 () 11) and can form a ring, when forming a ring, R1 () lb, R101. Each is a C 1 to 6 alkyl group. Κ · is a non-nucleophilic counter ion) . The above R1Qla, R1() ib, "(η. may be the same or different, specifically alkyl such as methyl, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl Base, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl, etc. Alkenyl group such as vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. carbonylalkyl such as 2-carbonylcyclopentyl, 2-carbonylcyclohexyl, etc., or 2-carbonylpropyl, 2-cyclopentyl-2-carbonylethyl, 2·cyclohexyl-2-carbonylethyl, 2-(4-methylcyclohexyl)-2-carbonylethyl, etc. aryl group 'Phenyl, naphthyl, etc., or P-methoxyphenyl, m-methoxyphenyl, fluorenyl-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl-62 - 200920791, m-tert-butoxyphenyl, etc., oxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl' 4-tert-butyl Alkylphenyl such as phenyl, 4-butylphenyl or dimethylphenyl, alkylnaphthyl such as methylnaphthyl or ethylnaphthyl, methoxy a dialkoxy group such as a dialkylnaphthyl group such as an alkoxynaphthyl group such as a ethoxylated naphthyl group, a dimethylnaphthyl group or a diethylnaphthyl group; a dimethoxynaphthyl group; a diethoxynaphthyl group; An an aralkyl group such as a benzyl group, a phenylethyl group, a phenethyl group, etc. an arylcarbonylalkyl group such as '2-phenyl-2-carbonylethyl, naphthyl)-2-carbonylethyl, 2-aryl-2-mercaptoethyl group such as 2-(2-naphthyl)-2-carbonylethyl, etc. K_ non-nucleophilic counter-ion ions such as halide ions such as chloride ions and bromide ions , fluoroalkyl sulfonate such as trifluoromethanesulfonate, iota, yttrium-trifluoroethane sulfonate, nonafluorobutane sulfonate, p-toluenesulfonate 'benzenesulfonate, 4-fluorobenzene An alkyl sulfonate such as a sulfonate or an arylsulfonate such as 1,2,3,4,5-pentafluorobenzenesulfonate or a methanesulfonate or butanesulfonate.

R [Chemical 1 1 > 102a 104a. j^l02b R104b KK (Plb) (wherein R1()2a, R^b are each a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms; R1G3 is a linear, branched or cyclic fluorenyl group having a carbon number of 丨10. R104a and Rioo are each a 2-carbonyl group having a carbon number of 3 to 7. κ- is a non-nucleophilic counter ion. ). Specific examples of the above R1Q2a and R1G2b are, for example, methyl, ethyl, propyl 'isopropyl, η-butyl, sec-butyl, tert-butyl, pentyl, hexyl, g-63-200920791, octyl, Cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl and the like. R103, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, hydrazine, hydrazine, 4 _ ring hexyl, 〖, 2 ring Hexyl, 1,3 -cyclopentyl, 1,4-cyclooctyl, 1,4-cyclohexane, and the like. Rl〇4b is, for example, 2·carbonylpropyl, 2fluorenylcyclopentyl, 2-p-cyclohexyl, 2-cyclocycloheptyl or the like. Κ-, as described by the formulas (PIa-1), (Pla-2) and (Pla-3). [1 2] N2 R105—SOj-C—S〇2-R106 (P2) (wherein 'R and R are linear ^' chain or ring-shaped or halogenated yards of carbon ^ to 12, A substituted or unsubstituted aryl fluorinated aryl group having 6 to 20 carbon atoms, or a aryl group having 7 to 12 carbon atoms.

R

R group, octyl group, etc. fluoroethyl methoxyphenyl methyl butyl, chloroethyl η alkyl such as methyl, ethyl, propyl, isopropyl butyl, sec-butyl, tert-butyl, Pentyl, hexyl, heptyl, pentyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, and Orthodox. Halogenated alkyl groups such as trifluoromethyl, 1,1,1-trifluoroethyl, 丨丨丨_= group, nonafluorobutyl and the like. Aryl groups such as phenyl, P-methoxyphenylphenyl, fluorenyl-methoxyphenyl, ethoxyphenyl, p_tert • butoxy, m-tert-butoxyphenyl, etc. An alkylphenyl group such as a phenyl group, a 2-methylphenyl phenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl*phenyl group or a dimethylphenyl group. The halogenated aryl group is, for example, a gas phenyl phenyl group, a 1,2,3,4,5-pentafluorophenyl group or the like. Aralkyl groups such as, benzyl, benzene -64 - 200920791, and the like. [Chemical 1 3] ^^108 j^1〇9 r107—so2-on=c—c=no-so2-r107 (P3) (wherein R1()7, R1Q8, and R1Q9 are carbon numbers 1 to 12 a linear, branched or cyclic alkyl or halogenated alkyl group, an aryl group having 6 to 20 carbon atoms or a halogenated aryl group, or an aralkyl group having 7 to 12 carbon atoms. R1 μ, R1 μ may be bonded to each other. When a cyclic structure is formed and a cyclic structure is formed, R1()8 and R1()9 are each a linear or branched alkyl group having a carbon number of 1 to 6). And an alkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group or an aralkyl group as defined by R1()5, R1()6. Further, the alkylene group of R1()8, R1()9 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or the like. 【化1 4】 Ο 〇

R101a—S-CH2-S—R101b II II ο ο (Ρ4) (wherein R 1 °1 a, R 1Q1 b are the same as above). -65 - 200920791 【化1 5】 Ο

II R1x10/N-〇-SO2-Rln c II o (PS) (wherein R11() is a aryl group having 6 to 10 carbon atoms, a stretching group having a carbon number of 1 to 6 or a carbon number of 2 to 6 Alkenyl alkenyl group, some or all of the hydrogen atoms contained in the group may be further a linear or branched alkyl or alkoxy group having 1 to 4 carbon atoms, a nitro group, an ethyl fluorenyl group, or a phenyl group. Substituted. R111 is a linear, branched or substituted alkyl, alkenyl or alkoxyalkyl group, a phenyl group, or a naphthyl group having 1 to 8 carbon atoms, and some or all of the hydrogen atoms in the group An alkoxy group or alkoxy group having 1 to 4 carbon atoms; a phenyl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an ethyl fluorenyl group; a carbon number of 3 to 5 An aromatic group; or a chlorine atom or a gas atom substituted). Wherein R11Q is an extended aryl group such as ' 1,2-phenylene, ι,8-naphthyl, etc., and an alkyl group such as 'methyl, ethyl, trimethyl, tetramethyl, phenyl , alkenyl-2,3-diyl, etc., an alkenyl group such as, i,2-extended vinyl '1 phenyl-1,2-vinyl, 5-norpinene-2,3 - Diji and so on. The alkyl group of R111 is, for example, the same as 111()13 to the 'alkenyl group, for example, vinyl, 1-propenyl, allyl, 1-butenyl, 3-butenyl, isoprenyl, 1 -pentenyl, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 1-heptenyl, 3- Heptenyl '6-heptenyl, 7-octenyl, etc., alkoxyalkyl such as 'methoxymethyl' ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxy Methyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl-66-200920791, pentyloxyethyl, Hexyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl 'propoxybutyl, methoxy A pentyl group, an ethoxypentyl group, a methoxyhexyl group, a methoxyheptyl group, and the like. Further substituted alkyl having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, etc., alkane having 1 to 4 carbon atoms An oxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a η-butoxy group, an isobutoxy group, a tert-butoxy group or the like, which may be a carbon number of 1 to 4 Alkoxy, nitro or acetoxy substituted phenyl such as phenyl, tolyl 'p-tert-butoxyphenyl, p-ethyl phenyl, p-nitrophenyl, etc. The heteroaromatic group of 3 to 5 is, for example, a pyridyl group, a furyl group or the like. Specifically, for example, the following photoacid generator. Diphenyl trifluoromethanesulfonate 1^, trifluoromethanesulfonic acid (p-tert-butoxyphenyl)phenyl iodine gun, P-toluene acid diphenyl iodine gun, p-toluenesulfonic acid ( P-tert-butoxyphenyl)phenyl-iron, triphenylsulfane triphenylsulfide, trifluoromethanesulfonic acid (P_tert-butoxyphenyl) diphenylsulfide, trifluoromethanesulfonate Acid bis(P-tert_butoxyphenyl) phenyl sulfide gun, tris(P-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, P-toluenesulfonic acid triphenylsulfide gun, P -toluenesulfonic acid (P-tert•butoxyphenyl) diphenyl sulfide gun, P-toluenesulfonic acid bis(p-tert-butoxyphenyl)phenylsulfurate, P-toluenesulfonic acid tri P-tert-butoxyphenyl)sulfur, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfur gun of butanesulfonic acid, trimethylsulfur trifluoromethanesulfonate, p-toluene Trimethylsulfonium acid, cyclohexylmethyl (2-carbonylcyclohexyl)sulfur trifluoromethanesulfonate, cyclohexylmethyl (2-carbonylcyclohexyl)sulfur gun, trifluoromethanesulfonic acid Dimethylphenyl sulfide gun, p-toluenesulfonic acid di-67- 200920791 methylphenyl sulfide gun, trifluoromethanesulfonate Acid dicyclohexyl phenyl sulphur gun, p-toluenesulfonic acid dicyclohexyl phenyl sulphur gun, trinaphthyl trifluoromethane sulfonate trifluoromethanesulfonate, cyclohexylmethyl (2-carbonylcyclohexyl) sulfide Gun, trifluoromethanesulfonic acid (2-norbornyl)methyl (2-carbonylcyclohexyl) sulphur gun, extended ethyl bis[methyl(2-carbonylcyclopentyl) sulphide difluoromethane sulfonate a salt of 1,2'-naphthylmethylidene tetrahydrothiophene trifluoromethanesulfonate or the like. Bis(phenylsulfonium)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonate)醯)diazomethane, bis(η-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane,bis(η-propyl Sulfonium) diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane'bis(η-pentylsulfonyl)diazomethane, bis(isopentyl) Sulfonium) diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonium-l-(tert-butylsulfonate) Diazomethane, 1-cyclohexylsulfonium-l-(tert-pentylsulfonyl)diazomethane, l-tert-pentylsulfonium-l-(tert-butylsulfonyl)diazomethane, etc. Methane derivatives. Bis--0-(p-toluenesulfonyl)-α-dimethylglyoxime-bis-indole-(P-toluenesulfonyl)-α-diphenylglyoxime, double-0-(p-toluene Sulfonium dicyclohexylethylenediazine, bis-indole-(p-toluenesulfonyl)-2,3-pentanedione ethanedioxime, bis-indole-(indole-toluenesulfonyl)-2-methyl-3 , 4-pentanedione, ethylenedioxime, bis-indole-(η·丁院醯)-α·dimethylglyoxime, bis--0-(η-butanesulfonyl)-α-diphenyl乙二,, 〇-〇-(η-butanesulfonyl)-α-dicyclohexylethanediamine, bis-indole-(η-丁院醯)-2,3-pentanedione ethanedioxin, Bis--0-(η-butanesulfonyl)-2·methyl·3,4-pentanedione oxime, bis-indole-(methanesulfonyl)dimethylglyoxime, bis-68- 200920791 〇-(Trifluoromethanesulfonate)-α-dimethylglyoxime, bis- 0-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, double- 〇-(tert-butanesulfonium)-α-dimethylglyoxime, bis-indole-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-indole-(cyclohexane) Sulfonium)-α-dimethylglyoxime, bis-indolyl-(phenylsulfonyl)-α-dimethylglyoxime, bis-indole-(fluorene-fluorobenzenesulfonyl)-α-dimethyl Ethanol, double-0-(p-te Rt-butylbenzenesulfonate)-α-dimethylglyoxime, bis--0-(xylylenesulfonyl)-α-dimethylglyoxime, double-0-(sulfonate)-α- An ethylenediazine derivative such as dimethylglyoxime. bisnaphthylsulfonium methane, bistrifluoromethylsulfonium methane, bismethylsulfonium methane, bisethylsulfonium methane, bispropylsulfonyl methane, Double-milled derivatives such as diisopropylsulfonium methane, bis-indole-toluenesulfonium methane, bisphenylsulfonyl methane, etc. 〇2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropyl A-ketosulfonic acid derivative such as carbonyl-2-(p-toluenesulfonyl)propane. Diterpene derivative such as diphenyldifluorene or dicyclohexyldifluoride. P-toluenesulfonic acid 2,6-dinitrate Nitrobenzyl sulfonate derivatives such as benzyl benzyl ester, p-toluenesulfonic acid 2,4-dinitrobenzyl ester, 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3 a sulfonate derivative such as tris(trifluoromethanesulfonyloxy)benzene 1, 1,2,3-tris(p-toluenesulfonyloxy)benzene. N-hydroxysuccinimide methanesulfonate, N -hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propane sulfonate N-hydroxysuccinimide 2-propane sulfonate, N-hydroxysuccinimide pentane sulfonate, N-hydroxy amber succinimide 1-octane sulfonate, N-hydroxy amber succinimide P-tosylate, N--69- 200920791 hydroxy amber succinimide P-methoxybenzene sulfonate, N-hydroxy succinimide 2 chloroethane sulfonate, N-hydroxy amber Aminobenzenesulfonate, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2 -naphthalene sulfonate, N-hydroxy-2-phenylsuccinimide methane sulfonate, N-hydroxymaleimide methane sulfonate, N-hydroxymaleimide ethane sulfonate, N-hydroxy-2-phenylmaleimide methane sulfonate, N-hydroxypentamethylene imide methane sulfonate, N-hydroxypentamethylene benzene sulfonate, N-hydroxy quinone Amine methane sulfonate, N-hydroxy quinone benzene sulfonate, N-hydroxy quinone imine trifluoromethane sulfonate, N-hydroxy quinone imine P-toluene sulfonate, N-hydroxynaphthalene Dimethyl sulfoxide methane sulfonate, N-hydroxynaphthyl imidazolium benzene sulfonate, N-hydroxy-5-norpinene-2,3 -Dicarboxy quinone imide methane sulfonate, N-hydroxy-5-norpinol-2,3-dicarboxy quinone imine trifluoromethane sulfonate, N-hydroxy-5-norpinene-2,3 a sulfonate derivative of an N-hydroxyquinone imine compound such as a dicarboxy quinone imine P-toluenesulfonate. Among them, triphenylsulfonium trifluoromethanesulfonate, p-tert-butoxyphenyl diphenyl sulfide, trifluoromethanesulfonic acid tris(P-tert-butyl) Oxyphenyl) sulfur gun, P-toluenesulfonic acid triphenylsulfur gun, P-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfuric iron, p-toluenesulfonic acid tris(p- Tert-butoxyphenyl)sulfur gun, trinaphthylsulfur trifluoromethanesulfonate, cyclohexylmethyl (2-carbonylcyclohexyl)sulfur trifluoromethanesulfonate, trifluoromethanesulfonic acid (2-lower) Spinosa) methyl (2-carbonylcyclohexyl) sulphur gun, 1,2'-naphthylcarbonylmethyltetrahydrothiophene trifluoromethanesulfonate and other gun salts, bis(phenylsulfonyl)diazomethane, double (p-toluenesulfonate) diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(η-butyl-70-200920791 sulfonamide)diazomethane, bis(isobutylsulfonate)diazomethane , bis (sec_ butyl sulfonate) diazomethane, bis(η-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonate)diazomethane Iso-diazamethane derivative, bis-indole-(p-toluenesulfonate)-α-di Ethylene dioxime derivatives such as bis-indole, bis-indole _(n-butanesulfonyl)-0!-dimethylglyoxime, diterpene derivatives such as bisnaphthylsulfonium methane, N-hydroxy amber Yttrium imide methane sulfonate, hydroxy hydroxy succinimide trifluoromethane sulfonate, N-hydroxy amber succinimide 1-propane sulfonate, N-hydroxy amber succinimide 2 - propane sulfonate, N -hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxynaphthylimine methanesulfonate, N-hydroxynaphthalene a sulfonate derivative of an N-hydroxyquinone imine compound such as an amine benzenesulfonate. The photoacid generator may be used singly or in combination of two or more kinds, and the photoacid generator is added in an amount of 100% by mass relative to the base polymer (the ruthenium-containing compound (A-1) and (A-2) obtained by the above method). The portion (100 parts by mass of the total of the ruthenium-containing compounds (Al) and (A-2), the same hereinafter) is preferably from 0.01 to 50 parts by mass, more preferably from 0.05 to 40 parts by mass. Further, a surfactant may be added to the present invention as necessary. The surfactant is preferably a nonionic substance, a perfluoroalkyl polyethylene oxide, an alkyl fluoride, a perfluoroalkylamine oxide, a perfluoroalkyl ethylene oxide adduct, A fluorine-containing organosiloxane compound. For example, Flora "FC-430", "FC-431", "FC-4430" (both Sumitomo 3M (share) system), Saflon "S-141", "S-145", "KH -10", "KH-20", "KH-30", "KH-40" (all manufactured by Asahi Glass Co., Ltd.), Unitek "DS-401", "DS-403", "DS-451" (All are Daikin Industrial Co., Ltd.), Meikai-71 - 200920791 All "F-8151" (Daily Ink Industry Co., Ltd., "Χ-70_092", "X-70-093" (both For Shin-Etsu Chemical Co., Ltd., etc. It is preferably Flora "FC-443 0", "ΚΗ-20", "KH-30", "X-70-093". Addition amount of surfactant The effect of the present invention may be a general amount 'but 0 to 10 parts by mass, particularly preferably 〇 to 5 parts by mass relative to 100 parts by mass of the base polymer. The present invention is applicable to a ruthenium-containing film which is etched. The same photoresist film is formed on the substrate by a composition for forming a film containing ruthenium by spin coating, etc. The solvent is evaporated after spin coating, and the baking treatment for promoting the crosslinking reaction is preferably carried out in order to prevent the upper photoresist film from being mixed. Baking temperature 50 to 500 ° C It is preferable to carry out 10 to 3 sec seconds. The temperature range of the singularity varies depending on the structure of the device to be manufactured, but it is preferably 400 ° C or less in order to reduce thermal damage of the device. Further, the present invention can be processed After forming the sand-containing film with the underlying film formed on the processed portion of the substrate, a photoresist film is formed thereon to form a pattern. At this time, the processed portion of the substrate to be processed, for example, has a low capacitance of 3 or less. The insulating film, the low-permittivity insulating film after one processing, the inorganic film containing nitrogen and/or oxygen, the metal film, etc. More specifically, the substrate to be processed may form a processed layer (processed portion) on the base substrate. The base substrate is not particularly limited, and materials different from those of the layer to be processed such as Si, amorphous (α-Si)' p-Si, SiO 2 , SiN, SiON, W, TiN, and A1 can be used. The processed layer may be Si, SiO 2 , SiN, SiON, p-Si, a - S i, W, W - S i, a 1 , C u, A1-S i , etc. and various low dielectric films and their anti-etching The film is generally formed to have a thickness of -72 to 200920791 of 50 to 10,000 nm, particularly preferably 100 to 5,000 nm. A commercially available organic anti-reflection film may be formed between the ruthenium-containing film and the upper photoresist film. The structure of the anti-reflection film is formed of a compound having an aromatic substituent. The anti-reflection film is required to be dried. When the uranium replicates the pattern of the upper photoresist film, there is no etching load on the upper photoresist film. For example, the thickness of the upper photoresist film is 80% or less, and the dry etching load is preferably 50% or less. The antireflection film at this time preferably has an adjusted minimum reflection of 2% or less, preferably 1% or less, more preferably 0.5% or less. When the ruthenium-containing film of the present invention is used in an exposure step using ArF excimer laser light, a general ArF excimer laser light composition can be used as the upper photoresist film. The known photoresist composition for ArF excimer laser light has many candidates, and the main component of the positive type is a resin which is soluble in an aqueous alkali solution and a photoacid generator by decomposing an acid unstable group by an action of an acid. The basic substance for suppressing acid diffusion, the main component of the negative type is a resin which is insoluble to the alkali aqueous solution by the action of an acid and a photoacid generator, a crosslinking agent, and a base for inhibiting acid diffusion. Sexual substances, so there is only a difference in properties regardless of the use of any resin. The known resins are roughly classified into a poly(meth)acrylic acid, a COMA (Cyclo Olefin Maleic Anhydride) system, a COMA-(meth)acrylic acid mixture system, a R〇MP (Ring Opening Methathesis Polymerization) system, and a polypyromycin system. In the case where the photoresist composition using a poly(methyl)-propyl sulphuric acid resin is introduced into the alicyclic skeleton by a branch to ensure corrosion resistance, the resolution performance is superior to that of other resin systems. It is known that the ArF excimer laser resist composition using a poly(meth)acrylic resin is a plurality of units, and the positive type is ensured by the main function - 73-200920791 for the corrosion resistance unit, The unit in which the action of the acid is decomposed and changed into a unit of alkali solubility, a unit for ensuring adhesion, or the like, or a unit in which the above two or more functions are combined in one unit constitutes a polymer. Among them, a (meth) acrylate having an acid labyrinth group having an adamantane skeleton, which has an acid solubility as a unit of alkali solubility, has a holding of a spinach. The (meth) acrylate of the acid-unstable group of the alkane and the tetracyclododecane skeleton (Japanese Laid-Open Patent Publication No. 2003-8443-8) can impart high resolution and corrosion resistance. In addition, it is particularly preferable to use a unit for ensuring adhesion, and it has a (meth) acrylate having a lactone ring on the lower side of the caprolactone (International Publication No. 00/01 684), and has a peptone. A branched (meth) acrylate (JP-A-2000-159758) and a (meth) acrylate having a hydroxyadamantyl branch (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei. High resolution. Further, the polymer contains a unit of an alcohol for functional group which is acidic by substitution of a fluorine in the adjacent position (for example, Polym. Mater. Sci. Eng. 1 99 7. 77. pp 449), which can impart swelling to the polymer. Since it has a physical property and a high resolution, it is a photopolymer which is particularly suitable for the recent impregnation method. However, since the polymer contains fluorine, it has a problem of lowering the corrosion resistance. The ruthenium-containing film for use in the etching mask of the present invention is particularly suitable for such an organic photoresist composition which is difficult to ensure corrosion resistance. The ArF excimer laser resist composition containing the above polymer further contains a photoacid generator, a basic compound, and the like, and the photoacid generator used is almost the same as the film composition for forming a ruthenium-containing film of the present invention. Things, especially gun salt, are good for sensitivity and resolution. Further, there are a large number of known basic substances, and a number of examples are disclosed in Japanese Laid-Open Patent Publication No. 2000-146. After the etched mask is formed with a ruthenium-containing film layer, a photo resist layer is formed on top of the photomask composition solution, and a spin coating method using a ruthenium-containing film layer is preferably used. The photoresist is spin-coated and pre-baked, preferably at 80 to 180 ° C for 10 to 300 seconds. Thereafter, exposure is performed, and then post-baking (PEB) is performed, and a photoresist pattern is obtained after development. The etching step of etching the mask with a film containing germanium is carried out using a furan gas, a nitrogen gas, a carbonic acid gas or the like. The etching mask of the present invention has a characteristic that the film containing ruthenium has a uranium engraving speed with respect to the gas, and the film of the upper photoresist film is reduced. Further, in the multilayer photoresist method using the ruthenium-containing film of the present invention, there is no underlayer film between the ruthenium-containing film of the present invention and the substrate to be processed. When the underlayer film is an etching mask of the substrate to be processed, the underlayer film is preferably an organic film having an aromatic skeleton, and when the underlayer film is a sacrificial film or the like, the organic film may be contained in an amount of 15% by mass or less.矽 material. The underlying film is specifically known to have a large number of organic films having an aromatic skeleton, and is described in JP-A-2005-128,509, 4,4'-(9H-芴-9-ylidene) bisphenol novolac. In addition to the resin (having a molecular weight of 11,000), a known two-layer photoresist method such as a resin such as a novolac resin and a three-layer photoresist method of a photoresist film can be used. In addition, in order to make the heat resistance higher than that of the general novolak, it is possible to introduce a 4'-(9H-芴-9-ylidene) bisphenol novolac resin-like polycyclic skeleton, and a polyethylenimine resin (for example, Opened No. 2004-153125). In the layered photoresist method using the uranium engraved mask with the underlying film as the substrate to be processed, the organic film is formed by replicating the pattern of the photoresist pattern into the film containing the ruthenium. Since the film of the pattern is reproduced again, it is required to have a high corrosion resistance with respect to the conditions of the substrate to be processed by the uranium engraving, in addition to the etching process for etching conditions in which the film containing ruthenium exhibits high corrosion resistance. The organic film for the underlayer film may be used as a primer film in a conventional three-layer photoresist method or a two-layer photoresist method using a tantalum photoresist composition, and is disclosed in Japanese Laid-Open Patent Publication No. 2005-128509, 4 , 4'-(9H-芴-9-ylidene) bisphenol novolak resin (molecular weight: 11,000), other resins such as novolac resin, known as double-layer photoresist and 3-layer light The photo-resistance underlayer film material of the resistive method can be used. Further, in order to make the heat resistance higher than that of the general novolak, a polycyclic ring-like skeleton similar to the 4'-(9H-芴-9-ylidene) bisphenol novolak resin can be introduced. JP-A-2004- 1 53 1 25). The organic film may be formed on the substrate by a spin coating method or the like using a composition solution and an image resist composition. After the photoresist underlayer film is formed by a spin coating method or the like, it is preferable to perform baking for evaporating the organic solvent. It is preferably carried out at a baking temperature of 8 Torr to 300 ° C for 1 to 300 seconds. The thickness of the underlayer film is not particularly limited and varies depending on etching conditions, but is preferably 10 nm or more, particularly preferably 50 nm or more, and 50,000 nm or less. The thickness of the film containing ruthenium according to the present invention is preferably 1 nm or more and 20 〇 nm. Hereinafter, the thickness of the photoresist is 1 nm or more and 300 nm or less. The three-layer photoresist method using a ruthenium-containing film using the etching mask of the present invention is as follows. This step is 'first made by spin coating equal to the machine film made on -76-200920791. The organic film has a function as a mask for etching the substrate to be processed, and therefore preferably has high corrosion resistance, and is preferably required to be mixed with the upper etching mask in the film containing the germanium. Or acid to crosslink. The etching mask obtained by using the composition of the present invention in the above manner is formed of a film containing ruthenium and a photoresist film. The photoresist film may be exposed to a pattern by using a light source such as KrF excimer laser light, ArF excimer laser light or F2 laser light according to a certain method, and then heat-treated under the condition of the respective photoresist film. After the development process using a developing solution, a photoresist pattern can be obtained. Secondly, the photoresist pattern is an etching mask, and etching is performed with respect to the organic film by a dry etching condition in which the etching speed of the film containing germanium is higher, for example, etching using a fluorine-based gas excimer. The etching process of the anti-reflection film and the ruthenium-containing film hardly affects the pattern change due to the uranium engraving of the photoresist film size, and a film pattern containing ruthenium is obtained. Then, for the substrate having the ruthenium-containing film pattern of the above-mentioned replica resist pattern, the dry etching condition of the underlying organic film is higher, for example, reactive dry etching is performed using an oxygen-containing gas excimer. Or the underlying organic film is etched by reactive dry etching using a hydrogen-nitrogen-containing gas excimer. This etching step generally results in the loss of the uppermost photoresist layer in addition to the pattern of the underlying organic film. Further, in the dry etching treatment of the substrate to be processed by using the obtained underlying organic film as an etching mask, for example, when fluorine-based dry etching or chlorine-based dry etching is used, the processed substrate can be processed with more precision. [Embodiment] Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, -77-200920791 However, the present invention is not limited to the description. Synthesis of ruthenium-containing compound (A-1) [Synthesis Example 1] 200 g of methanol, 200 g of ion-exchanged water, and 35% hydrochloric acid ig were placed in a 1,000 ml glass flask, and 50 g of tetraethoxy decane and methyl trimethyl group were further added at room temperature. A mixture of oxydecane l〇〇g and phenyltrimethoxydecane l〇g. After directly hydrolyzing and condensing at room temperature for 8 hours, 30,000 ml of propylene glycol monoethyl ether was added thereto, followed by concentration under reduced pressure to obtain a propylene glycol monoethyl ether solution containing hydrazine compound 1 (300 g). The polystyrene-converted molecular weight of the material was measured, and as a result, M w = 2, 〇 〇 〇. [Synthesis Example 2] 50 g of tetraethoxy decane of Synthesis Example 1, 100 g of methyltrimethoxy fluorene, and benzene were replaced by methyl methoxy methoxy decane i 〇〇 g and phenyl trimethoxy decane 2 〇 g. In the same manner as the mixture of methoxy decane and 1 〇g, the same operation gave a propylene glycol monoethyl ether solution containing 3 g of a sand compound 2 (polymer concentration: 19%). The polystyrene-converted molecular weight of the article was measured and the result M w = 3,0 0 〇. [Synthesis Example 3] In addition to replacing the ion father with water 60 g, 6 5 % nitric acid 5 g, tetramethoxy fluorene 7 〇 g, methyl dimethoxy decane 7 〇 g, phenyl trimethoxy decane 10 g And butyl monomethyl _ substituted methanol of synthesis example 1 60 g, ion exchange water -78- 200920791 20 (^, 35% hydrochloric acid 1 §, tetraethoxy decane 50 叾, methyl trimethoxy decane 100 g, benzene Other than the same operation, a solution of the butanediol monomethyl ether containing ruthenium compound 3 (polymer concentration: 20%) was determined by the same procedure as in the case of propylene trimethoxy decane and propylene glycol monoethyl ether. The molecular weight in terms of styrene was found to be Mav = 2,500. [Synthesis Example 4] 260 g of ion-exchanged water and 35% of HCl were placed in a 10,000 ml glass flask, and 70 g of tetramethoxy decane and methyltrimethoxy were further added at room temperature. a mixture of 25 g of decane, 25 g of a decane compound of the following formula [i], and phenyltrimethoxydecane 1 〇g. The mixture was directly hydrolyzed and condensed at room temperature for 8 hours, and then methanol was produced by distillation under reduced pressure. 800ml and propylene glycol monopropyl ether 300ml, after separating the aqueous layer, repeat 100 times, add 100ml of ion-exchanged water to the remaining organic layer and stir. After the operation of liquid separation and liquid separation, 200 ml of propylene glycol monopropyl ether was added to the remaining organic layer, and concentrated under reduced pressure to obtain 300 g of a propylene glycol monopropyl ether solution containing ruthenium compound 4 (polymer concentration: 20%). The chloride ion of the obtained solution was analyzed by a chromatograph, and the result was not confirmed. The polystyrene-converted molecular weight of the product was measured, and the result was Mw = 1,800.

[Synthesis Example 5] -79- 200920791 200 g of ethanol, ion-exchanged water WOg, methanesulfonic acid was placed in a 1,000 ml glass flask, and tetramethoxy decane 4 〇g, methyltrimethoxy decane 1 was further added at room temperature. 〇g 'A mixture of 5 〇g of a decane compound of the following formula [ii] and 10 g of phenyltrimethoxydecane. After directly hydrolyzing and condensing at room temperature for 8 hours, methanol as a by-product was distilled off under reduced pressure, and then 800 ml of ethyl acetate and 300 ml of ethylene glycol monopropyl ether were added. After the aqueous layer was separated, 100 ml of ion-exchanged water was added three times to the remaining organic layer, and the mixture was stirred, allowed to stand, and liquid-separated. 200 ml of ethylene glycol monopropyl ether was added to the remaining organic layer, and concentrated under reduced pressure to give a solution of the succinimide compound 5 in ethylene glycol monopropyl ether (300 g) (polymer concentration: 2%). The result of analysis of the methanesulfonic acid ion of the obtained solution by ion chromatography was judged to be 99% of the removal reaction. The polystyrene-converted molecular weight of the product was measured, and as a result, Mw = 2, l〇〇. [Chemical 1 7 (CH30) 3Si

[ϋ] Synthesis of ruthenium-containing compound (A - 2 ) [Synthesis Example 6] 500 g of ethanol, 25 〇g of ion-exchanged water, and 2.5 g of 25% tetramethylammonium hydroxide were placed in a l'〇00mi glass flask, 55 The mixture was stirred while a mixture of tetraethoxynonane 9 7 § and methyltrimethoxy 矽 k 7 3 g was added dropwise over 2 hours. After stirring at 5 C for 15 hours, it was cooled to room temperature, and then 3 g of a 20% aqueous maleic acid solution was added. Add propylene glycol-propyl ether i 〇 〇 〇 }} -80- 200920791 After the solution, the solution was concentrated to 900 ml, and then 2,000 ml of ethyl acetate was added. After washing with 300 ml of water, the ion parent was washed twice, and after separating, the ethyl acetate was concentrated under reduced pressure to obtain 900 g of a propylene glycol monopropyl ether solution containing a sand compound 6 (polymer concentration: 7%). The tetramethylammonium ion of the obtained solution was analyzed by an ion chromatograph, and as a result, it was judged that 98% of the reaction product was removed. The polystyrene-converted molecular weight of the product was measured, and as a result, Mw = about 1,000,000. [Synthesis Example 7] In place of the mixture of tetraethoxy oxane 10 g, methyl trimethoxy decane 58 g and phenyl trimethoxy decane I 〇 g, 97 g of tetraethoxy decane of Synthesis Example 6 was used. In the same manner as the mixture of tris-methoxydecane 73 g, 900 g (polymer concentration: 7%) of a propylene glycol monopropyl ether solution containing hydrazine compound 7 was obtained in the same manner. The tetramethylammonium ion of the obtained solution was analyzed by an ion chromatograph, and it was judged that 98% of the reaction product was removed. The polystyrene converted molecular weight of the material was measured, and as a result, Mw = about 100,000. [Examples and Comparative Examples] The fluororesin filter of 0·1 μηι was mixed with the chopped compounds 1 to 7 obtained in the above Synthesis Example, the acid, the thermal crosslinking accelerator, the solvent, and the additive at the ratios shown in Table 1. The respective components for forming a film containing ruthenium were prepared by filtration, and each was represented by S 〇1 · 1 to 1 〇. -81 - 200920791 [Table π Formation of film composition containing ruthenium

No. Antimony compound (parts by mass) Thermal crosslinking accelerator (parts by mass) (parts by mass) Solvent (parts by mass) Water/stabilizer (parts by mass) Other additives (parts by mass) Example 1 Sol.l Compound 1 (3.6) Compound 6 (0.4) TPSOAc (0.04) Maleic acid (0.04) Propylene glycol monoethyl ether (100) Water (10) Stabilizer 1 (5) • fm* 实施 Example 2 Sol.2 Compound 2 (3 -6) Compound 6 (0.4) TPSOH (0.04) Oxalic acid (0.02) Propylene glycol monoethyl ether (100) Water (5) Stabilizer 2 (5) J \ \\ Example 3 Sol.3 Compound 3 (3-6 Compound 7 (0.4) TPSC1 (0.04) TMAOAc (0.003) Maleic acid (0.01) Butanediol monomethyl ether (100) Water (5) Stabilizer 3 (5) Example 4 Sol.4 Compound 4 (3) -6) Compound 6 (0.4) TPSMA (0.04) TMAOAc (0.003) Maleic acid (0.01) Oxalic acid (0.01) Propylene glycol monopropyl ether (100) Water (5) Stabilizer 4 (5) > frrr- M Example 5 Sol.5 Compound 5 (3.2) Compound 6 (0.4) Compound 7 (0-4) TPSN (0.04) Maleic acid (0.01) Oxalic acid (0.01) Ethylene glycol monopropyl ether (100) Water (5) Stabilizer 5 (5) Sister y\\\ Example 6 Sol.6 Compound 1 (1_8) Compound 2 (1.8) Compound 6 (0.4) TPSMA (0.04) Maleic acid (0.01) Propylene glycol monoethyl ether (100) Water (3) Stabilizer 1 (5) TPSNf (0.02) Example 7 Sol.7 Compound 1 (3-6) Compound 6 (0.4) TPSOAc (0.04) Maleic acid (0.01) Propylene glycol monoethyl ether (100) Water (〇) Stabilizer 1 (5) fiE / V Comparative Example 1 Sol.8 Compound 1 (4.0) TPSOAc (0.04) y y\\s Propylene glycol monoethyl ether (100) Water (5) Stabilizer 1 (5) Μ ^\\\ Comparative Example 2 Sol.9 Compound 1 (4.0) MJ \ w Maleic acid (0.01) Propylene glycol Propyl ether (100) Water (5) Stabilizer 1 (5) Μ j\ w Comparative Example 3 Sol. 10 Compound 1 (4.0) TPSOAc (0.04) Maleic acid (0.01) Propylene glycol monopropyl ether (100) Water (5) Stabilizer 1 (〇) M -82- 200920791 TPSOAc: Triphenylsulfide acetate (photodegradable thermal crosslinking accelerator) TPSOH: Triphenylsulfide hydroxide (photodegradable thermal crosslinking accelerator) TPSC1: Triphenylsulfide chloride (photodegradable thermal crosslinking accelerator) TPSMA: maleic acid mono(triphenylsulfur gun) (photodegradable thermal crosslinking accelerator) TP SN : triphenyl nitrate Sulfur gun (photodegradable thermal crosslinking accelerator) TMAOAc: tetramethylammonium acetate (non-light) Solutions for thermal crosslinking accelerator) TPSNf: triphenylsulfonium nonafluorobutanesulfonate hospital record basis acid (photoacid generating agent) of [18]

Stabilizer 1:

Stabilizer 3:

-83- 200920791

First, the composition of the underlying film material containing 4,4'-(9H_芴-9-ylidene) bisphenol novolak resin (molecular weight: 11,000) (Japanese Patent Laid-Open Publication No. 2005-128589) (Resin 2) 8 parts by mass and 1 part by mass of the solvent) were spin-coated on a silicon wafer, and heated at 200 ° C for 1 minute to form an underlying organic film having a film thickness of 30 onm. Further, the underlying organic film material may be any of the above-mentioned other resins including the novolak resin, and any of the known underlayer film materials in the multilayer photoresist method. Next, Sol.l to 10 was spin-coated, and after heating at 200 °C for 1 minute, a film of a sand having a film thickness of 10 nm was formed. Next, in order to form the upper photoresist film, the following ArF excimer laser light resist composition (Resistl) was dissolved in PGMEA (propylene glycol monomethyl ether) containing 0.1% by mass of FC-43 0 (manufactured by Sumitomo 3M Co., Ltd.). In the acetate) solution, it was filtered and filtered using a 0.1 μm fluororesin filter. -84- 200920791 【化1 9】 Rouge

〇 (Me is a methyl group and Ee is an ethyl group). Mw = 6,800 1 〇 parts by mass photoacid generator: triphenylsulfur gun nonafluorobutane sulfonate 〇. 2 parts by mass of basic compound: triethanolamine oxime. 02 parts by mass of the composition is applied to the intermediate layer After 1 260 (TC baking for 60 seconds, a film photoresist layer with a film thickness of 200 nm was formed. Next, an ArF exposure device (manufactured by Nikon Co., Ltd.: S305B, NA 0.68, σ 0.8 5 2/3 wheel body illumination) , Cr mask) exposed, and then baked at 10 ° C (PEB) for 90 seconds, and then developed with 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution to obtain a positive pattern. The shape of the 90 nm L/S pattern is shown in Table 2. -85- 200920791 [Table 2] Shape of the pattern

No. Pattern shape Sol.l Good Sol.2 Good Sol.3 Good Sol.4 Good Sol.5 Good Sol.6 Good Sol.7 Good Sol.8 Foot shape Sol.9 Film shape Sol.10 Good example 1 EXAMPLE 2 EXAMPLES Example 4 Example 5 Example 6 Example Comparative Example 1 Comparative Example 2 Comparative Example Any of the examples showed a pattern of no undercut and under-mixing in the vicinity of the substrate. Next, a test for resistance to dry etching is carried out. After the above composition Sol. 1 to 10 was spin-coated, it was heated at 200 ° C for 1 minute to form a film 1 to 10 having a film thickness of 100 nm. The film, the underlayer film and the photoresist film were subjected to a saturation test under the following etching conditions (1), and the results are shown in Table 3. (1) Etching test using CHFs/CF4 gas. Device. Dongjin Electronics Co., Ltd. Drying device TE-8500P Etching conditions (1): Casing pressure 40.0Pa

RF power 1,3 00 W clearance 9mm -86- 200920791 3 0 m 1 /mi η 3 0 m 1 /mi η 1 OOml/min 1 0 sec chf3 gas flow rate cf4 gas flow Ar gas flow treatment time [Table 3] CHF3 /CF4 system gas dry etching rate to form a film composition containing ruthenium containing film CHF3/CF4 gas dry etching rate (nm/min) Example 1 Sol.l Film 1 400 Example 2 Sol. 2 Film 2 500 Example 3 Sol. 3 Film 3 450 Example 4 Sol. 4 Film 4 250 Example 5 Sol. 5 Film 5 200 Example 6 Sol. 6 Film 6 500 Example 7 Sol. 7 Film 7 400 Comparative Example 1 Sol. 8 Film 8 400 Comparative Example 2 Sol. 9 Film 9 400 Comparative Example 3 Sol. 10 Film 10 400 Photoresist Film - 120 Underlayer Film - - 85 Next, investigate the 02 gas dryness shown in Table 4 by the following etching conditions (2). Erosion speed. As a result, the underlying film and the upper photoresist film were very slow. Therefore, the middle layer is an etched mask to copy the pattern to the bottom layer. Etching conditions (2): Reaction chamber pressure 60.0Pa RF power 600 W -87- 200920791 4 0 m 1 /m i η 6 0 m 1/m i η 9mm 2 0 s e c

Ar gas flow rate 气体 2 gas flow gap processing time [Table 4] 〇 2 system gas dry etching rate 〇 film 〇 2 system gas etching rate (nm / min) Example 1 Film 1 2 Example 2 Film 2 1 Example 3 Film 3 2 Example 4 Film 4 10 Example 5 Film 5 15 Example 6 Film 6 2 Example 7 Film 7 2 Comparative Example 1 Film 8 2 Comparative Example 2 Film 9 2 Comparative Example 3 Film 10 2 Photoresist Film - 250 Underlayer film - 210 Additional storage stability test was performed. The composition for forming a film containing ruthenium (Sol. 1 to 10) obtained above was stored in 3 (1 month after TC, and then coated again by the above method to test whether or not the film formability was changed. The results are shown in Table 5. -88-200920791 [Table 5] Preservation stability results The properties of the composition name after coating Example 1 Soil No film thickness variation, no pattern shape change Example 2 Sol. 2 No film thickness variation, no image Shape change example 3 Sol. 3 No film thickness variation, no pattern shape change Example 4 Sol. 4 No film thickness variation, no pattern shape change Example 5 Sol. 5 No film thickness variation, no pattern shape Variation Example 6 Sol. 6 No film thickness variation, no pattern shape change Example 7 Sol. 7 No film thickness variation, no pattern shape change Comparative Example 1 Sol. 8 Film thickness 5% increase, pattern peeling comparative example 2 Sol.9 No film thickness variation, pattern peeling Comparative Example 3 Sol.10 The film thickness was increased by 15%, and the pattern peeling was confirmed by the results of Table 5, and the composition of any of the examples had a temperature of 30 t for more than 3 months. It is converted into storage stability at room temperature for 6 months or more. It is confirmed from the above that the composition of the present invention contains bismuth. An excellent film lithography and qualitative characteristics of the composition using an exposure machine with a high NA of the first end of the pattern and may be formed by etching the substrate. -89-

Claims (1)

200920791 X. Patent Application No. 1 · A thermosetting composition for forming a film containing ruthenium, which is characterized by containing ( (A-1) a hydrazine-containing compound obtained by hydrolyzing and condensing a hydrolyzable hydrazine compound with an acid as a catalyst, (A-2) A ruthenium-containing compound obtained by hydrolyzing and condensing a hydrolyzable sand compound with a base as a catalyst, and (B) one or more kinds of LaHbX of the compound represented by the following general formula (1) or (2) (1) (wherein 'L is lithium, sodium, potassium, _ or planer, X is a hydroxyl group, or a carbon number of 丨 to 30 valence or a divalent or higher organic acid group, 3 is an integer above 丨, b is 〇 Or an integer of 1 or more, a + b is the valence of a hydroxyl group or an organic acid group) MaHbA (2) (wherein, Μ is a sulfur gun, an iodine gun or ammonium, and A is the above X or a non-nucleophilic counter ion, a, b is the same as above, a + b is the valence of a hydroxyl group, an organic acid group or a non-nucleophilic counter ion) (C) a monovalent or divalent or higher organic acid having a carbon number of 1 to 30, (D) having a ring The monovalent or divalent or higher alcohol (E) organic solvent of the substituent of the ether. -90- 200920791 2. The composition for film formation containing ruthenium according to the first aspect of the patent application, wherein the ruthenium-containing compound (A-1) contained therein is - can be derived from a mineral acid and a sulfonic acid One or more selected compounds are the ruthenium-containing compounds obtained by the step of hydrolytically condensing the hydrolyzable ruthenium compound by an acid catalyst to substantially remove the acid catalyst in the ruthenium-containing reaction mixture. 3. The thermosetting composition according to claim 1 or 2, which comprises a composition for a film containing ruthenium, wherein the ruthenium-containing compound (A-2) contained therein is hydrolyzable by using a base as a catalyst The ruthenium-containing compound obtained by the step of substantially removing the base catalyst in the ruthenium-containing reaction mixture obtained by hydrolytic condensation of the compound. 4. The composition for film formation containing ruthenium according to the heat-curing property of claim 1 or 2, wherein the general formula (2) is a tertiary sulfonium, a secondary iodine gun or a fourth-stage saddle. 5. The composition for film formation containing ruthenium according to the thermosetting property of the first or second aspect of the patent application, wherein the oxime of the general formula (2) is photodegradable. 6. The composition for film formation containing ruthenium according to the heat-curing property of claim 1 or 2, wherein the mass in the composition is (Α·1)>(Α-2). 7. A thermosetting composition according to claim 1 or 2, which forms a film composition containing ruthenium, further comprising a photoacid generator. 8. A thermosetting composition according to claim 1 or 2, which forms a composition for a film containing ruthenium, which additionally contains water. A film containing ruthenium formed by the composition of any one of items 1 to 8 of the patent application, wherein an organic film is formed on the substrate to be processed, and a film containing ruthenium is formed thereon. Further, a photoresist film is formed on the top of the film using a chemically-reinforced photoresist composition containing no antimony. After the photoresist film is processed by the pattern of -91 - 200920791, the film of the antimony film is patterned using the photoresist film pattern. The type of processing is a multi-layer photoresist method in which the underlying organic film is patterned by etching the patterned film containing the ruthenium, and then the processed organic film is used as an etching mask to etch the substrate to be processed. The film containing ruthenium. A film comprising ruthenium formed by the composition of any one of items 1 to 8 of the patent application, characterized in that, in the step of the multilayer photoresist method of claim 9 A ruthenium-containing film used in a multilayer photoresist method in which an organic anti-reflection film is interposed between a photoresist film obtained from a chemically-reinforced photoresist composition and a film containing ruthenium. 1 1. A substrate characterized by sequentially forming an organic film on a film containing ruthenium formed of a composition according to any one of items 1 to 8 of the patent application, and a photoresist thereon membrane. 12. A substrate, characterized in that an organic film is formed in sequence, the film comprising ruthenium formed by the composition of any one of items 1 to 8 of the patent application, an organic anti-reflection film, and The photoresist film above it. 13. The substrate according to claim 11 or 12, wherein the organic film is a film having an aromatic skeleton. 14. A method of forming a pattern, characterized in that, in a method of forming a pattern on a substrate, preparing a substrate as in claim 1 of the patent application, and exposing the pattern loop region of the photoresist film of the substrate, Forming a photoresist pattern on the photoresist film by developing a developing solution to form a photoresist pattern of the photoresist pattern as an etching mask to dry-etch the film containing the germanium, and then forming a pattern containing germanium The film is an etching mask to etch the organic film, and then the organic film formed in the pattern is used as a mask to etch the substrate to form a pattern on the substrate. -92- 200920791 15. A method for forming a pattern, which is characterized in that, in a method of forming a pattern on a substrate, 'the substrate of the substrate of claim 12 is prepared, and the pattern of the photoresist film of the substrate is prepared. After exposure in the loop field, a photoresist pattern is formed on the photoresist film by developing liquid imaging to form a photoresist pattern of the photoresist pattern as an etching mask to dry the organic anti-reflection film and the film containing the germanium. After etching, the organic film is etched by forming a pattern of the ruthenium-containing film as an etch mask, and then the substrate is etched by using the patterned organic film as a pattern to form a pattern on the substrate. 1 6 The method of forming a pattern according to the patent application No. 14 or 15 wherein the organic film is a film having an aromatic skeleton. 1 7 _ A method of forming a pattern as in the case of the patent application No. 14 or 15 'In the formation of a resist pattern, a photographic micro-etching method using a light having a wavelength of 300 Å or less is used. -93- 200920791 明说单无简ituu :# is the map of the map element: the table pattern represents the book without a set of one or two, if the case has a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: no