TWI378973B - Silicon-containing film-forming composition, silicon-containing film, silicon-containing film-bearing substrate, and patterning method - Google Patents

Description

1378973 IX. Description of the Invention [Technical Field] The present invention relates to a multilayer resist used in a process for producing a semiconductor element or the like as an intermediate layer, which is suitable for forming a middle layer by spin coating. A method of forming a pattern from a film containing ruthenium using a film containing ruthenium formed therefrom. [Prior Art] With the high integration and high speed of LSI, the speed is miniaturized. The lithography technique is suitable for the purpose of matching the miniaturization and shortening the wavelength, and appropriately selecting the photoresist composition corresponding thereto. The photoresist composition of the positive-type photoresist composition whose center is a single layer is a skeleton which has corrosion resistance with respect to the dry etching of the plasma of the use body, and the photoresist is dissolved by the photoresist mechanism. After the pattern is formed, the coating of the resist composition is dry-etched by the etching mask, but the film thickness of the photoresist film used is directly reduced, and when the width is wide, the solution of the photoresist film is lowered. Like performance, when using a pattern image of a film, the so-called aspect ratio collapse is excessively increased. Therefore, as the miniaturization requires thinning of the photoresist film, the processing method used for the substrate to be processed is a pattern of the photoresist film, and the film is finely processed by dry etching. The substrate for the film composition is used to make the pattern size by the light source to achieve a fine pattern. The single-layer positive type chlorine-based or fluorine-based gas dissolves the remaining portion of the photoresist pattern processing substrate, thereby reducing the pattern of the developing liquid to cause a photoresist, thereby causing a pattern to form a substrate, but the reality is -6- 1378973 The dry etching method can not achieve complete engraving between the photoresist film and the substrate to be processed, and the photoresist film is damaged during the processing of the substrate, causing the photoresist film to be collapsed in the substrate, so it cannot be Correctly copy the photoresist pattern to the board being processed. Therefore, with the miniaturization of the pattern, the photoresist composition is required to have higher dry etching properties. In addition, 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. Therefore, the use of i-line, KrF, and ArF is changed to a novolak resin. Polyhydroxystyrene and a resin having an aliphatic polycyclic skeleton. However, in reality, the etching rate of the above etching conditions is very fast, so that the corrosion resistance of the composition having the recent high resolution is lowered. Since it is necessary to dry and etch the substrate to be processed by a thinner and less resistant photoresist film, it is urgent to ensure that the materials and steps of the process are one of the methods for solving such problems. In the method, a photoresist film is interposed between the photoresist upper layer film and the substrate to be processed, and the etching film is different from the interlayer film of the photoresist upper layer film, and the pattern of the photoresist upper layer film is obtained, and the upper layer photoresist pattern is The dry etching mask is a method of replicating the pattern to the interlayer film by dry etching, and then using the interlayer film as a dry etching mask, and copying the pattern to the processing substrate by dry etching. In the double-layer resist method of the multilayer photoresist method, for example, the upper layer resist composition is a resin containing ruthenium, and the intermediate film is a method using a novolac resin (for example, JP-A-6-953-8). The ruthenium resin has good corrosion resistance with respect to reactive dry etching of oxygen plasma, but is easily removed using a fluorine-based gas phase molecule. In addition, the novolak resin is more easily removed by reactive dry etching of the 1789973 ion such as the use of the phase-based dry light after the use of the oxygen gas etchant, but the fluorine-based gas plasma and the chlorine system are used. The dry etching of gas plasma has good corrosion resistance. 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 the pattern is reproduced on the novolac film, and 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 layer film has a good etch--8-37878-inch selection ratio for the iridium-containing photoresist intermediate film, and thus can be dry-etched by using a fluorine-based gas plasma. 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 is formed by the double-layer photoresist method and has a pattern of noodle varnish film which is sufficiently resistant to dry etching. 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: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei 7-8 8 68 8 or the like), or a film obtained by spin coating, such as a SOG (spinning glass) film (for example, Patent Document 4: JP-A-5) 29 1 208 and the like, Non-Patent Document 1: J. Appl. Polym. Sci., Vol. 88, 636-640 (2 003)) and a crosslinkable sesquiterpene oxide film (for example, Patent Document 5: Table 2005-520354, etc., or a polydecane film (for example, Patent Document 6: JP-A-H11-60735). Among them, the SiO 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 SOG film, the crosslinkable sesquiterpene oxide 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 to form a photoresist pattern, but the above-described multilayer photoresist method can be used (for example, Patent Document 7: JP-A-2004-3495, 72, 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 most advanced N A exposure conditions 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 even more difficult to avoid the dry etching load when the upper layer of the photoresist for the antireflection film is processed to increase the dry etching load, especially when the film thickness of the photoresist film is thinner. 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 such as a spin coating type light absorbing ruthenium containing interlayer film is known. 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- 1378973 should be suppressed to the minimum introduction amount. In addition, when the photoresist film is processed by using the interlayer film as a dry etching mask, generally, the dry etching rate with respect to the reactive dryness using oxygen plasma is preferably smaller in order to increase the etching selectivity ratio of the intermediate film and the underlying film. Therefore, 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. In the currently known ruthenium containing interlayer film, a composition of the s OG film is formed, as disclosed in Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)) using KrF excimer thunder. Photolithographic lithography. 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 is very sensitive, so that even if the film thickness rise and the molecular weight change are not observed when the stanol group in the molecule is condensed, the shape change of the pattern from -11 to 1378973 can be observed. Previously, such highly reactive stanol groups were more stable when stored in an acidic state, for example, Non-Patent Document 2 (CJ Brinker and GW Scherer, a Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)) and other households have their own words. Further, Non-Patent Document 1: (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)), Patent Document 9 (Japanese Laid-Open Patent Publication No. 2004-157469), and Patent Document 10 (Opening 2004-1) 9 1 3 8 6), etc., has been disclosed to add water to enhance preservation stability. However, the ruthenium-containing compound produced by the method disclosed in the patent document may not completely prevent the condensation reaction of the stanol group from being "slowly change the ruthenium-containing compound in the composition over time". The properties of the ruthenium-containing film derived from the composition which produces the change. Therefore, use it in a refrigerated or frozen storage before use. When using it, return it to the temperature (usually 23 °C) and use it as soon as possible. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 9] Japanese Laid-Open Patent Publication No. 2004-157576 (Patent Document 10), JP-A-2004-191386, No. -12- 1378973 [Non-Patent Document 11] J. Appl. Polym. Sci., Vol. 8 8 63 6-640 (2003) [Non-Patent Document 12] CJ Brinker and GW Scherer, "Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)) OBJECT OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION An object of the present invention is to provide (1) a photoresist film formed on a film containing ruthenium formed on an organic film and having a light absorption pattern after forming a photoresist pattern. Performance, so that a good pattern can be formed even under high NA exposure conditions. (2) A photoresist film can be used on the upper layer of the film containing tantalum, and the bottom layer is used. A good dry etching mask is formed between the film to form a film containing ruthenium, (3) a composition for forming a film containing ruthenium having good stability, and a film containing ruthenium obtained from the composition, and containing ruthenium A substrate formed by a film, and a method of forming a pattern. In order to solve the problem, the inventors of the present invention have focused on the lithographic etching characteristics and stability of the composition for forming an intermediate film containing ruthenium, and found that the following components (B), (C), and (D) are (E) a component obtained by adding a hydrazine compound obtained by hydrolyzing and condensing a hydrolyzable hydrazine compound with an acid as a catalyst, and a hydrazine-containing compound obtained by hydrolyzing and condensing a hydrolyzable hydrazine compound with a base as a catalyst. (1) By suppressing the reflection of the yttrium-containing film under any high-NA exposure conditions of dry or liquid immersion by introducing a light-absorbing substituent described later, (2) having sufficient etching as a dry etching mask The present invention has been completed by selecting a film composition containing ruthenium which has a lithographic etching property without a change in performance over 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) And (2) 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, · χ is a hydroxyl group, or a carbon number of 丨 to 30 valence or a valence or more of an organic acid group, a is an integer of 1 or more, b An integer of 0 or more, a + b is the valence of a hydroxyl group or an organic acid group)

MaHbA (2) (wherein, Μ is a sulfur gun, iodine gun or ammonium, A is the above X or non-nucleophilic counter ion, a, b is the same as above, a + b is hydroxyl, organic acid group or non-nucleophilic (C) a valence of 1 to 30 or more organic acids, (D) a monovalent or divalent or higher alcohol having a substituent of a cyclic ether - 14378973 ( E) Organic solvents. (Applicant's patent scope 1). In general, a hydrolyzable hydrazine compound (hereinafter referred to as a monomer) is hydrolyzed by a hydrolyzable substituent bonded to a hydrazine atom to form a stanol group by an action of water under an acid catalyst. 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 a so-called oligomer, polymer, or yttrium-containing compound, which is hereinafter referred to as a sol. 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 (1 990), etc. that the specific pH can suppress the condensation. The reaction, in particular, non-patent document i (j. Appl. Polym. Sci., Vol. 88, 6 3 6 - 6 4 0 (2 0 0 3 )) has been described as stable at pH 1.5 (hereinafter referred to as stable pH). The present invention has found that the use of the component (C) to control the stability of the pH can improve the preservation stability. It is also known that the monomer can be different from the acid catalyst by the action of water under the alkaline catalyst to obtain high condensation. A ruthenium-containing compound (A-2) having a small stanol group (Non-Patent Document 2: (CJ Brinker and GW Scherer, ', Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing -15- 1378973 ", Academic Press, San Diego (1 990). However, since the cerium-containing compound (A-2) has a small terminal stanol group, even if only the cerium-containing compound (A-2) is formed into a cerium-containing film, Reducing the bond between the ruthenium-containing compound (A-2) to obtain a film having a lower density. Therefore, the inventors have found that When a composition containing a ruthenium-containing compound (A-1) having a large amount of a stanol group and a ruthenium-containing compound (A-2) having a small stanol group is formed, a ruthenium-containing film is formed, and a ruthenium-based group contains less ruthenium. Since the compound (A-2) is biased on the surface of the film, it is possible to form a film containing a ruthenium group having a small amount of sulfonyl groups on the surface of the film without adding a ruthenium-containing compound (A-2). The influence of the unavoidable stanol group is suppressed to a minimum, so that a well-shaped photoresist pattern can be formed. Further, the condensation of the stanol group remaining in the ruthenium-containing compound is suppressed at room temperature. It has been 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 storage stability of the composition can be improved by a leap. The high temperature of 0 ° C or higher and the acid catalyst of the thermal acid generator harden the cerium-containing compound. The present invention is used for the thermal crosslinking of the component (B) after the coating composition is heated and hardened. Acting to change the pH around the stanol group from a stable pH to an unstable pH ( pH3 can be in the vicinity, as described in Non-Patent Document 2 (CJ Brinker and GW Scherer, *Sο 1-Gel Science: The Physics and Chemistry of Sol-Gel Processing", Academic Press, San Diego (1990)), so Effectively hardens the film. Namely, it is possible to provide a fine film which is crosslinked more rapidly than the previously 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 obtain the lithographic etching property equivalent to that of the general organic antireflection film of -16-1378973. When the ruthenium-containing compound (A-2) having a small stanol group is partially biased on the surface at the beginning as described above, and the pH is changed during hardening to effectively promote the condensation reaction between the stanol groups, it is found that the stanol group is contained in a very small amount. The film of 矽. 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. Moreover, by combining the pH control, the stabilizer and the technique of adding a cross-linking catalyst, it is possible to obtain a composition which is hardened at room temperature and hardened at the time of hardening, and thus can have a stability equivalent to that of the prior 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 -17-1378973 was allowed to maintain a stable pH, and it was only necessary to store a less stable composition due to the excess amount of stanol groups. 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). Since the stability region of the stanol is acidic, the pH balance in the composition is lowered and reduced when the composition is not added by the alkali catalyst used in the production of (A-2) (A-2). The stability of the composition. Therefore, after the removal of the alkaline catalyst for the production 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 first to third aspects of the patent application. The composition for film formation containing ruthenium is sclerosing, wherein the general formula (2) is a three-stage sulphur gun, a secondary iodine gun 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 Μ 1378973 of the general formula (2) is photodegradable (No. 5 of the patent application scope) ). 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 improves the hardenability of the ruthenium-containing compound while obtaining a good lithographically etched shape. The present invention provides a thermosetting composition for forming a film containing ruthenium 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 ruthenium-containing compound (A_2) having a small stanol group, the fineness of the film containing ruthenium after hardening is lowered. As a result, the effective component in the photoresist film is transferred to the film containing ruthenium, and the shape of the photoresist pattern after lithography is deteriorated. In order to prevent this result, it is necessary to contain a sufficiently rich crosslinkable ruthenium-containing compound (A-1). When the mass of the ruthenium-containing compound (A_丨) in the composition is more than that of the ruthenium-containing compound (A-2), it can have sufficient cross-linking reactivity to form a fine film, so that the photoresist pattern after lithography 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- 1378973 The present invention provides a thermosetting composition for forming a film containing ruthenium according to any one of claims 1 to 7, which additionally contains water (Application No. 8) ❶ adding water to make After the stanol group in the ruthenium-containing compound is activated, 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 11). -20- 1378973 - A substrate is characterized in that an organic film is sequentially formed, and a sand-containing film formed on the organic film by the composition of any one of claims 1 to 8 and an organic defense A reflective film, and a photoresist film thereabove (patent application item 12). The substrate of claim 11 or 12, wherein the organic film is a film having an aromatic skeleton (Patent No. 13 of the patent application). a method for forming a pattern, characterized in that, in the method of forming a pattern on a substrate, 'preparation of the substrate as in claim 11 of the patent application, and 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 The organic film is etched for etching the mask, and the substrate is etched 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) 0. - Method for forming a pattern In the method of forming a pattern on a substrate, preparing a substrate as in claim 12 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 the uranium on the organic anti-reflection film and the ruthenium-containing film to form a patterned ruthenium-containing film. Etching the mask to etch the organic film, and then forming the pattern of the organic film as a mask Etching the substrate to form a pattern on the substrate (Patent Application range 1 5). The method of forming a pattern according to claim 14 or 15, wherein the organic film is a film having an aromatic skeleton (patent application No. 16-21-13878). For example, the method for forming a pattern of the patent application No. 14, 15 or 16 is used in the formation of a photoresist pattern, and the photolithography etching method using a light having a wavelength of 300 nm or less (Application No. 17 of the patent application) 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 lithography step, it can be an organic film having sufficient corrosion resistance during substrate etching, so that it can be etched. 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 lithography of a wavelength of 300 nm or less, particularly 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 a high etching selectivity is obtained between the organic material and the organic material, the formed photo resist pattern can be sequentially copied to the germanium-containing intermediate film and the organic underlayer film by a dry etching 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- 1378973 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).

m3Si(OR){ 4 · m 1 · m 2 •m3) (3) (R is a fluorenyl group having 1 to 3 carbon atoms, and R1, R2 and R3 are each the same or different hydrogen atom, or a carbon number of 1 to 30% of the organic group, ml 'm2, m3 is 0 or 1. ml+m2 + m3 is 0 to 3, particularly preferably 〇 or 1). It is a substance obtained by hydrolyzing and condensing one or a mixture of two or more selected from the monomers represented by the general formula (3), wherein the organic group means a group containing carbon, additionally contains hydrogen, or may contain nitrogen. , oxygen, sulfur, antimony, etc. The organic group of R1, R2, and R3, such as 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, and the like One or more hydrogen atoms are substituted by an epoxy group, an alkoxy group, a hydroxyl group or the like, and a group of -〇·, -CO-, _0C0_, -COO·, -OCOO -, etc., will be described later. ) the base represented by the group, and the organic group containing a 矽 矽 bond. In the monomer represented by the general formula (3), R1, R2 and R3 are preferably, for example, a hydrogen atom, a methyl group, an ethyl group, an η-propyl group, an iso-propyl group, an n-butyl group or an iS0·butyl group. Sec-butyl, t-butyl, η·pentyl, 2-ethylbutyl, 3-ethylbutyl' -23- 1378973 2,2-diethylpropyl, cyclopentyl, n-hexyl An alkynyl group such as an alkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group or an allyl group or an alkynyl group, or an aryl group such as a light-absorbing phenyl group or a tolyl group or an aryl group such as 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 The oxoxane is preferably tetramethoxy decane, tetraethoxy decane ruthenide such as ml = l, m2 = 0' m3 = 0, alkoxy decane, such as 'trimethoxy decane, triethoxy Base decane, tri-n-propoxy decane, tri-iso-propoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane 'methyl three -iS0-propoxydecane 'ethyltrimethoxydecane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltri-iso-propoxydecane, vinyltrimethoxy矽, vinyl triethoxy oxime, B-tris-n-propoxy sand, ethylene tri-iso-propoxy decane, η-propyl trimethoxy decane, η-propyl three Ethoxy decane, η-propyltri-n-propoxydecane, η-propyltri-iso-propoxydecane, i-propyltrimethoxydecane, i-propyltriethoxydecane, I-propyl tri-n-propoxy sulane, i-propyl tri-iso-propoxy sand , η·butyltrimethoxydecane, η-butyltriethoxydecane, η-butyltri-n-propoxydecane, η-butyltri-iso-propoxydecane, sec-butyl Trimethoxy decane, sec_butyl-i-diethoxy oxime, sec-butyl-tri-n-propoxy oxalate, sec-butyl-tri-iso-propoxy decane, t-butyl Trimethoxy decane, butyl butyl triethoxy decane, t-butyl tri- η propoxy decane, t-butyl tri-iS0 - propoxy decane, cyclopropyl trimethoxy decane, cyclopropyl three Ethoxy decane, cyclo-24-1378973 propyl-tripropoxydecane, cyclopropyl-tri-iso-propoxydecane, cyclobutyltrimethoxydecane, cyclobutyltriethoxydecane, ring Butyl-tri-n-propoxydecane, cyclobutyl-tri-iso-propoxydecane, cyclopentyltrimethoxydecane, cyclopentyltriethoxydecane, cyclopentyl-tri-n- Propoxydecane, cyclopentyl-tri-iso-propoxydecane, cyclohexyltrimethoxydecane, cyclohexyltriethoxydecane, cyclohexyl-tri-n-propoxydecane, cyclohexyl-tri- Iso-propoxydecane, cyclohexenyltrimethoxynonane, cyclohexenyl three Oxoxane, cyclohexenyl-tri-n-propoxydecane, cyclohexenyl-tris-is-propoxydecane, cyclohexenylethyltrimethoxydecane, cyclohexenylethyl Triethoxy decane, cyclohexenylethyl-tri-n-propoxy decane, cyclohexenylethyl, tri-iso-propoxy decane, cyclooctyltrimethoxydecane, cyclooctane Triethoxy decane, cyclooctyl-tri-n-propoxydecane, cyclooctyl-tri-iso-propoxydecane, cyclopentadienylpropyltrimethoxynonane, cyclopentane Alkenylpropyltriethoxydecane, cyclopentadienylpropyl-tri-n-propoxydecane, cyclopentadienylpropyl-tri-iso-propoxydecane, dicycloheptenyltrimethyl Oxydecane, dicycloheptenyltriethoxydecane, dicycloheptenyl-tri-n-propoxydecane, bicycloheptenyl-tri-iso-propoxydecane, bicycloheptyltrimethyl Oxydecane, dicycloheptyltriethoxydecane, dicycloheptyl-tri-n-propoxydecane, dicycloheptyl-tri-iS0-propoxydecane, adamantyltrimethoxydecane, Adamantyl triethoxy decane, adamantyl-tri-n-propoxy decane Adamantyl - Silane three -iso- propoxy and the like. Further light absorbing monomers such as phenyltrimethoxydecane, phenyltriethoxydecane, phenyltri-n-propoxydecane, phenyltri-iso-propoxydecane, benzyltrimethoxy Sand courtyard, octyl diethoxylated samarium, sylvestre tri-n-propoxy sulphate-25-1378973, benzyl tri-iso-propoxy decane, tolyl trimethoxy decane, tolyl-B Oxylate sand, methyl-based di-n-propoxy sand, tolyl di-iso-propoxydecane, phenethyltrimethoxydecane, phenethyltriethoxydecane, phenethyl -η-propoxydecane, phenethyltris-iS0_propoxydecane, naphthyltrimethoxydecane, naphthyltriethoxydecane,naphthyltri-n-propoxydecane,naphthyltri-- Iso-propoxydecane, and the like. Preferred are methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, η- Propyltrimethoxydecane, n-propyltriethoxylate, iso-propyltrimethoxylate, iso-propyltriethoxydecane, η-butyltrimethoxydecane, n-butyl Triethoxy decane, iso-butyl trimethoxy decane, iso-butyl triethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, cyclopentyl trimethoxy decane, Cyclopentyltriethoxydecane, cyclohexyltrimethoxydecane, cyclohexyltriethoxydecane, cyclohexenyltrimethoxydecane, cyclohexenyltriethoxydecane, phenyltrimethoxydecane, Phenyltriethoxydecane 'benzyltrimethoxydecane, benzyltriethoxydecane, phenethyltrimethoxydecane, phenethyltriethoxydecane. For example, ml = l, m2 = l' m3 = 0, alkoxy decane, for example, dimethyldimethoxydecane, dimethyldiethoxydecane, methylethyldimethoxydecane, Methyl ethyl diethoxy decane, dimethyl-di-n-propoxy decane, dimethyl-di-iso-propoxy decane, diethyl dimethoxy decane, diethyl diethyl Oxydecane, diethyl-di-n-propoxydecane, diethyl-di-iso-propoxydecane, di-n-propyl dimethoxydecane, di--26- 1378973 η- Propyldiethoxydecane, di-n-propyl-di-n-propoxydecane, di-n-propyl-di-iso-propoxydecane, di-iS0-propyldimethoxy Decane, di-iso-propyldiethoxydecane, di-iso-propyl-di-n-propoxydecane, di-iso-propyl-di-iso-propoxydecane, di-η- Butyl dimethoxy decane, di-η-butyl diethoxy decane, di-η-butyl di-η-propoxy decane, di-η-butyl di-iso-propoxy decane, Di-sec-butyl dimethoxydecane, di-sec. butyl diethoxy decane, di-sec-butyl-di-n-propoxy decane, di-sec-butyl-di-iso - Propoxy decane, di-t-butyl dimethoxy decane, di-t-butyl diethoxy decane 'di-t-butyl-di-n-propoxy decane, di-t-butyl -di-iso-propoxydecane, di-cyclopropyldimethoxydecane, di-cyclopropyldiethoxydecane, di-cyclopropyl-di-n-propoxydecane, di- Cyclopropyl-di-isopropoxydecane, di-cyclobutyldimethoxydecane, di-cyclobutyldiethoxydecane, di-cyclobutyl-di-n-propoxydecane, two -cyclobutyl-di-iso-propoxydecane, di-cyclopentyldimethoxydecane, di-cyclopentyldiethoxydecane, di-cyclopentyl-di-n-propoxydecane , di-cyclopentyl-di-iso-propoxydecane, di-cyclohexyldimethoxydecane, di-cyclohexyldiethoxydecane, di-cyclohexyl-di-n-propoxydecane, Di-cyclohexyl-di-iso-propoxydecane, di-cyclohexenyldimethoxydecane, di-cyclohexenyldiethoxydecane, di-cyclohexenyl-di-n-propyl Oxoxane, di-cyclohexenyl-di-iso-propoxydecane, dicyclohexenylethyldimethoxydecane, di-cyclohexenylethyldiethoxy Alkane, di-cyclohexenylethyl-di-n-propoxydecane, di-cyclohexenylethyl-di-iso-propoxydecane, di-cyclooctyldimethoxydecane, Di-cyclooctyldiethoxy decane, di-cyclooctyl-di-n-propoxy 矽-27- 1378973 alkane, di-cyclooctyl-di-iso-propoxy decane, two - cyclopentadienylpropyl dimethoxydecane, di-cyclopentadienylpropyl diethoxy decane, dicyclopentadienylpropyl-di-cardopropoxy decane, di-ring Pentadienylpropyl-di-iso-propoxydecane, bis-bicycloheptenyldimethoxydecane, bis-bicycloheptenyldiethoxydecane, bis-bicycloheptenyl- Di-n-propoxydecane, bis-bicycloheptenyl-di-iso-propoxydecane, bis-bicycloheptyldimethoxydecane, bis-bicycloheptyldiethoxydecane, Bis-dicycloheptyl-di-η-propoxydecane, bis-bicycloheptyl-di-iso-propoxydecane, bis-adamantyl dimethoxydecane, bis-adamantyldiethyl Oxydecane, 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, ml = l, m2 = l, m3 = l one alkoxy decane, for example, trimethyl methoxy decane, trimethyl ethoxy decane, dimethyl ethyl methoxy decane, dimethyl Ethyl 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- 1378973-based methoxy decane, dimethyl phenethyl ethoxy decane, and the like. Preferred is trimethylmethoxydecane 'dimethyl ethyl methoxy decane, dimethyl phenyl methoxy decane, dimethyl benzyl methoxy decane, dimethyl phenyl ethyl methoxy 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 selected from the group consisting of an epoxy group, a vine group, an aristocratic group, and a group selected from the group. The organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (3) is a group represented by the following general formula (4) (P-Qi-(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 11 (CH2CH-) > a carbon number of 1 to 4) An oxy group, an alkyl carboxyoxy group having 1 to 6 carbon atoms or a carbonyl group having 1 to 6 carbon atoms, (^, (^, (^ and q4 are each independently _ CqH(2q.p)Pp-( Where P is the same as above, p is an integer from 〇 to 3, q is an integer from 〇 to 10 (but q = 0 is a single bond), u is an integer from 0 to 3, and S2 is independently -0-, - CO-, -OCO-, -COO- or -OCOO-.vl, v2, v3 are each independently 0 or 1. Further, τ is a divalent group 'τ 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 Q2 and Q3 in T is not particularly limited. The reactivity from the three-dimensional factor and the availability of a commercially available reagent for the reaction may be considered. Appropriate choice) -29- 1378973

[Chemical 2] τ= v □ Ο 〇 0 ^ ^ Q Ο Ο Ο

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- 1378973 【化3】

-31 - 1378973

OH

OH OCH·* OH OCH3 O-

〇H OH (si) \^\^OCOCH3 (Si), [Chemical 5

(Si) r^/r

OCH 3 (Si)

OH och3 .OCOCHq ) (Si) OCOCH3 •(Si) •(Si)

OCH

3

Further, the organic groups of R1, R2 and R3 may be, for example, an organic group containing a fluorene-hydrazine bond, for example, the following -32-1378973 [Chemical 6] ch3 H3C-0i-Chh S wears Qi) ch3 (Si) CH3 9H3 HjC^Si·—Si—CH3 〆CH3 (Si) CHj CH3 9H3 H3C*Si—Si—Si—QHj CH3 CH3 (Si)

(SO '(Si) CHjCHjCHa CH3CH3CH3CH3 H3C-S1-Si-Si-CH3 H3C-S1-Si-Si-S1-CH3 CH3fJ (Si) CH3 (Si) CH3 ch3 ch3 H3C'SrCH3 H^Si-Si-SiSj 3 ^3c-4'-ch?H3 (Si) H3C CH3 HA into pHs h3c-〒, 〒-ch3 H3C-Si^ Si-CH3 HiC ) bH3CH3 (sir H c ?H3 PH3 H3C, Si-Si-CH3 / \ Ιλ H3C-Si Si-CH3

Hjd y>" 'CH, l ch3 (sr) 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 used. One or more compounds selected from the group consisting of inorganic acids, aliphatic sulfonic acids and aromatic sulfonic acids are acid catalysts, and the monomers are hydrolyzed and condensed. The acid catalysts used at this time are, for example, hydrofluoric acid, hydrochloric acid, and bromine. Hydrogen acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, etc. The amount of catalyst used is relative to the monomer 1 molar ίο·6 Up to 10 moles, preferably 1 〇 5 to 5 moles, more preferably 10-4 to 1 moles. When the monomer is hydrolyzed and condensed to obtain a sand-containing compound, the amount of water added is relative to the bond. The hydrolyzable substituent of the monomer is preferably from 〇〇1 to 100 mol' per 1 mol, more preferably from 0.05 to 50 mol, more preferably from 1 to 3〇-33 to 1378973 mol. When it exceeds 100 m, it will make it economical. The operation method is as follows: the monomer is added to the catalyst water to dissolve in a dense reaction. At this time, the organic solvent can be added to the catalyst to dissolve in water. The diluent monomer is carried out simultaneously or both. The reaction temperature is preferably from 5 to 80 ° C. It is preferably a method of aging at 80 ° C and then 20 to 80 ° C when the monomer is dropped. Aqueous solution or diluted monomer organic alcohol, ethanol, 1-propanol, 2-propanol, 1-butanol '2-propanol, acetone 'acetonitrile, tetrahydrofuran, toluene, cyclohexanone, methyl-2- N-amyl ketone, butanediol monomethyl acid, ethylene glycol monomethyl ether, butanediol-ethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether ether, propylene glycol Methyl ether acetate, propylene glycol monoethyl pyruvate, butyl acetate, ethyl 3-methoxypropionate, ethyl acetate tert-butyl vinegar, tert-butyl acetate butyl ether acetate, 7- Butyl lactone and the mixed name of these solvents are preferably soluble. Examples, alcohols such as 1-propanol and 2-propanol, ethylene glycol, propylene glycol monomethyl ether, Propylene glycol monomethyl ether, ethylene glycol alcohol monoethyl ether 'propylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether 'ethylene glycol-propylene derivative, acetone, acetonitrile, Tetrahydrofuran Among them, it is particularly preferred to be a boiling point of less than 100 ° C. I use a device that is too large to start hydrolytic condensation [in the middle, or organic solvent is 〇 to 100 ° C, the temperature is maintained at 5 to the solvent is preferably , methyl butanol, 2-methyl-1-alkane, ethyl acetate, alkyl ether, propylene glycol monoether 'propylene glycol monoethylene, diethylene glycol dimethyl ether acetate, ester, 3-ethoxypropyl, Propylene glycol-tert-"products, such as 'methanol, ethanol alcohol and other polyvalent alcohols, butan methyl ether, butyl ether, butanediol ether and other polyvalent alcohols -34- 1378973 organic solvent usage It is preferably f 1,000 ml with respect to the monomer 1 molar, and particularly preferably 0 to 50 ml. The amount of organic solvent used The reaction vessel is too large and uneconomical. Thereafter, a catalyst neutralization reaction may be carried out as necessary, and the alcohol formed by the condensation reaction may be decompressed to obtain an aqueous solution of the reaction mixture. The amount of the alkaline substance to be used may be preferably 2 equivalents with respect to the acid for the catalyst. The test substance may be an object which is indicative of water, and may be a substance. Then, the reaction mixture is removed from the reaction mixture to form a reaction temperature. The heating temperature of the reaction mixture depends on the type of alcohol produced by the added organic reaction, but is preferably 0 to 10 (TC, preferably 9 ° C. More preferably, it is 15 to 80 ° C. At this time, the degree of decompression will be divided by the organic solvent and alcohol type, the exhaust device, the condensation device, and the addition, but preferably below atmospheric pressure, and at an absolute pressure of 80 kPa. It is more preferable that the absolute pressure is 50 kPa or less. In this case, it is difficult to accurately understand the amount of alcohol, but it is desirable to remove 80% by mass or more of the alcohol produced. Secondly, the method for removing the acid catalyst by the acid used for the hydrolysis condensation can be removed from the reaction mixture. After mixing the water and the ruthenium-containing compound, the ruthenium-containing compound is extracted with the agent. The organic solvent used at this time is preferably a ruthenium-containing compound which is separated from the mixed water double layer. For example, ethanol, 1-propanol , 2-propanol, 1-butanol, 2-butanol '2-methyl alcohol, acetone, tetra-furfuran, toluene' hexanyl, ethyl acetate, cyclomethyl-2-n-amyl ketone, butyl Glycol monomethyl ether, propylene glycol monomethyl glycol monomethyl ether, butanediol Ethyl ether, propylene glycol-ethyl I 0 to too much neutralization except for hydrolysis: 0.1 is any alcohol. Solvent and 10 to the catalyst for removal because of the heat to be removed. Organic soluble, soluble, methanol g - 1 - propanone, ether, ether, ethyl-35- 1378973 diol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl hydrazine, ethylene glycol monopropyl ether, propylene glycol Ethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3 -ethyl ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-tert-butyl ether acetate, r-butyl lactone, methyl isobutyl ketone, cyclopentyl Methyl ether and mixtures thereof. 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, dibutyl Monoethyl ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate, ethylene glycol monoethyl ether + ethyl acetate, butanediol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + acetic acid Ethyl ester, 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-propanol + cyclopentyl methyl ether, propylene glycol monomethyl ether + cyclopentyl methyl ether, ethylene glycol monomethyl ether + cyclopentyl Methyl ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentyl methyl ether 'ethylene glycol one Ether ether + cyclopentyl methyl acid, methanol + propane -36 - 1378973 diol methyl ether acetate , ethanol + propylene glycol methyl ether acetate, 1-propanol + propylene glycol methyl ether acetate, 2-propanol + propylene glycol methyl hydrazine 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 glycol monoethyl ether + propylene glycol methyl ether acetate, propylene glycol monopropyl A composition such as, but not limited to, a composition such as a base ether + propylene glycol methyl ether acetate, ethylene glycol monopropyl ether + propylene glycol methyl ether acetate. The mixing ratio of the water-soluble organic solvent to the water-insoluble organic solvent can be appropriately selected as '100 parts by mass with respect to the poorly water-soluble organic solvent, and the water-soluble organic solvent may be 0.1 to 1, 〇〇〇 by mass, preferably 1 to 500. The part by mass is more preferably 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 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 can be one or more times, and even if it is washed more than one time, only the washing effect is obtained, so it is 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, etc., which can be used for the acid catalyst for the reaction. And choose the right one. In the above-described operation of removing the catalyst, the amount of the catalyst for the reaction to be added to 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 -37-1378973 is equivalent to the effect of the substantial division operation, so 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 kind of the reaction solvent to be removed and the extraction solvent, but is preferably from 0 to 100 ° C, more preferably from 10 to 90 ° C, still more preferably from 15 to 80 ° C. Further, the degree of pressure reduction at this time varies depending on the type of the extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably at most atmospheric pressure, and preferably at an absolute pressure of 80 kP a or less, more preferably The absolute pressure is below 50 kPa. Changing the solvent at this point will make the cerium-containing compound unstable. This is because the final solvent and the ruthenium-containing compound are phase-to-phase, and in order to prevent the addition of the stabilizer, the component (C) described later can be used. The amount of addition is from 0 to 25 parts by mass, preferably from 0 to 15 parts by mass, more preferably from 0 to 5 parts by mass, based on 100 parts by mass of the cerium-containing compound in the solution before solvent exchange, but added in an amount of 0.5 parts by mass. The above is better. If necessary, the solvent before the solvent exchange may be added with the component (C) for solvent exchange. 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. Therefore, it is preferably a solution state of a moderate concentration. The concentration at this time is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less. The final solvent to be added to the cerium-containing compound solution is preferably an alcohol-based solvent, and particularly preferably an alkyl ether such as an alkyl ether, propylene glycol or dipropylene glycol such as ethylene glycol, diethylene glycol or triethylene glycol. Specific examples are preferably butanediol monomethyl ether-38-1378973, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl acid, propylene glycol monoethyl ether, ethylene glycol-B. Ethyl 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 to 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 is 〇 to 100 ° C, preferably 10 to 80 ° C. Further, it is heated to 10 to 50 ° C when dripping water, and then preferably aged at 20 to 80. When an organic solvent is used, it is preferably a water-soluble substance, 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, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, dibutyl Alcohol 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 A polyvalent alcohol condensate derivative such as an acid ester or propylene glycol monopropyl ether, or a mixture thereof. The organic solvent can be used in the same amount as described above. The post-treatment of the resulting reaction mixture can be carried out in the same manner as described above to give a hydrazine-containing compound. The molecular weight of the obtained ruthenium-containing compound can be adjusted by controlling the reaction conditions at the time of polymerization, but when a weight average molecular weight exceeds 100,000, a foreign matter and a coating spot may be generated depending on the case, and therefore, it is preferably used at 100,000 or less. More preferably from 200 to 50,000, particularly preferably from 300 to 30,000. The data on the above weight average molecular weight is represented by polystyrene-converted molecular weight measured by gel permeation chromatography (GPC) using an RI detector and polystyrene as a standard substance, using -39 to 1378973. 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 sand-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, dimethyl monoethanolamine, monomethyl Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine , N,N-dimethylaminopyrrolidine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide , tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like. The amount of the catalyst used is from 1 -6 to 10 mols, preferably from 10·5 to 5 mols, more preferably from 10·4 to 1 mol to 40 to 1378973, with respect to the oxime monomer 1 molar. The amount of water obtained by hydrolytic condensation to obtain a ruthenium-containing compound from such monomers is preferably from 0.01 to 100 moles per mole of the hydrolyzable substituent bonded to the monomer, and preferably from 5 to 50 moles. i to 30 m. More than 1 Torr 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 〇, preferably 5 to 80 °C. Further, it is preferably maintained at 5 to a degree when the monomer is dropped, and then it is preferably aged at 20 to 80 °C. It can be added to the aqueous solution of the catalyst or dilute the monomer for the organic solvent 'methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, Toluene, ethyl diacid, cyclohexanone, methyl-2·η-amyl ketone, butanediol monopropylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethylene glycol monoethyl Ether, ethylene glycol monoethyl ether, propylene glycol dimethyl glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol acetate, ethyl pyruvate, butyl acetate, 3-methoxy propyl Acid ethoxypropionic acid ethyl vinegar, acetic acid tert-butyl vinegar, propionic acid tert-butanol-tert-butyl ether acetate, r-butyl lactone, and the like, preferably water soluble in such solvents For example, methanol, 1-propanol, 2-propanol and the like, ethylene glycol, propylene glycol and the like are multivalent, and the added ear is preferably 0.1% without hydrolysis condensation or organic to 1 0 0 °c 80 ° C temperature agent is preferably alcohol, 2-methyl toluene, ethyl methyl ether, ether, propyl ether, diethyl ether ethyl ether, 3-ester, propylene mixture, ethanol, Alcohol, Ding II-41 - 1378973 Alcohol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether And a polyvalent alcohol condensate derivative such as propylene glycol monopropyl ether ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran or the like. Among them, it is particularly preferred to have a boiling point of 100 ° C or less. The amount of the organic solvent to be used is preferably from 〇 to 1,000 ml, particularly preferably from 0 to 500 ml, depending on the monomer. The reaction container is too large and uneconomical when the amount of the organic solvent used is too large. 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 acidic substance which can be used for neutralization at this time is preferably from 0.1 to 2 equivalents based on the base of the catalyst. The acidic substance may be acidic 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 depends on the organic solvent to be added and the type of alcohol produced by the reaction, but is preferably from 1 to 〇〇. (:, preferably from 1 〇 to 90 ° C, more preferably from 15 to 801. Also, the degree of decompression at this time will be due to the type of organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature. The difference is preferably less than atmospheric pressure, more preferably 80 kPa or less, and more preferably 50 kPa or less. In this case, it is difficult to accurately know the amount of alcohol removed, but it is preferable to remove 80% by mass or more. Next, in order to remove the catalyst for hydrolysis condensation, the sand-containing compound may be extracted by an organic solvent. The organic solvent used at this time is preferably a substance which can dissolve the ruthenium-containing compound 'mixed water and can be separated by two layers. For example. ,methanol,ethanol, -42-1378973 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, acetic acid Ester, cyclohexanone, .methyl-2-n-pentyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol Ethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, polypropylene Dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate , 3-ethoxypropionate ethyl ester, tert-butyl acetate, tert-butyl propionate, propylene glycol-tert-butyl ether acetate, 7-butyl lactone, methyl isobutyl ketone, ring Butyl methyl ether and mixtures of these, etc.

Further, 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 monoethyl ether + ethyl acetate, dibutyl Alcohol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl hydrazine + 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 acid + methyl isobutyl ketone , methanol + cyclopentyl methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + cyclopentyl methyl ether, 2-43- 1378973 propanol + cyclopentyl methyl acid, propylene glycol- a Ether ether + cyclopentyl methyl acid, ethylene glycol monomethyl ether + cyclopentylmethyl Ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether 4 cyclopentyl methyl ether, ethylene glycol monopropyl ether +cyclopentyl methyl ether 'methanol + propylene glycol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, 1-propanol + propylene glycol methyl acid acetate, 2-propanol + propylene glycol methyl ether Acetate, propylene glycol monomethyl ether + propylene glycol methyl hydrazine acetate, ethylene glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate, ethylene a composition 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 not limited thereto 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 from 0.1 to 1,000 parts by mass, preferably from 1 to 500 parts by mass, per 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 0.01 to 100 L with respect to 1 L of the cerium-containing compound solution, preferably 5 to 50 L, more preferably 0.1 to 5 L. The washing method may be that the separated water layer is left to stand after mixing both sides in the same container. The number of times of washing may be one or more times, but even if it is washed more than 10 times, only the washing effect is obtained, so it is 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. Further, in the present invention, the basic catalyst is substantially removed, and the alkaline catalyst for allowing the reaction of the ruthenium-containing compound -44-1378973 is 10% by mass or less, which is less than the mass%. After removing the test catalyst, the final solvent is added to the ruthenium-containing compound solution, and then the solvent exchange is performed under reduced pressure to obtain a ruthenium-containing compound solution. The temperature at which the dissolution is carried out depends on the type of the extraction solvent to be removed, but is preferably 100 ° C, more preferably 10 to 90 ° C, still more preferably 15 to 801. The degree of decompression at any time varies depending on the type of extraction solvent to be removed, the venting apparatus and the heating temperature, but is preferably at most atmospheric pressure, and preferably at a pressure of 80 kPa or less. More preferably, the absolute pressure is 5 kPa. the following. The final solvent to be added to the cerium-containing compound solution is preferably an alcohol-based solvent, preferably an alkyl ether such as ethylene glycol, diethylene glycol or triethylene glycol, or an alkyl ether such as 'propylene or dipropylene glycol. Specific examples are preferably, butanediol monoether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol-ethyl, propylene glycol monoethyl ether 'ethylene glycol monoethyl ether, butanediol one Propyl propylene glycol monopropyl ether, ethylene glycol monopropyl ether, and the like. Further, other reaction operations such as starting the hydrolysis reaction by adding water or an aqueous organic solvent or an organic solvent of the monomer. At this time, the catalyst may be in a monomer or a monomeric organic solvent, or added to water or an aqueous organic solvent. The reaction temperature may be 0 to 1 〇〇 ° C, preferably 10 to 8 (TC. It is preferably heated to 10 to 50 ° C when water is introduced, and then heated to 20 to 80. Preferably, when using an organic solvent Preferred are water-soluble substances, for example, methanol alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanone, tetrahydrofuran, acetonitrile, butanediol Monomethyl ether, propylene glycol-i is 5, the agent is transferred to, this, condensed absolute, special diol methyl ether ether, into the single addition agent to drip into, ethanol, methyl-45- 1378973 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 a polyvalent alcohol condensate derivative such as ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl phthalate acetate, propylene glycol monopropyl ether, and the like a mixture of the like, etc. The amount of the organic solvent used may be the same as that obtained in the foregoing amount, and the post-treatment may be carried out in the same manner as described above. Antimony compound (A-2) The molecular weight of the obtained antimony-containing compound (A-2) can be adjusted by controlling the reaction conditions in the polymerization except for the monomer selection, but when a weight average molecular weight exceeds 10,000,000, it may be produced depending on the situation. Foreign matter and coated spots are therefore preferably used below 8,000,000, preferably from 200 to 5,000,000, more preferably from 300 to 3,000. The data on the above weight average molecular weight is 'by using RI Gel permeation chromatography (GPC) of a detector or a light scattering detector, expressed in terms of polystyrene-converted molecular weight measured by using polystyrene as a standard substance. The composition for forming a film containing ruthenium according to the present invention may be The product produced under alkaline conditions may further contain two or more kinds of ruthenium-containing compounds (A-2) having different compositions and/or reaction conditions. Further, a thermal crosslinking accelerator (B), an acid (C), and a stabilizer (D) may be contained. And the organic solvent (E) is added to the above-mentioned ruthenium-containing compound (Al) or (A-2) to obtain a composition for forming a film containing ruthenium. The ruthenium-containing compound (A-1) and the ruthenium-containing compound ( A-2) better · for, the former is more than the latter [ie, the ratio of (Α-1)>(Α-2)] is two-46 - 1378973. More preferably, the addition amount of (A) is (0) with respect to (Al) 100 parts by mass (A-2); (A-2) S50 parts by mass, preferably 0 <(Α·2)$30 parts by mass, more preferably 0 <0>; (A-2)S 20 parts by mass. To further promote the formation of the ruthenium-containing film of the present invention The crosslinking reaction requires a thermal crosslinking accelerator for the component (B), which is a compound represented by the general formula (1) or (2).

LaHbX (1) (wherein L is lithium, sodium, potassium, rubidium or planer, 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 〇 or an integer of 1 or more, a + b is the number of hydroxyl groups or organic acid groups).

MaHbA (2) (where ' is a sulphur gun, iodine gun or ammonium, preferably a three-stage sulphur gun, a secondary iodine gun or a quaternary ammonium, especially a photodecomposable substance, ie a triphenyl sulphur gun Compound, diphenyl iodonium compound. Α is the above-mentioned Χ or non-nucleophilic counter ion, a, b is the same as above, a + b is the value of hydroxyl group, organic acid group or non-nucleophilic counter ion number). The compound represented by the general formula (1) is an alkali metal organic acid salt. For example, 'lithium, sodium, potassium, rubidium, planing hydroxy acid, formate, acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, citrate , citrate, oleate, stearate, linoleate, linolenate, -47-1378973 benzoate, citrate, isophthalate, terephthalate, water a monovalent salt such as salicylate, trifluoroacetate, chloroacetate, 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 linnate, lithium benzoate, lithium niobate, lithium benzoate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium difluoroacetate, lithium monochloroacetate, Lithium dichloroacetate lithium lithium trichloroacetate, lithium hydroxide, lithium hydrogen oxalate, lithium hydrogen malonate, lithium methyl propyl dihydrogenate, lithium ethyl acrylate, lithium propyl propyl hydride, butyl Lithium hydrogen malonate, lithium monomethylpropionate, lithium diethylmalonate, lithium hydrogen succinate, lithium hydrogen methacrylate, lithium hydrogen glutarate, lithium hydrogen adipate, Yikang Lithium hydrogen phosphate, lithium hydrogen maleate, lithium hydrogen fumarate, lithium hydrogen citrate, lithium hydrogen citrate 'lithium hydrogen hydride, lithium oxalate, lithium propionate, lithium methylmalonate Lithium, propyl propionate, lithium butyl malonate, lithium dimethylmalonate, lithium diethyl acrylate, lithium succinate, lithium methyl succinate lithium lithium hexanoate, Lithium benzoate, horse Lithium acid, lithium fumarate, lithium citrate, lithium citrate, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butyrate, sodium valerate, sodium hexanoate, sodium heptanoate, sodium octoate, cesium Sodium, sodium citrate, sodium oleate, sodium stearate, sodium linoleate, sodium linolenate, sodium benzoate, sodium citrate-48-1378973, sodium isophthalate, sodium terephthalate, salicylic acid Sodium, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, sodium trichloroacetate, sodium hydroxide, sodium hydrogen oxalate, sodium hydrogen malonate, sodium methylmalonate , sodium ethyl malonate, sodium propylmalonate, sodium butyl methacrylate, sodium dimethylmalonate, sodium diethylmalonate, sodium succinate, methyl Sodium hydrogen succinate, sodium hydrogen glutarate, sodium hydrogen adipate, sodium itaconate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium citrate, sodium hydrogen citrate, sodium hydrogencarbonate, Sodium oxalate, sodium malonate, sodium methylmalonate, sodium ethylmalonate, sodium propylmalonate, sodium butylmalonate, sodium dimethylmalonate, diethylmalonic acid Sodium, amber Sodium, sodium methyl succinate, sodium glutarate, sodium adipate, sodium itaconate, sodium maleate, sodium fumarate, sodium citrate, sodium citrate, sodium carbonate, potassium formate, acetic acid Potassium, potassium propionate, potassium butyrate, potassium valerate, potassium hexanoate, potassium heptate, potassium octoate, potassium citrate, potassium citrate, potassium oleate, potassium stearate, potassium linoleate, potassium linolenate , potassium benzoate, potassium citrate, potassium isophthalate, potassium terephthalate, potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, trichloro Potassium acetate, potassium hydroxide, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen methyl malonate, potassium hydrogen propyl malonate, potassium propyl malonate, potassium butyl crotonate, two Potassium methylmalonate, potassium diethylmalonate, potassium hydrogen succinate, methyl succinate, hydrazine, potassium hydrogen glutarate, hydroquinone adipate, 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 glutarate-49- 1378973, potassium adipate, potassium itaconate, horse Potassium acid, potassium fumarate, potassium citrate, potassium citrate, potassium carbonate, and the like. The compound represented by the formula (2) is a sulfonium compound, an iodonium compound or an ammonium compound represented by '(Q-1), (Q-2) and (Q-3). R2 s6 , R' 【化 7】 r205 R204 〇205 \ /Κ R207 丨 > Θ ,206 A Ιθ Θ A ,Ν© R21〆, R: R208 Θ (Q-2) (Q-3)

(QD (wherein R204, R205, and R2G6 are each a linear one having a carbon number of 1 to 12; a branched or cyclic alkyl group, an alkenyl group, a carbonylalkyl group or a carbonylalkenyl group, and having a carbon number of 6 to 20 a substituted or unsubstituted aryl group, or an aralkyl group or an arylcarbonylalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like. Further, R205, R2 <)6 Rings can be formed, and R2 0 5 and R 2 0 (each is an alkyl group having 1 to 6 carbon atoms). A- is a non-nucleophilic counter ion 〇R2 0 7 , R 2 08 , • R209 , R 2 形成0 is the same as R2 04, R20 5 . R206 > but may be a hydrogen atom. R207 and r2 0 8 , R2 0 7 and R2 0 8 and r2 1) 9 may form a ring, and when forming a ring, R2()7 and R2°8 And R 2 0 7 and R208 and R209 are an alkylene group having a carbon number of 3 to 10). The above R 2 04, R2 05 , R206 , 1 R207 , R 208 , R209 , R210 may be the same or different from each other. For example, methyl, ethyl 'propyl, isopropyl η-butyl, se ( E-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl-cyclohexyl, cycloheptyl, cyclopropylmethyl, 4·methylcyclohexyl, cyclohexylmethyl , alkaloid, adamantyl, etc. Alkenyl groups such as, for example, vinyl-50-1378973, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. carbonylalkyl such as 2- Carbonylcyclopentyl, 2-carbonylcyclohexyl, etc., or 2-carbonylpropane, 2-cyclopentyl-2-carbonylethyl, 2-cyclohexyl-2-carbonylethyl, 2-(4-cyclohexyl) -2_carbonylethyl, etc. aryl such as phenyl, naphthyl, etc., or methoxyphenyl, m-methoxyphenyl, fluorenyl-methoxyphenyl, ethoxybenzene, p-tert Abutoxyphenyl, alkoxyphenyl such as m-tert-butoxyphenyl or 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, tert -Alkylphenyl group such as butylphenyl, 4-butylphenyl or dimethylphenyl, phenylnaphthyl, ethylnaphthalene Alkylene naphthyl such as alkylnaphthyl, methoxynaphthyl or ethoxynaphthalene, dialkylnaphthyldimethoxynaphthyl such as dimethylnaphthyl or diethylnaphthyl, and diethyl An alkane such as a methoxynaphthyl group such as a dialkoxynaphthyl group such as a benzyl group, a phenylethyl group or a phenethyl group. An arylcarbonylalkyl group such as 2-yl-2-carbonylethyl ' 2- ( 1-aryl-2-carbonylethyl such as 1-naphthyl)-2-carbonylethyl, 2-(2-naphthyl)-2-ylethyl, etc. A non-nucleophilic counter ion 'Hydroxide ion, formic acid ion' acid ion, propionic acid ion, butyric acid ion, valeric acid ion, hexanoic acid ion 'acid ion, octanoic acid ion, citrate ion, citrate ion, oleic acid ion, fatty acid ion, sub Oleic acid ion, linolenic acid ion, benzoic acid ion, methyl benzoic acid ion, P-Bubutylbenzoate ion, phthalic acid ion isophthalic acid ion, terephthalic acid ion, salicylic acid ion, trifluoro acid ion Monochloroacetic acid ion, dichloroacetic acid ion, trichloroacetic acid ion fluoride ion, chloride ion, bromide ion, iodide ion, acid ion, chlorate ion, perchlorate ion, bromine Ionic, iodic acid ion oxalate ion, malonate ion, methylmalonic acid ion, ethylmalonyl P- group s 4-methylphenyl phenyl hexanyl P-, B, N, detach 51 - 1378973, propylmalonate, butylmalonate, dimethylmalonate, diethylmalonic acid ion, succinic acid ion, methyl succinate ion, glutaric acid ion, Adipic acid ion, itaconic acid ion, maleic acid ion, fumaric acid ion, citraconic acid ion, citrate ion, carbonate ion, and the like. Specific sulfur gun compounds such as triphenylsulfuric acid formic acid, triphenylsulfuric acid gun, triphenylsulfur propionate, triphenylsulfonium butyrate, triphenylsulfonium valerate, triphenylhexanoate Sulfur gun, triphenylsulfuric acid heptanoic acid, triphenylsulfuric acid octanoic acid gun, triphenylsulfuric acid citrate, triphenylsulfuric acid citrate, triphenylsulfuric acid oleic acid gun, triphenylsulfuric acid stearic acid gun , linoleic acid triphenyl sulfide gun, linolenic acid triphenyl sulfide gun, benzoic acid triphenyl sulfide gun, P-methyl benzoic acid triphenyl sulfide gun, pt-butyl benzoic acid triphenyl sulphur gun, Triphenylsulfuric acid citrate, triphenylsulfuric acid isophthalate, triphenylsulfuric acid terephthalate, triphenylsulfuric acid salicylate, triphenylsulfuric acid triphenylsulfonate, trifluoro Triphenylsulfuric acid acetate, triphenylsulfuric acid monochlorosulfuric acid, triphenylsulfuric acid dichloroacetate, triphenylsulfonium trichloroacetate, triphenylsulfuric acid hydroxide, triphenylsulfonium oxalate, C Diphenyl trisulfide disulfide, triphenylsulfuric acid methyl malonate, triphenylsulfuric acid ethyl malonate, triphenylsulfur propyl malonate, triphenylsulfur butyl malonate Bismuth, dimethylmalonic acid Phenylsulfur gun, diethylphenylmalonate triphenylsulfur gun, triphenylsulfide succinate, triphenylsulfuric acid methyl succinate, triphenylsulfonium glutarate, triphenyl adipate Thiopurine, itaconic acid triphenylsulfide gun, triphenylsulfonium maleate triphenylsulfonium citrate, triphenylsulfuric citrate, triphenylsulfonium citrate triphenyl carbonate Sulfur gun, triphenylsulfide chloride, triphenylsulfonium bromide, triphenylsulfide gun, triphenylsulfur gun, triphenylsulfur chlorate, triphenylsulfide perchlorate , triphenyl sulfonate bromine, triphenyl-52 - 1378973 thiopurine, bis-triphenyl sulphate oxalate, bis-triphenyl sulphide malonate, dimethyl succinate , bis-triphenylsulfonium oxalate, bis-triphenylsulfonium propyl malonate, bistriphenylsulfonium butyl malonate, bistriphenylsulfonium dimethylmalonate, Diethyl malonate bistriphenyl sulphide, bistriphenylsulfinium succinate, bistriphenylsulfonium methyl succinate, bistriphenyl sulphate glutaric acid, bistriphenyl adipate Sulfur gun, itaconic acid bistriphenylsulfonium, maleic acid bistriphenyl Da, phthalic acid bis triphenyl guns, citraconic acid bis triphenyl pan, bis triphenyl citrate Yi carbonate, bis triphenyl gun. Further, specific iodonium compounds such as diphenyl iodonium formate, diphenyl iodine acetate, diphenyl iodonium propionate, diphenyl iodonium butyrate, diphenyl iodine valerate, caproic acid Phenyl iodine gun, diphenyl iodine heptanoic acid, diphenyl iodine octanoate, diphenyl iodonium citrate, diphenyl iodonium citrate, diphenyl iodonium oleate, diphenyl stearyl Iodine, diphenyliodonium linoleate, linolenic acid diphenyl iodine gun, diphenyl iodonium benzoate, diphenyl iodine gun P-methylbenzoate, diphenyl iodine pt-butyl benzoate Gun, diphenyl iodine citrate, diphenyl iodine isophthalate, diphenyl iodonium terephthalate, diphenyl iodine salicylate, diphenyl iodine trifluoromethanesulfonate, Diphenyl iodine trifluoroacetate, diphenyl iodine monochloroacetate, diphenyl iodonium dichloroacetate, diphenyl iodine trichloroacetate, diphenyl iodine hydroxide, diphenyl iodonium oxalate , diphenyl iodonium malonate, diphenyl iodonium methyl malonate, diphenyl iodonium ethyl malonate, diphenyl iodine propyl malonate, diphenyl urethane dibenzoate Base iodine gun, dimethyl propylene Acid diphenyl iodine gun, diphenyl iodonium diethyl malonate, diphenyl iodine succinate, diphenyl iodonium methyl succinate, diphenyl iodonium glutarate, adipic acid Phenyl iodonium, itaconic acid diphenyl iodine gun, Malay-53- 1378973 diphenyl iodonium iodide, diphenyl iodonium fumarate, diphenyl iodine bismuth citrate diphenyl iodine gun , diphenyl iodine gun, diphenyl iodine bromide diphenyl sulfonium bromide, diphenyl iodide iodine gun, diphenyl iodonium diphenyl iodonium diphenyl iodine gun, diphenyl iodine perchlorate Gun, diphenyl iodonium diphenyl iodonium citrate, bis-diphenyl iodine oxalate, bis-diphenyl phenyl methacrylate, bis-diphenyl thiocyanate, ethyl malonate Diphenyl iodide malonate bis-diphenyl iodine gun, butyl malonic acid bis diphenyl iodonium methyl malonate bis diphenyl iodine gun, diethyl malonate bis diphenyl iodine Succinic acid bisdiphenyl iodine gun, methyl succinic acid bisdiphenyl iodine gun, pentane diphenyl iodine gun, adipic acid bisdiphenyl iodine gun, itaconic acid bisdiphenyl hydrazine, maleic acid double Diphenyl iodonium, bis-diphenyliodonium fumarate, bis-diphenylbenzene Iodine gun, diphenyliodonium citrate bis yi, bis diphenyl carbonate and the like. In addition, specific ammonium compounds such as tetramethylammonium formate, ammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium valerate tetramethylammonium, tetramethylammonium heptanoate , tetramethylammonium octoate, tetraammonium citrate, tetramethylammonium citrate, tetramethylammonium oleate, tetramethylammonium oleate, tetramethylammonium oleate, tetramethylammonium linolenate, benzoic acid Methylammonium methyl benzoic acid tetramethylammonium, pt-butylbenzoic acid tetramethylammonium tetramethylammonium, tetramethylammonium isophthalate, tetramethyl terephthalate, tetramethyl salicylate Ammonium, tetramethylammonium trifluoromethanesulfonate, trifluoroethylammonium chloride, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, tetramethylammonium triacetate, tetramethylammonium hydroxide, oxalic acid Tetramethylammonium, propyldimethylammonium, methylmalonium tetramethylammonium, ethylmalonic acid tetramethylammonium gun, mirror, chlorine, iodine, iron, iron, diacid iodonate Aromatic tetramethyl, hexylmethyl, sub-p-, thioglycolic acid tetrachloroacetic acid tetra, propyl-54 - 1378973-based malonic acid tetramethylammonium, butylmalonic acid tetramethylammonium, dimethyl C Tetramethylammonium, tetramethylammonium diethylmalonate, tetramethylammonium succinate, tetramethylammonium methacrylate, tetramethylammonium glutarate, tetramethyl saddle adipic acid, clothing Tetramethylammonium tetramine, tetramethylammonium maleate, tetramethylammonium fumarate, tetramethyl citrate, tetramethyl citrate, tetramethyl carbonate, tetramethyl chlorinated , tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium chlorate, tetramethylammonium perchlorate, tetramethylammonium bromide, tetramethylmethane, Bis-tetramethyl oxalate, bis-tetramethylammonium malonate, dimethylammonium dimethic acid, bis-tetramethylammonium acrylate, bis-methylammonium propyl malonate, butyl Bis-tetramethylammonium malonate, bis-tetramethylammonium dimethylmalonate, bistetramethylammonium monoethylmalonate, bistetramethylammonium succinate, bis-tetramethylammonium Base ammonium, bistetramethylammonium glutarate, bistetramethylammonium adipate, bistetramethylammonium itaconate, bistetramethylammonium maleate, bistetramethylammonium fumarate, citrine Acid bistetramethylammonium, bistetramethylammonium citrate, bistetramethyl carbonate , tetrapropylammonium formate 'tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium valerate, tetrapropylammonium hexanoate, tetrapropylammonium heptanoate, octanoic acid Propylammonium, tetrapropylammonium citrate, tetrapropylammonium citrate, tetrapropylammonium oleate, tetrapropylammonium stearate, tetrapropylammonium linoleate, tetrapropylammonium linolenate, benzoic acid Tetrapropylammonium, tetrapropylammonium P-methylbenzoate, tetrapropylammonium pt-butylbenzoate, tetrapropylammonium citrate, tetrapropylammonium isophthalate, tetrapropyl terephthalate Ammonium, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, tetrapropylammonium dichloroacetate, tetrapropyltrichloroacetate Ammonium, tetrapropylammonium hydroxide, tetrapropylammonium oxalate, tetrapropylammonium malonate, methylmalonic acid-55- 1378973 tetrapropylammonium, tetrapropylammonium ethylmalonate, propylpropane Tetrapropylammonium dipropyl butyl malonate, tetrapropylammonium dimethylmalonate, tetrapropylammonium dicarboxylate, tetrapropylammonium succinate, tetrapropylammonium methyl succinate Tetrapropylammonium diphosphate Tetrapropylammonium, tetrapropylammonium tetraacetate, tetrapropylammonium fumarate, tetrapropylammonium citrate, tetrapropylammonium phosphate, tetrapropylammonium carbonate, chlorinated tetra Propylammonium, tetraammonium bromide, tetrapropylammonium iodide, tetrapropylammonium nitrate, tetrapropylammonium chlorate, tetrapropylammonium hydride, tetrapropylammonium bromide, tetrapropylammonium iodate, oxalic acid Bis-ammonium, bis-tetrapropylammonium malonate, bis-tetrapropylammonium methylmalonate, bis-tetrapropylammonium malonate, bis-propylammonium propylmalonate, butyl-propylidene-tetrapropyl Base ammonium, bis-tetrapropylammonium dimethylmalonate, diethyl propylene ditetrapropylammonium, bistetrapropylammonium succinate, bis-tetrapropylammonium glutarate Bis-tetrapropylammonium adipate, ditetraammonium itaconate, bistetrapropylammonium maleate, bistetrapropylammonium fumarate, propylammonium citrate, bistetrapropylammonium citrate, carbonic acid Bis-tetrapropylammonium, ammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate tetrabutylammonium, tetrabutylammonium hexanoate, tetrabutylammonium heptanoate, octanoic acid Tetraammonium, tetrabutylammonium citrate, tetrabutylammonium citrate, oil Tetrabutylammonium acid, tetrabutylammonium acid, tetrabutylammonium linoleate, tetrabutylammonium linolenate, tetrabutylammonium anhydride, tetrabutylammonium p-methylbenzoate, pt-butyl amic acid Tetrabutylammonium, tetrabutylammonium citrate, tetrabutylammonium isophthalate, tetrabutylammonium dicarboxylate, tetrabutylammonium salicylate, tetraammonium trifluoromethanesulfonate, tetrabutyltrifluoroacetate Ammonium, tetrabutylammonium monochloroacetate, dichloroethylammonium chloride, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, ammonium oxalate, propylene glycol, malonyl propyl tetrapropylethyl Acidic acid double saddle, propyl bis tetratetrabutyl, pentyl butyl stearin, benzoic acid, p-phenylbutyric acid, tetratetrabutyl-56- 1378973, ammonium, malonic acid, tetrabutylammonium, methylmalonic acid Tetrabutylammonium, tetrabutylammonium ethylmalonate, tetrabutylammonium propylmalonate, tetrabutylammonium butylmalonate, tetrabutylammonium dimethylmalonate, diethylpropane Tetrabutylammonium dicarboxylate, tetrabutylammonium succinate, tetrabutylammonium methyl succinate, tetrabutylammonium glutarate, tetrabutylammonium adipate, tetrabutylammonium itaconate, maleic acid Tetrabutylammonium, fumaric acid Butyl ammonium, tetrabutylammonium citrate, tetrabutylammonium citrate, tetrabutylammonium carbonate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutyl nitrate Ammonium, tetrabutylammonium chlorate, tetrabutylammonium perchlorate, tetrabutyl bromo, tetrabutylammonium phthalate, ditetrabutyl oxalate, bis-tetrabutylammonium malonate, methyl propyl Di-tetrabutylammonium diamine, bis-tetrabutylammonium ethyl malonate, bis-tetrabutylammonium propyl malonate, bis-tetrabutylammonium butyl acrylate, bis-tetramethyl dimethyl malonate Base ammonium, ditetrabutylammonium diethyl malonate, bis-tetrabutylammonium succinate, bis-tetrabutylammonium methyl succinate, bis-tetrabutylammonium glutarate, bis-tetrabutylammonium adipate , bis-butylammonium itaconate, bis-tetrabutylammonium maleate, bis-tetrabutylammonium fumarate, bis-tetrabutylammonium citrate, bis-tetrabutylammonium citrate Ammonium, etc. 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 to be added is preferably from 1 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-57-378798 acid, heptanoic acid, octanoic acid, citric acid, citric acid, oleic acid, stearic acid, linoleic acid, Linolenic acid, benzoic acid, citric acid, isophthalic acid, terephthalic acid, salicylic acid 'difluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid , ethylmalonic acid, propyl malonic acid, butyl malonic acid 'dimethylmalonic acid, diethyl malonic 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 〇〇1 to 15 parts by mass, more preferably 0.1 to 5 parts by mass, per part by mass of the ruthenium-containing compound (A_1) & (a_2). Further, it is preferable to add the above organic acid to the pH of the composition, and to add it to 〇SpHS7, preferably 〇.3SPH core 6.5, more preferably 0·5$ρΗ $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

〇 -58- 1378973

-59- 1378973

Wherein R9 (5a is a hydrogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, and R9l〇-(CH2CH20)nl-(CH2)n2- (wherein OSnl彡) 5,0Sn2S3, R91 is a hydrogen atom or a methyl group), or R9 2 0·[ CH(CH3)CH20]n3-(CH2)"- (wherein 0$ n3S 5, OS n4S 3, R92 is a hydrogen atom or a R9()b is a hydroxyl group, a linear, branched or cyclic monovalent hydrocarbon group having 1 or 10 carbon atoms and having 1 or more hydroxyl groups, HO-(CH2CH20)n5-(CH2) N6-(wherein IS n5S 5, 1$ n6 each 3), or H0-[CH(CH3)CH20]n7-(CH2)n8- (where 1$ n7S 5,1$ n8S 3) the above stabilizer It may be used singly or in combination of two or more kinds. The amount of the stabilizer added is preferably 0.001 to 50 parts by mass, more preferably 0.01 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. Among them, a compound having a cyclic ether derivative and a substituent of a bicyclic ring having an oxygen atom at the bridgehead is preferably used. To make the acid charge more stable, it can be sent to the composition containing bismuth compounds The composition containing the cerium-containing compound of the present invention may be used in the same manner as the organic solvent used in the production of the cerium-containing compound, preferably -60-1378973 as a water-soluble organic solvent. Preferably, it is an alkyl ether such as ethylene glycol, diethylene glycol or triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, etc. Specifically, for example, 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 An organic solvent selected from the group consisting of ether, ethylene glycol monopropyl ether, etc. The composition of the present invention may be added with water. When water is added, the cerium-containing compound may be hydrated to enhance the lithographic etching property. The water content of the solvent component of the composition may be It is more than 50% by mass and preferably not more than 50% by mass, preferably from 0.3 to 30% by mass, more preferably from 0.5 to 20% by mass. When the amount of each component is too large, the uniformity of the coating film is deteriorated, and the worst It will bounce off. If the amount is too small, the lithography performance will be reduced. The total amount of the aqueous solvent to be used is preferably from 50,000 to 1,000,000 parts by mass, particularly preferably from 400 to 50,000 parts by mass, based on 1 part by mass of the base polymer. The present invention can use a photoacid generator, the present invention. The photoacid generator used is, for example, (A-Ι) the following general formula (Pla-1), (Pla-2) or (Plb) gun salt, (A-Π) the following general formula (P2) Nitromethane derivative, (A-III) an ethylenediazine derivative of the following general formula (P3), (A-IV) a biguanide derivative of the following general formula (P4), (AV) the following general formula ( P5) N-hydroxy quinone imine compound sulfonate, (A-VI) yS-keto sulfonic acid derivative, (A-VII) diterpene derivative, -61 - 1378973 (Α·νΐΙΙ) nitro group A benzyl sulfonate derivative, a (Α-ΙΧ) sulfonate derivative or the like. [化1 0 >l〇la一

R mb R101a_^.R101c (Pla-1) (Pla-2) (wherein R1Qla, R1Qlb, and R1Qle are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, a carbonylalkyl or carbonylalkenyl 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, some or all of which may be Further, R1 < nb and RltMe may form a ring, and when ring is formed, RIGlb, each of which is a C 1 to 6 alkyl group, K' is a non-nucleophilic counter ion). The above RIGIa, R1() lb, Rl()le may be the same or different, and the specific alkyl group is, for example, 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 groups such as vinyl, 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. An aryl group such as phenyl, naphthyl or the like, or P-methoxyphenyl, m-methoxyphenyl, fluorenyl-methoxyphenyl, ethoxyphenyl, p-tert-butoxybenzene Alkyl-62- 1378973, alkoxyphenyl group such as m-tert-butoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4- Tert-butylphenyl, 4-butylphenyl, dimethylphenyl, etc. alkylphenyl, methylnaphthyl, ethylnaphthyl and the like alkylnaphthyl, methoxynaphthyl, ethoxynaphthalene a dialkoxynaphthyl group such as a dialkylnaphthyl group such as alkoxynaphthyl group, dimethylnaphthyl group or diethylnaphthyl group; dimethoxynaphthyl group or diethoxynaphthyl group; An aralkyl group such as a benzyl group, a phenylethyl group, a phenethyl group or 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-ion ions such as chloride ions, bromide ions, etc., trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, nonafluorobutanesulfonic acid An aryl-based salt such as a salt such as a fluoroalkyl sulfonate, a p-toluenesulfonate, a besylate, a 4-fluorobenzenesulfonate or a 1,2,3,4,5-pentafluorobenzenesulfonate An alkyl sulfonate such as methanesulfonate or butane sulfonate. [1 1 R102a R102b 104a·

R

-gt_Ri〇3_S^Rl« κ κ (Plb) (wherein R1G2a and RIG2b are each a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R103 is a linear chain having a carbon number of 1 to 10. a branched, branched or cyclic alkyl group. R1G4a, R1G4b are each a 2-carbonylalkyl group having a carbon number of 3 to 7. κ- is a non-nucleophilic counter ion) Specific of the above RM2a, R1G2b, for example, Base, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, pentyl, hexyl 'hepta-63- 1378973, octyl, cyclopentyl, cyclohexyl, ring Propylmethyl, 4., cyclohexylmethyl and the like. R1G3, for example, methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl, 1,2-cyclohexyl, 1,3-cyclopentyl 1,4,1,4-cyclohexane di-methyl, and the like. R1 (Ua, Rl <) 4b, for example, 2-indolecarbonylcyclopentyl, 2-carbonylcyclohexyl, 2-carbonylcycloheptyl, etc. (Pla-1), (PU-2) and (PU-3) Description of things. Φ [Chemical 1 2] R105—S〇2~ C - s〇2-r106 (P2) (wherein R1Q5 and R1Q6 are linear, alkyl or halogenated alkyl groups having 1 to 12 carbon atoms, carbon number 6 to 20 substituted or non-halogenated aryl groups, or aralkyl groups having 7 to 12 carbon atoms). RIQ5' Rlfl6 alkyl such as methyl, ethyl, propyl η-butyl, sec-butyl, tert-butyl, pentyl, hexyl, pentyl, cyclopentyl, cyclohexyl, cycloheptyl , drop the base,. Halogenated alkyl groups such as trifluoromethyl, 1,1,1-trifluoroethyl, 1-yl, nonafluorobutyl and the like. An aryl group such as phenyl, P-methoxyphenylphenyl, fluorenyl-methoxyphenyl, ethoxyphenyl, p_teft_, m-tert-butoxyphenyl, etc. An alkylphenyl group such as methylphenylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenylphenyl or dimethylphenyl. Halogenated aryl groups such as phenyl, 1,2,3,4,5-pentafluorophenyl and the like. The aralkyl group is, for example, a methylcyclohexyl group, a propyl group, a fluorenyl group, a 1,4-cyclohexyl group, a propyl group, or a 2-. K · , for example, a branched or cyclic substituted aryl or isopropyl, heptyl, octyl, or the like, 1,1-trifluoroethyl, m-methoxybutoxyphenyl, 3 -methyl, 4-butylfluorophenyl, chloro, phenethyl-64- 1378973

[化1 3] r1❶, r1❶9

1(V, II R107—S〇2_ O—N= C—C=Γί—O _ S〇2~R107 (P3) (in the formula, Rli) 7, R1", Rl()9 is the carbon number 1 to a linear, branched or cyclic fluorenyl or dentate fluorenyl group of 12, an aryl or halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R108, R1G9 may mutually The bond forms a ring structure, and when the ring structure is formed, each of R1 °8 and R1C9 is a linear or branched alkyl group having a carbon number of 1 to 6.

RlQ7, r1〇8, alkyl group of r109, alkyl halide, aryl, halogenated aryl 'aralkyl group, as defined by R1. 5, R1Q6. Further, R108 'R1 is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. 【化1 4】 Ο 〇

R101s—S-CH2-S—R101b II II ο ο (Ρ4) (wherein R 1 01 a, R1 01 b are the same as above). -65- 1378973 【化1 5】 Ο

II C\ R〇-〇_S〇2-Rm

C

II 〇(P5) (wherein R11() is an exoaryl group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or an extended alkenyl group having 2 to 6 carbon atoms, which are contained in the group Some or all of the hydrogen atoms may be additionally substituted by a straight or branched chain or a pendant oxy group, a nitro group, an ethyl fluorenyl group or a phenyl group having 1 to 4 carbon atoms. R 1 11 is a carbon number of 1 to 8. a linear, branched or substituted alkyl, alkenyl or alkoxyalkyl group, a phenyl group, or a naphthyl group. Some or all of the hydrogen atoms in the group may be additionally substituted with a carbon number of 1 to 4 An oxy group or an alkoxy group; 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 heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom; Replace). Wherein R11() is an extended aryl group such as 1,2-phenylene, 1,8-naphthyl, etc., an alkyl group, a methyl group, an ethyl group, a methyl group, a tetramethyl group, a benzene group. Ethyl extended ethyl, norbornane-2,3-diyl, etc., alkenyl group, such as, 1) 2 · vinyl, 1-phenyl-1,2-vinyl, 5-pentaneene , 3 · Diji and so on. The alkyl group of Riii is as 'the same as R1Qla to RiQi. Alkenyl such as vinyl, fluorenyl, allyl, 1-butenyl, 3-butenyl, isoprenyl, fluorenyl-pentenyl, 3-pentenyl, 4-pentenyl, dimethylallyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, heptenyl, 3-pentenyl, 6-heptenyl, 7_ Octenyl and the like 'alkoxyalkyl group such as methoxymethyl, ethoxymethyl 'propoxymethyl, butoxymethyl, pentoxymethyl, hexyloxymethyl, heptyloxy Methyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl-66- 1378973, pentyloxyethyl, hexyloxyethyl, methoxypropyl, Ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, methoxy A hexyl 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, an η-butoxy group, an isobutoxy group, a tert-butoxy group or the like may be an alkyl group having 1 to 4 carbon atoms. Alkoxy, nitro or ethyl hydrazine substituted phenyl, such as phenyl, tolyl, p-tert-butoxyphenyl, p-ethylindenylphenyl, p-nitrophenyl, etc., carbon number 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 iodine trifluoromethanesulfonate, p-tert-butoxyphenyl phenyl iodine gun, p-toluenesulfonic acid diphenyl iodine gun, P-toluenesulfonic acid (p -tert-butoxyphenyl)phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (P-tert-butoxyphenyl) diphenyl sulfide gun, trifluoromethane Sulfonic acid bis(p-tert-butoxyphenyl) phenyl sulfide gun, tris(p-tert-butoxyphenyl)sulfur trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, P-toluenesulfonic acid (p-tert-butoxyphenyl) diphenyl sulfide gun, P-toluenesulfonic acid bis(p-tert-butoxyphenyl)phenyl sulfide gun, p-toluenesulfonic acid (p-tert-butoxyphenyl)sulfur gun, triphenylsulfur hexafluorobutanesulfonate, triphenylsulfide butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, P-toluene Trimethylsulfonium sulfonate, cyclohexylmethyl (2-carbonylcyclohexyl) sulfonium p-toluenesulfonate cyclohexylmethyl (2-carbonylcyclohexyl) sulphur gun, trifluoromethane sulfonate Acid dimethyl phenyl sulphur gun, P-toluenesulfonic acid di-67- 1378973 methyl phenyl sulphur gun, trifluoromethane sulfonic acid Hexyl phenyl sulphur gun, P-toluenesulfonic acid dicyclohexyl phenyl sulphur gun, trinaphthyl sulfonate trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-carbonylcyclohexyl) sulphur gun, three Fluoromethanesulfonic acid (2-norbornyl)methyl(2-carbonylcyclohexyl)sulfur gun, exoethyl bis[methyl(2-carbonylcyclopentyl)sulfur trifluoromethanesulfonate], 1, An anthracene salt such as 2'-naphthylcarbonylmethyltetrahydrothiophene trifluoromethanesulfonate. Bis(phenylsulfonium)diazomethane, bis(P-toluenesulfonate)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(isopropylsulfonium)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(η-pentylsulfonyl)diazomethane, bis(isopentyl) Sulfonium) diazomethane, bis (sec-amyl dilatation) diazomethyl, bis (tert-pentyl diazide) diazo-methyl hydrazine, 1-cyclohexyl expansion - l- (tert-butyl expansion)醯)diazomethane, 1-cyclohexylsulfonium _l-(tert-pentylsulfonium)diazomethane, hydrazine "p-pentylsulfonium-1-(tert-butylsulfonate)diazomethane, etc. Diazomethane derivative. Bis-〇-(P-toluenesulfonate)-α-dimethylglyoxime, bis-〇·(ρ_toluenesulfonyl-diphenylethylenediguanide, bis-indole-( ρ-Toluenesulfonate·· α-Dicyclohexylethylenediene, bis-indole-(Ρ_toluene)-2,3-pentanedione Second, double 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( , 双- 〇- (n-Dingyuan expanded diphenylethylene bimonthly arch, bis-indole-(η-butanesulfonyl)-α · dicyclohexylethylene dioxime, double-〇_ (η _醯 醯 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) )醯 醯 醯 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Trifluoroethanesulfonate)-α-dimethylglyoxime, bis-indole-(tert-butanesulfonyl)-α-dimethylglyoxime bis- 0-(perfluorooctanesulfonate) )-α-dimethylglyoxime, bis-indolyl-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-indole·(phenylsulfonyl)-α-dimethylglyoxime , double-0-(ρ-fluorobenzenesulfonyl)dimethylglyoxime, bis-(-p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime double- 〇-( Xylene derivative such as xylene sulfonate)-α-dimethylglyoxime or bis- 0-(sulfonium sulfonate)-α-dimethylglyoxime. Bis-trifluoromethylsulfonium methane, bismethylsulfonium methane, bisethylsulfonium methane, bispropylsulfonium methane, diisopropylsulfonyl methane, bis-indole-toluenesulfon methane, diphenylsulfonate飒Methane and other biguanide derivatives 〇2-cyclohexylcarbonyl-2-(ρ-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, etc. /3-ketosulfonic acid Derivatives Diterpene derivatives such as diphenyl diindole and dicyclohexyl difluorene. A nitrobenzyl sulfonate derivative such as 2,6-dinitrobenzyl p-toluenesulfonate or 2,4-dinitrobenzyl p-toluenesulfonate. 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3_tris(p-toluenesulfonyloxy) a sulfonate derivative such as benzene. Ν-hydroxy amber ylide imide methane sulfonate, hydrazine-hydroxy amber imidate trifluoromethane sulfonate, hydrazine hydroxy succinimide ethane sulfonate, hydrazine-hydroxy succinimide 1-propane sulfonate Acid ester, hydrazine-hydroxysuccinimide 2-propane sulfonate, hydrazine-hydroxysuccinimide 1-pentane sulfonate, hydrazine-hydroxysuccinimide 1-octane sulfonate, hydrazine-hydroxyl Amber succinimide ρ-tosylate, Ν--69- 1378973 hydroxy amber succinimide P-methoxybenzene sulfonate, N-hydroxy amber succinimide 2-chloroethane sulfonate, N- Hydroxy amber ylidene benzene sulfonate, N-hydroxy amber succinimide-2,4,6-trimethylbenzene sulfonate, N-hydroxy amber succinimide 1-naphthalene sulfonate, N-hydroxy amber醯imino 2-naphthalene sulfonate, N-hydroxy-2-phenyl succinimide 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 imide methane sulfonate, N-hydroxy quinone benzene sulfonate, N-hydroxy quinone Amine trifluoromethane sulfonate, N-hydroxy quinone imine P-toluene sulfonate, N-hydroxynaphthyl imidazolium 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, a sulfonate derivative of an N-hydroxy quinone imine compound such as N-hydroxy-5-norpoline-2,3-dicarboxy quinone imine P-toluenesulfonate. Among them, triphenylsulfur trifluoromethanesulfonate, p-tert-butoxyphenyl diphenylsulfur gun, trifluoromethanesulfonic acid tris(p-tert- Butoxyphenyl)sulfur, p-toluene mineral triphenylsulfonate, P-toluene acid extension (p-tert-butoxyphenyl)diphenylsulfonium, p-toluenesulfonic acid tris(p) -ter t-butoxyphenyl)thioindole, trinaphthylsulfur trifluoromethanesulfonate, cyclohexylmethyl (2-carbonylcyclohexyl)sulfur trifluoromethanesulfonate, trifluoromethanesulfonic acid (2 -norbornyl)methyl(2-carbonylcyclohexyl)sulfur gun, 1,2'-naphthylcarbonylmethyltetrahydrothiophene trifluoromethanesulfonate and other gun salts, bis(phenylsulfonyl)diazomethane , bis(P-toluenesulfonate)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(11-butyl-70- 1378973 sulfonamide)diazomethane, bis(isobutylsulfonate) heavy Nitrogen methane, bis(sec-butylsulfonyl)diazomethane, bis(η-propylsulfonyl)diazomethane, bis(isopropylase)diazomethane, bis(tert-butylsulfonate) Diazomethane derivatives such as diazomethane, bis-indole-(p-toluenesulfonate)-α· Dimethyl hydrazine, bis- 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( 乙 乙 乙 乙 、 、 、 、 、 、 、 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基 羟基Imine methane sulfonate ' Ν-hydroxy amber ylide ylide trifluoromethane sulfonate, Ν-hydroxy amber succinimide 1-propane sulfonate, Ν-hydroxy amber succinimide 2-propane sulfonate, Ν_Hydroxysuccinimide 1-pentane sulfonate, Ν-hydroxy succinimide ρ-toluene sulfonate, Ν-hydroxynaphthalene dimethyl imidate methane sulfonate, hydroxynaphthyl dimethyl sulfonate a sulfonate derivative of a quinone-hydroxy quinone imine compound such as an amine benzene sulfonate. The photoacid generator may be used singly or in combination of two or more kinds, and the amount of the photoacid generator added is 100% by mass relative to the base polymer (the ruthenium-containing compound (Α-1) and (Α-2) obtained by the above method). The portion (the total amount of the ruthenium-containing compound (Al), (Α-2), 100 parts by mass, the same applies hereinafter) is preferably from 1 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 · 4 3 0", "FC-431", "FC-443 0" (both Sumitomo 3 (share) system), Saflon "S-141", "S-145" 'ΚΗ-10', 'ΚΗ-20', 'ΚΗ-30', 'ΚΗ-40' (all are Asahi Glass Co., Ltd.), Unyed "DS-401", "DS-4 03", "DS-451" (both Daikin Industries Co., Ltd.), Meike-71 - 1378973, "F-8151" (Daily Ink Industry Co., Ltd., "χ_7〇·〇92", "X- 70-093" (both Shin-Etsu Chemical Co., Ltd.), etc. It is preferably Flora "FC-4430", "KH-20", "KH-30", "X-70-093". The amount of the active agent to be added may be a normal amount without impairing the effects of the present invention, but is 0 to 10 parts by mass, particularly preferably 0 to 5 parts by mass, per 100 parts by mass of the base polymer. The present invention is applicable to an etching mask The ruthenium-containing film can be formed on the substrate by a composition for forming a film containing ruthenium by a spin coating method, etc. The solvent is evaporated after spin coating, and the crosslinking reaction is preferably carried out in order to prevent the upper photoresist film from being mixed. Bake it with baking. Degree 50 to 50 (1 to 3 seconds at TC is preferred. The temperature range of the device is different depending on the structure of the device to be manufactured, but it is preferably 400 t or less in order to reduce the thermal damage of the device. According to the invention, after the sand-containing film is formed on the processed portion of the substrate to be processed, a photoresist film is formed thereon to form a pattern. At this time, the processed portion of the substrate to be processed is, for example, k値 is a low-permittivity insulating film of 3 or less, a low-permittivity insulating film after primary processing, an inorganic film containing nitrogen and/or oxygen, a metal film, etc. More specifically, the substrate to be processed may be formed on a base substrate. The substrate to be processed (the portion to be processed). The basic substrate is not particularly limited, and Si, amorphous sand (α-Si), p-Si, SiO 2 , SiN, SiON, W, TiN, A1, etc. can be used. The material of the processing layer. The processed layer used may be Si, SiO 2 , SiN, SiON, p-Si, a - S i, W, W - S i, A1, C u, A

Si and other low dielectric films and their anti-etching films generally have a thickness of -72 to 1378973 of 50 to 10,000 nm, and particularly preferably 100 to 5,000 nm. In the present invention, a commercially available organic anti-reflection film can be formed between the above-mentioned ruthenium-containing film and the upper photoresist film. The structure of the antireflection film at this time is formed of a compound having an aromatic substituent. The antireflection film needs to have no etching load on the upper photoresist film when the pattern of the upper photoresist film is replicated by dry etching. For example, it is preferable that the thickness of the upper photoresist film is 80% or less and the dry etching load is 50% or less. The antireflection film at this time is preferably adjusted to have a 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(methyl)acrylic acid system, a COMA (Cyclo Olefin Maleic Anhydride) system, a COMA-(meth)acrylic acid mixture system, and a R〇MP (Ring Opening M ethathesis Ρ ο 1 ymerizati). ο η), polypyrene, etc., in which a photoresist composition using a poly(meth)acrylic resin is introduced into the alicyclic skeleton by a branch to ensure corrosion resistance, so the resolution performance is higher than that of other resin systems. Excellent" The ArF excimer laser photoresist composition known to use poly(meth)acrylic resin is a large number, and the positive type is used by the main function to ensure the corrosion resistance of -73-1378973. A unit which is converted into an alkali-soluble unit by the action of an acid and a unit for ensuring adhesion, or a unit comprising a unit having two or more of the above-described functions in a single unit constitutes a polymer. Among them, a (meth) acrylate having an acid-labile group having an adamantane skeleton, which is an acid-retaining group having an adamantane skeleton, is used as a unit having an alkali change in acidity (Japanese Unexamined Patent Publication No. Hei 9-73173) And the (meth) acrylate of the acid-unstable group of the tetracyclododecane skeleton (Japanese Laid-Open Patent Publication No. 2003-84438) can impart high resolution and corrosion resistance. In addition, the unit for ensuring adhesion is particularly preferably used, and has a (meth) acrylate having a lactone ring on the lower side of the lactone ring (International Publication No. 00/0166), which has a bad fall. A (meth) acrylate having a hydroxy adamantyl group and a (meth) acrylate having a hydroxyadamantyl branch (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. Corrosion resistance and 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 strontium salts, are good for sensitivity and resolution. Further, there are a large number of known basic substances, and a number of examples -74-1378973 have been disclosed in Japanese Laid-Open Patent Publication No. 2005-146252, and a film layer containing ruthenium may be prepared by using an appropriate selection. It is preferable to use a photo-resist composition solution to form a photo-resist layer on the top side, and to use a spin coating method using a film layer containing ruthenium in the same etching mask. 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 high etching rate with respect to the gas and reduces the film of the upper photoresist film. 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 content of the cerium is 15% by mass or less in addition to the organic film. Containing antimony materials. The underlying film is specifically known to have a large number of organic films having an aromatic skeleton. For example, JP-A-2005-1285 09, 4,4'-(9H-芴-9-ylidene) bisphenol novolac Other than the varnish resin (molecular weight: 11, yttrium), a known two-layer photoresist method such as a resin such as a novolac resin and a three-layer photoresist method may 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 multi-75-1378973 layer photoresist method using the underlayer film as the etched mask of 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 etching, 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, 〇〇〇), other resins such as novolak resin, known as double-layer photoresist method and 3 layers The photoresist film of the photoresist method can be used. Further, in order to make the heat resistance higher than that of the general novolak, a polycyclic skeleton such as a 4'-(9H-芴-9-ylidene) bisphenol novolac resin can be introduced, and a polyamidene resin (for example, JP-A-2004-153125). 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 preferred to perform baking in order to evaporate the organic solvent. It is preferably carried out at a baking temperature of 80 to 300 ° C for 10 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 00 Å or less. The thickness of the sand-containing film of the present invention is preferably Lnm or more and 200 nm or less, and the thickness of the photoresist film is 1 nm or more and 300 nm or less. The three-layer photoresist method using the ruthenium-containing film using the etching mask of the present invention is as follows. In this step, a film of -76-1378973 is first formed on the substrate to be processed by spin coating. 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 above anti-reflection film and the film containing ruthenium is hardly affected by the etching of the size of the photoresist film to affect the pattern change, and a film pattern containing ruthenium can be 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 uranium 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 substrate to be processed can be more precisely etched. [Embodiment] Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, -77-1378973, but the present invention is not limited to the description. Synthesis of ruthenium-containing compound (A-1) [Synthesis Example 1] Methanol 2008, ion-exchanged water 2008, 35% hydrochloric acid 1 § was placed in a 1,000 ml glass flask, and tetraethoxy decane 5 〇g was further added at room temperature. A mixture of 100 g of methyltrimethoxydecane and phenyltrimethoxydecane. After directly hydrolyzing and condensing at room temperature for 8 hours, propylene glycol monoethyl ether 300 ml' was added and concentrated under reduced pressure to obtain a hydrazine-containing compound! The propylene glycol monoethyl ether solution was 300 g (polymer concentration 21%). The polystyrene-converted molecular weight of the material was measured, and as a result, Mw = 2,000. [Synthesis Example 2] 50 g of tetraethoxy decane of Synthesis Example 1, 100 g of methyl trimethoxy fluorene, and phenyl trimethyl group were replaced by methyltrimethoxydecane 10 〇g and phenyltrimethoxydecane 2 〇g. In the same manner as the mixture of 10 g of oxoxane, the same operation of the propylene glycol monoethyl ether solution containing hydrazine compound 2 was carried out at 300 g (polymer concentration: 9%). The polystyrene-converted molecular weight of the product was measured, and as a result, Mw = 3, 〇〇〇. [Synthesis Example 3] In addition to 260 g of ion-exchanged water, 5 g of 65% nitric acid, 7 g of tetramethoxy fluorene, 70 g of methyltrimethoxydecane, phenyltrimethoxydecane l〇g, and butanediol The ether was replaced with methanol 6 〇g of Synthesis Example 1, ion-exchanged water-78-1378973 200 g, and 35°/. Butyl glycol monomethyl ether solution containing hydrazine compound 3 was treated in the same manner as lg, hydrochloric acid 50 g, methyltrimethoxydecane 100 g, phenyltrimethoxydecane 10 g and propylene glycol monoethyl ether. 3 〇〇g (polymer concentration 20%). The polystyrene-converted molecular weight of the product was measured, and as a result, Mw = 2,500 00 » [Synthesis Example 4] 260 g of ion-exchanged water and 35% of HCl hydrochloric acid were placed in a 玻璃ml glass flask, and then added at room temperature. A mixture of 70 g of tetramethoxydecane, 25 g of methyltrimethoxydecane, 25 g of a decane compound of the following formula [i], and phenyltrimethoxydecane. After directly hydrolyzing and condensing at room temperature for 8 hours, methanol by-produced was distilled off under reduced pressure. After adding 800 ml of ethyl acetate and 300 ml of propylene glycol monopropyl ether, the aqueous layer was separated, and 100 ml of ion-exchanged water was added three times to the remaining organic layer, stirred, left standing, and liquid-separated, and then propylene glycol- 200 ml of propyl ether was added to the remaining organic layer, and concentrated under reduced pressure to give a propylene glycol monopropyl ether solution of hydrazine compound 4 (300 g). The chloride ion of the obtained solution was analyzed by an ion chromatograph, and the result was not confirmed. The polystyrene-converted molecular weight of the material was measured, and the result was Mw = 1, 80 0 »

(CH30)3Si [Synthesis Example 5] -79- [i] 1378973 200 g of ethanol, 100 g of ion-exchanged water, and 3 g of methanesulfonic acid were placed in a 1,000 ml glass flask, and 40 g of tetramethoxydecane was further added at room temperature. A mixture of methoxytrimethoxydecane l〇g, 50 g of a decane compound of the following formula [ii], and phenyltrimethoxydecane l〇g. After directly hydrolyzing and condensing at room temperature for 8 hours, methanol as a by-product was distilled off under reduced pressure, and then ethyl acetate (100 ml) and ethylene glycol monopropyl acid (30 ml) were added. After the aqueous layer was separated, 100 ml of ion-exchanged water was added to the remaining organic layer for 3 times, and the mixture was stirred, allowed to stand, and liquid-separated. Ethylene glycol monopropyl ether 2 〇〇 ml was added to the remaining organic layer, and concentrated under reduced pressure to give a hexane (yield: 20%). The methanesulfonic acid ion of the obtained solution was analyzed by an ion chromatograph, and it was judged that 99% of the reaction product was removed. The polystyrene-converted molecular weight of the product was measured, and as a result, Mw = 2,100. [Chemical 1 7

(CH30)3Si [ϋ] Synthesis of antimony-containing compound (Α·2) [Synthesis Example 6] Ethanol 500 §, ion-exchanged water 250 § '25% oxidized tetramethylammonium 2.5 g was placed in a 1,000 ml glass flask. The mixture was stirred at 55 Torr while a mixture of 97 g of tetraethoxy decane and 73 g of methyltrimethoxy decane was added dropwise over 2 hours. After stirring at 55 t for 1 hour, it was cooled to room temperature, and then 3 g of a 20% aqueous maleic acid solution was added. After adding 1,000 ml of propylene glycol monopropyl ether to -80-1378973, the solution was concentrated to 900 ml, and then 2,000 ml of ethyl acetate was added. After washing twice with 300 ml of ion-exchanged water and liquid separation, ethyl acetate was concentrated under reduced pressure to obtain 900 g of a propylene glycol monopropyl ether solution containing ruthenium compound 6 (polymer concentration: 7%). 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 molecular weight of the polyphenylene oxide in this product was measured, and as a result, Mw = about 1,000,000. [Synthesis Example 7] In place of the mixture of 100 g of tetraethoxydecane, 58 g of methyltrimethoxydecane and 10 g of phenyltrimethoxydecane, the tetraethoxy oxane 97g of the synthesis example 6 and the methyltrimethoxy group were replaced. In the same manner as the mixture of 73 g of decane, the same operation was carried out to obtain 900 g of a propylene glycol monopropyl ether solution containing hydrazine compound 7 (polymer concentration: 7%). The tetramethylammonium ion of the obtained solution was analyzed by an ion chromatograph, and it was judged that the reaction product was removed at 98 °/. . The polystyrene converted molecular weight of the material was measured, and as a result, Mw = about 100,000. [Examples and Comparative Examples] The cerium-containing compounds 1 to 7 obtained in the above Synthesis Examples, the acid 'thermal crosslinking accelerator, the solvent, and the additives were mixed at a ratio shown in Table 1, and then filtered with a fluororesin filter of Ο.ίμηι. Each of the films for forming a film containing ruthenium is prepared, and each is represented by S 〇1 · 1 to 1 0. -81 - 1378973 [Table i] Forming a film composition containing ruthenium

No. Antimony compound (parts by mass) Thermal crosslinking accelerator (parts by mass) Acid (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) Μ /\\\ 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) 实施 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) Μ / 1 \> 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 (3) Stabilizer 4 (5) /» 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) M j \ w 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 (9) Stabilizer 1 (5) j\w Comparative Example 1 Sol.8 Compound 1 (4-0) TPSOAc (0.04) Μ /W' t Propylene glycol monoethyl ether (100) Water (5) Stabilizer 1 (5) M j\\\ Comparative Example 2 Sol.9 Compound 1 (4.0) No maleic acid (0.01) Propylene glycol monopropyl ether (100) Water (5) Stabilizer 1 (5) Sister /* 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) Group yi \\ -82- 1378973 TPSOAc: Triphenylsulfide acetate (photodegradable thermal crosslinking accelerator) TPSOH: triphenylsulfonium hydroxide (photodegradable thermal crosslinking accelerator) TPSC1: chlorine Triphenylsulfur gun (photodegradable thermal crosslinking accelerator) TPSMA: maleic acid mono(triphenylsulfanthrene) (photodegradable thermal crosslinking accelerator) TPSN: triphenylsulfuric acid nitrate (photolysis) Thermal crosslinking accelerator) TMAOAc: tetramethylammonium acetate (non-photodecomposable heat exchange) Joint accelerator) TPSNf: triphenylsulfur gun nonafluorobutane sulfonate (photoacid generator) [Chem. 1 8]

Stabilizer 3

Stabilizer 4:

-83- 1378973 Stabilizer 5 : 八a y—〇H Γ°^Γ

First, the composition of the underlying film material containing 4,4'-(9Η-芴-9-ylidene) bisphenol novolak resin (molecular weight 11, 〇〇〇) (JP-A-2005-128509) (tree S曰28 mass parts, solvent 100 parts by mass) on a spin-coated sand wafer, heated at 200 ° C for 1 minute, and then formed into a film to form a film thickness of 300 rirn of the underlying organic film. 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. Subsequently, Sol. 1 to 10 were spin-coated, and after heating at 200 ° C for 1 minute, a film of ruthenium having a film thickness of 100 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 acetate) containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.). In the salt solution, it was filtered by a filter made of a fluororesin of 0.1 μm. -84- 1378973 【化1 9】 Rouge

(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 second (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, The Cr mask was exposed and baked (PEB) at 10 ° C for 90 seconds, and then developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution to obtain a positive pattern. The shape of the pattern of 90 nm L/S, the results are shown in Table 2. -85- 1378973 [Table 2] Pattern shape

No. Fig. Shape Example 1 Sol. 1 Good Example 2 Sol. 2 Good Example 3 Sol. 3 Good Example 4 Sol. 4 Good Example 5 Sol. 5 Good Example 6 Sol. 6 Good Example 7 Sol.7 Good Comparative Example 1 Sol.8 Footing shape Comparative Example 2 Sol.9 Negative film shape Comparative Example 3 _ Sol.10 Good

In any of the embodiments, there is no pattern of skirting, undercutting, and miscellaneous mixing in the vicinity of the substrate. Next, the dry etching resistance test was carried out. After the above compositions Sol. 1 to 10 were spin-coated, the film was formed by heating at 200 ° C for 1 minute to form a film having a film thickness of 100 nm, Film 1 to 10», under the following etching conditions ( 1) An etching test was performed on the film, the underlayer film, and the photoresist film, and the results are shown in Table 3. (1) Etching test using CHF3/CF4 gas: Device: Tokyo Electron Co., Ltd. Dry etching device TE-8500P Etching conditions (1): Casing pressure 40.0Pa

RF power 1,300W clearance 9mm -86- 1378973 30ml/min 3 0m 1 /m i η 1 OOml/min 1 0 s e c chf3 gas flow cf4 gas flow

Ar gas flow processing 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, the 〇2 series shown in Table 4 was investigated by the following etching conditions (2). Gas dry etching rate. 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 600W -87- 1378973 40ml/min 60 ml/min 9mm 20sec

Ar gas flow 〇2 gas flow gap processing time [Table 4]

〇2 system gas dry etching rate 矽 film 02 gas etching rate Γηιη/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 A storage stability test was additionally carried out. The above-mentioned composition for forming a film containing sand (Sol. 1 to 10) was stored at 3 ° C for 1 month, 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. Expressed. -88- 1378973 [Table 5] Preservation stability result Composition property after coating Example 1 Sol. 1 No film thickness variation, no pattern shape change Example 2 Sol. 2 No film thickness variation 'No pattern 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 change 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. l〇 film thickness increased by 15%, pattern peeling was confirmed by the results of Table 5, and the composition of any of the examples had 3 (more than 3 months under TC, It is converted into storage stability at room temperature for 6 months or more. From the above, the composition of the present invention and the film containing ruthenium have excellent stability and lithographic characteristics. The composition is exposed at the highest NA of the apex. The machine can form a pattern and can be processed by etching. -89-

Claims (1)

1378973 Patent Application No. 097125095 Patent Revision of the Chinese Patent Application No. 119. August . 曰 、 、 、 、 、 、 、 、 、 、 、 、 、 、 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请 申请1) using one or more compounds selected from the group consisting of inorganic acids and sulfonic acid derivatives as an acid catalyst by using the following general formula (3) R 1 m 1 S i ( Ο R) (4-m 1 (3) (wherein R is an alkyl group having 1 to 3 carbon atoms, and R1 is a methyl group, an ethyl group, a phenyl group, and the following formula: (In the above formula, (Si) represents a group selected from the group represented by the bonding site of hydrazine; and one or a mixture of two or more selected from the hydrolyzable chopping compounds represented by 0 or 1) is hydrolyzed. (A-2) hydrolytic condensation of one or a mixture of two or more selected from the hydrolyzable hydrazine compounds represented by the above formula (3) using a base as a catalyst (B) one or more selected from the group consisting of a mirror compound represented by the following general formulae (Q·1) and (Q·3) and an ammonium compound as a thermal crosslinking accelerator: 1378973 R material month 1 anger page (Le R2?4 X* p205s^) e p206 A R207 〇〇8 R210 ΘA (Q-3) (Qi) (wherein R204, R205, and R206 each represent a phenyl group, and R207, R208, R2e9, and R2IG each represent a methyl group, and represent a hydroxide ion, a formate ion, an acetate ion, and a propionic acid ion. Butyric acid ion, valeric acid ion, hexanoic acid ion, heptanoic acid ion, octanoic acid ion, citric acid ion, citric acid ion, oleic acid ion, stearic acid ion, linoleic acid ion, linolenic acid ion, benzoic acid ion, P-methylbenzoic acid ion, Pt-butyl benzoate acid ion 'capric acid ion, isophthalic acid ion, terephthalic acid ion, salicylic acid ion, trifluoroacetic acid ion, monochloroacetic acid ion, dichloroacetic acid Ion, trichloroacetate ion, nitrate ion 'chlorate ion, perchlorate ion, bromate ion, iodic acid ion, oxalate ion, malonate ion, methylmalonate ion, ethylmalonate ion, C Malonate, butylmalonate, dimethylmalonate, diethylmalonic acid ion, succinic acid ion, methyl succinate ion, glutaric acid ion, adipic acid ion, clothing Kang acid ion, maleic acid ion, fumaric acid Non-nucleophilic counterions selected from the group consisting of citrate, citrate, and carbonate ions; (C) from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, and octanoic 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, two Chloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid , succinic acid, methyl succinic acid, glutaric acid -2- 1378973 h 丨 丨 II page II (this), adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and citric acid a selected organic acid; (D) a monovalent or higher valence alcohol having a cyclic ether as a substituent (except for furan methyl alcohol and tetrahydrofuran methyl alcohol); (E) an organic solvent (however, having a ring shape) Except for the monovalent or divalent or higher alcohol in which the ether is a substituent). 2. The thermosetting composition according to claim 1 of the invention, which comprises a ruthenium-containing film composition, wherein the ruthenium-containing compound (A-1) is selected from the group consisting of inorganic acids and sulfonic acid derivatives. The ruthenium-containing compound obtained by the step of substantially removing the acid catalyst in the ruthenium-containing reaction mixture obtained by hydrolyzing and condensing the above hydrolyzable ruthenium compound as an acid catalyst. 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) contains a hydrolyzable hydrazine 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 thermosetting composition according to claim 1 or 2, which forms a composition for a film containing cerium, wherein the hydrolyzable cerium-containing compound is tetramethoxy decane, tetraethoxy decane, methyl trimethoxy Decane, phenyltrimethoxydecane, and Selected from the decane compounds shown. 5. The thermosetting composition of claim 1 or 2 forms a composition for the film containing yttrium, which is composed of oxalic acid, maleic acid, and formic acid. An organic acid selected from the group consisting of acetic acid, propionic acid, and citric acid. 6. The thermosetting composition according to claim 1 or 2, which forms a composition for a film containing cerium, wherein the component (E) is ethylene glycol. And dialkyl glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol and one of the alkyl ethers of pentanediol are selected. 7. The composition for film formation containing ruthenium according to the thermosetting property of claim 1 or 2, wherein the composition (A-2) satisfies 〇<lt;>; (A-2) S50. 8. The thermosetting composition according to claim 1 or 2, which forms a film composition containing ruthenium, further comprising a photoacid generator. 9. The thermosetting composition according to claim 1 or 2, which forms a film composition containing ruthenium, further containing water. A film comprising ruthenium formed by the composition of any one of items 1 to 9 of the patent application, characterized in that after the organic film is formed on the substrate to be processed, a ruthenium-containing film is formed thereon. a film, and then using a chemically-reinforced photoresist composition containing no antimony to form a photoresist film, and patterning the photoresist film, and patterning the film containing germanium using the photoresist film pattern And then processing the underlying organic film by etching the film pattern containing the ruthenium as an etching mask, and then using the processed organic film as an etching mask to etch the substrate to be processed by the multilayer photoresist method A film containing ruthenium formed by the composition of any one of items 1 to 9 of the patent application, characterized in that it is a multilayer light as described in claim 10 of the patent application. In the step of the resistive method, a multilayer of an organic anti-reflection film is interposed between the photoresist film and the film containing germanium obtained from the chemically-enhanced photoresist group 1387973 _ 'h. - a film containing ruthenium used in the photoresist method. 12 - a substrate characterized by sequential formation An organic film comprising a ruthenium-containing film formed of the composition of any one of items 1 to 9 of the patent application, and a photoresist film thereon. 13. A substrate characterized by The organic film is formed on the organic film, the film containing ruthenium formed by the composition of any one of items 1 to 9 of the patent application, the organic antireflection film, and the photoresist film thereabove. The substrate of claim 12 or 13, wherein the organic film is a film having an aromatic skeleton. • A method of forming a pattern, wherein the method of forming a pattern on a substrate is prepared as in the method of applying The substrate of the 12th patent of the patent, after exposing the pattern loop field of the photoresist film of the substrate, forming a photoresist pattern on the photoresist film by developing a developing solution to form the light of the photoresist pattern The resist film is an etching mask to dry-etch the film containing the germanium, and then the organic film is etched by forming a patterned germanium-containing film as an etching mask, and then the patterned organic film is used as a mask to the substrate. Etching to form a pattern on the substrate. The method of forming a pattern on a substrate, preparing a substrate according to claim 13 of the patent application, exposing the pattern loop region of the photoresist film of the substrate, and developing the image with a developing solution Forming a photoresist pattern on the photoresist film to form a photoresist pattern of the photoresist pattern as an etching mask, dry etching the organic anti-reflection film and the film containing the germanium, and then forming a pattern containing The film is etched by the etching mask to etch the organic film, and then the organic film of the type A is patterned to etch the substrate to form a pattern on the substrate. 1378973 (4) 丨曰 丨曰 It page (this) 17. The method of forming a pattern of the invention of claim 15 or 16, wherein the organic film is a film having an aromatic skeleton. 18. The method for forming a pattern according to claim 15 or 16, wherein the photoresist pattern is formed In the case of the type, a photographic micro-etching method using light having a wavelength of 3 OOnrn or less is used. -6-