TW200848451A - Silicon-containing polymer, method for synthesizing the same, film-forming composition, silica film and method for forming the silica film - Google Patents

Abstract

Disclosed is a method for synthesizing a silicon-containing polymer, which comprises a step for adding a first liquid containing at least one hydrolyzable silane compound selected from hydrolyzable silane monomers (A) and hydrolyzable polycarbosilanes (B) to a second liquid containing water and a catalyst, thereby causing hydrolysis-condensation of the hydrolyzable silane compound.

Description

200848451 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cut polymer, a method for synthesizing the same, a composition for forming a film, a cerium oxide film, and a method for forming the same. [Prior Art] Conventionally, as the interlayer insulating film of a semiconductor element or the like, a cerium oxide (Si 2 ) film formed by a vacuum process such as a CVD method is often used. However, in recent years, in order to form an interlayer insulating film having a more uniform thickness of a sentence, a so-called SGG (SPin on Glass) film, which is mainly composed of a hydrolyzed product of four alkoxylated dreams, is also used. Type insulating film. In addition, with the high integration of semiconductor elements and the like, there has been development of an interlayer dielectric film having a low dielectric constant containing a polyorganosiloxane as a main component of organic SOG. However, with further integration and multilayering of semiconductor elements and the like, superior electrical insulation between conductors is required, and therefore, interlayer insulation having good storage stability and lower dielectric constant and mechanical strength is required. membrane. Further, in the manufacturing process of the semiconductor device, a CMP (Chemical Mechanical Planarization) step for flattening the insulating layer and various cleaning steps are performed. Therefore, in addition to the dielectric constant characteristics of the interlayer insulating film and the protective film which can be applied to a semiconductor device, it is required to have mechanical strength and resistance to corrosion due to the chemical solution. As a material having a low dielectric constant, there are proposed a composition comprising a mixture of fine particles obtained by condensing an alkoxy group in the presence of ammonia and a basic partial hydrolyzate of a burnt-oxygen yarn (Japan) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The coating liquid obtained is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. However, according to the material of the ruthenium ruthenium, the nature of the reaction product is not stable, and the dielectric constant, cracking property, mechanical strength, and adhesion of the coating 2 are large, which is disadvantageous to the industry. Sexual production. In addition, the proposal has a method of preparing a (four) liquid film by mixing a polycarbon solution with a poly-wet solution and forming a low-medium (four) number of film (Japanese Patent Laid-Open No. 127152) Bulletin, Japan Special; :2 "45317]) However, this method will have the problem that the carbon decane and the poly y, the y y knives are partially dispersed in the uneven state, and the application is also used. A method for producing an organic oxalic acid compound obtained by hydrolyzing and condensing a carbon-containing smectite oligomer after the production of a carbaryl compound (International Publication No. 2/〇98955) The material obtained by the method belongs to a material which is poor in stability of the reaction product and is suitable for long-term storage, and has a problem of poor adhesion to the substrate. The proposal of 4 is to hydrolyze and condense the high-scoring carbon to obtain the electric coefficient insulation. Method for forming a film (U.S. Patent No. 6 ' ^ ', but after applying a polymer onto a substrate, it is necessary to perform a ripening treatment with ammonia, a trimethyl sulphate treatment, and a high temperature hardening process. Processing is not suitable OBJECT OF THE INVENTION The object of the present invention is to provide a semiconductor element which is expected to be highly integrated and multilayered, and to suppress generation and storage stability of coarse particles. a ruthenium-containing polymer formed by an insulating ruthenium having a low dielectric constant and low hygroscopicity, excellent mechanical, strength, and chemical resistance, and a method for forming the same, and a film forming composition containing the above ruthenium-containing polymer The present invention has another object of the present invention to provide a cerium oxide film having a low dielectric constant and a low hygroscopicity and superior in mechanical strength and chemical resistance, and a method and method for forming the same. - a method for synthesizing a polymer containing a Zeolite, comprising: containing at least one hydrolyzable decane compound selected from the group consisting of (A) a hydrolyzable decane monomer and (B) a hydrolyzable polycarbane The first liquid is added to the second liquid containing water and a catalyst to hydrolyze the hydrolyzable decane compound. In the present invention, the term "hydrolyzable" means that the polymer having ruthenium is produced. In the method for synthesizing the above-mentioned ruthenium-containing polymer, when the second liquid is added to the second liquid, the temperature of the second liquid can reach 4 (rc or more). In the method for synthesizing the polymer of the above formula, the (A) hydrolyzable calcined monomer may be a pyrotechnic compound selected from the group of compounds represented by the following general formula (1M3).

RaSi(〇R1)4_a · (1) (wherein R represents a hydrogen atom, a fluorine atom or a monovalent organic group; R1 means a monovalent organic group; and a means an integer of 1 to 3). 97104568 7 200848451

Si(0R2)4 ······(2) (wherein R2 means a monovalent organic group.) R'(R40)3-bSi-(R7VSi(〇R5)3, cR' ••...( 3) [In the formula, R3~R6 are the same or different, and the division is gentleman. ^^ The knife is not a monovalent organic base; b, and c are different or different from each other. "Value, R is a group represented by an oxygen atom, a phenyl group or a -(CH2), - (wherein, a paw, you. n ^ , an integer of 1 to 6 of the methyl group); d means ϋ or 1. 〕, the above (Β) hydrolyzable polycarbon shows the structural unit of the carbon stone

The method for synthesizing the above-mentioned ruthenium-containing polymer allows the shixi firing system to have the following general formula (4). [Chemical 1]

••...(4) In the formula, 'r is selected from hydrogen atom, tooth atom, meridine, alkoxy group, i-milyl group, nucleobase group, w acid group, trifluoromethyl lysyl group, alkyl group, aromatic group. a group consisting of allyl and epoxypropyl groups; R9 is selected from the group consisting of a tooth atom, a mesogenic group, an alkoxy group, a decyloxy group, a benzyl group, a methyl group, and a trihalite group. The groups f'Rl°, ^11 are the same or different from each other in the group consisting of a base group, a base group, an allyl group and a glycidyl group, which are selected from a halogen atom, a trans group, an alkoxy group, an acidoxy group, and a Wei group. A group of groups consisting of a group of acid groups, a trifluoromethyl group, a carbon number of 2 to 6, a ί, an aryl group, an allyl group, and an epoxy propyl group; R to R are the same or different, indicating Substituted or unsubstituted sub-$97104568 8 200848451 benzyl, alkylene, alkenyl, alkynyl, aryl; χ, y, z represent a value of 〇~10,000, respectively, and satisfy 5 <1 for + 2< 1 〇, 〇〇〇 condition. In the method for synthesizing the ruthenium-containing polymer, the hydrolyzable decane compound is the (A) hydrolyzable decane monomer and the (B) hydrolyzable polycarbosulfide, and the above (B) The hydrolyzable polycarbosilane complete hydrolysis condensate is 1 part by weight, and the above (A) hydrolyzable decane monomer is bwoo weight =. In the method for synthesizing the ruthenium-containing polymer, the catalyst is at least one selected from the group consisting of a basic compound, an acidic compound, and a metal chelate compound. In this case, the above basic compound may be a general formula or a nitrogen-containing compound. (XTxVNXY . . . . (5) (wherein X, X2, X3, and χ4 are independent hydrogen atoms, carbon number alkyl groups, burnt groups, aromatic groups or aryl groups; γ systems are halogens Atom = avalent anionic group; g means an integer of 1 to 4. Further, in this case, the acidic compound may be an organic acid. Alternatively, the metal chelate compound may be one of the following metals. a chelate compound, and eM(0R)f- (wherein Rl5 means chelation; i means a base of a metal, a sub.r16;:5, or a carbon number; An aromatic group of 6 to 20; f means a metal M having a carbon number of 4 Å, and e means an integer of 1 to f.] Spoon atom. The present invention-containing cerium-containing polymer is according to one aspect of the present invention. The composition for forming a film is a compound and an organic solvent. 3 The above-mentioned second-containing poly 97104568 200848451 A method for forming a cerium oxide-based film according to an aspect of the present invention includes a step of coating a composition on a substrate to form a coating film, and a step of subjecting the coating film to a hardening treatment. The present invention - the aspect of the dioxide film is based on the above two Obtained according to the method for forming a fossil cerium film. μ, according to the method for producing a polymer containing the sulphate, at least comprising selecting at least (hydroquinone) hydrolyzable decane monomer and (hydrazine) hydrolyzable polycarbon decane. The first liquid of the hydrolyzed (tetra) compound is added to the second liquid containing water and the catalyst, and the step of causing the hydrolyzable money compound to be brought into contact with water is excellent in storage stability and coarseness is suppressed. When the particles are generated, it is possible to obtain a polymer having a small variation in molecular weight and suppressing gelation. The above-mentioned film-forming composition contains the polymer of the group, the organic solvent, and the organic solvent. The molecular enthalpy of the above-mentioned cerium-containing polymer has less variation in the J-knife and has a uniform two-dimensional structure, thereby inhibiting gelation and lowering the electric constant, so

By using the above-mentioned film-forming composition to form a film, a ruthenium film, it is possible to obtain a mechanical strength and excellent typhos resistance, and there is no layer separation in the film, and a low insulating film. And "Electrical constant and hygroscopicity are all described above. The above-mentioned monocrystalline oxide system has a dielectric constant of light water ^ ^ ^ J ′ and is superior in mechanical strength, adhesion and endurance, and no layer separation in the film. [Embodiment] The polymer, the synthetic film thereof, and the method for forming the same, the cerium-containing method, the film-forming composition, and the cerium oxide system according to an embodiment of the present invention will be specifically described below. μ 97104568 10 200848451 ί. The ruthenium-containing polymer and the method for synthesizing the same according to the embodiment of the present invention, the method for synthesizing the ruthenium-containing polymer, from (1) a hydrolyzable residual monomer (hereinafter also referred to as "(1) component") and (8) hydrolyzability Polycarbonate Xi Xuan (hereinafter also referred to as "(8) component")" small) A hydrolyzable decane compound of the first sputum, to the sylvestre u 'added to the water and the catalyst = liquid to make the hydrolysis In the synthesis method of the dream-containing polymer of the embodiment of the present invention, when the compound is hydrolyzed and condensed, # is added to the second liquid, and is complicated. , right dipping, w ώ, liquid T U brother 2 liquid temperature is preferably 40 ° C or more, more than mot. When the temperature of the second liquid is less than (four), the degree of hydrolytic condensation will be low, and there will be a case where the effect of the present invention cannot be sufficiently obtained. In addition, the speed at which the first liquid is added to the second liquid + is different from the concentration of the complex in the liquid of the second liquid and the concentration of the catalyst in the second liquid, but is usually 30 minutes. 10 hours. Specifically, the rate of addition of the hydrolyzable compound per unit of the second liquid amount per unit time is preferably 1×10 −4 〜 lxio′g · min-i · g′ , more preferably 5×10 ～5×10 2 (g · min_i · gi). Once the hydrolyzable money compound is relative! The concentration of the liquid is preferably more preferably 2 to 30% by weight, more preferably 2 to 2% by weight. When the above concentration exceeds 50% by weight or less than 1% by weight, a polymer having a broad molecular weight distribution may be obtained. Further, by using a substrate obtained by using a component of U) and a component as a hydrolyzable compound and performing hydrolytic condensation, a film formation is obtained, and excellent drug resistance and hygroscopicity can be obtained. Low 97104568 11 200848451. The water content of the second liquid is preferably from 5 to 80% by weight, more preferably the possibility that the polymer having a water content of more than 8 Å is precipitated, and the reverse is not obtained by depolymerization obtained by the polymerization. Happening. "At the time of Μ% by weight", the concentration of the catalyst having the second liquid solution is preferably 0.005 to 1% by weight. If the upper and the f are mixed, and the y is 10% by weight, the concentration of the above catalyst is more than 10 When the weight is % and the red is less than .001% by weight, there will be a case where the molecular weight becomes too large: : particles, or the reaction may hardly proceed. The crude solution is a solvent such as an alcohol, which can be used in the first liquid. Specific examples will be described later. The solvent which can be used in the second liquid is preferably a solvent, and it is preferable to use each component of the solvent used in the first liquid. The composition is used in the case of 1 · 1 · ( A) ingredients

The component (A) is preferably selected from the following general formula (1) to (group 矽9 compound; (A) component can be condensed with the compound (8) component to form a heart (four) bond.) Heart or later RaSi(OR1)4.a ······(1) (wherein 'R means a hydrogen atom, an I atom or an organic valence organic group; a means an integer of 1-3.) Ίι

Si(〇R2)4 ······(2) (wherein R2 means a monovalent organic group.) R3b(R40)3-bSi-(R7)d~Si(0R5)3-〇R6c . .....(3) 97104568 12 200848451 [In the formula, 'R~R6 are the same or different, respectively, table * i-valent organic base ^ ′ c are the same or different, table * 〇 ~ 2 value; r7 means An oxygen atom, a phenyl group or a group represented by -(10)2 V (the +, m is an integer of 丄~6); d means 1 °] "the compound of the above general formula (i) which can constitute the component (A) ( Hereinafter, the compound (1), the compound represented by the above formula (2) (hereinafter referred to as "compound 2"), and the compound represented by the above formula (3) (hereinafter referred to as "compound 3") can be used. Display. Among them, the component (A) is preferably a compound and a compound 2, and in this case, the compound i and the compound 2 are used in an amount of the compound 1: compound 2 = 100:0 to 50:50. 1 · 1 · 1 · Compound 1 / Further, in (1), the monovalent organic group represented by R and R1 may, for example, be an alkyl group, a aryl group, an allyl group or a propylene group. Among them, the monovalent organic group represented by R is preferably an alkyl group or a phenyl group. The 'alkyl group can be, for example, a methyl group, an ethyl group, a propyl group or a butyl group, and a good number of slaves can be used. 5> These bases can be chain-like or branched, and can be replaced by hydrogen: It is a fluorine atom or the like. Examples of the aromatic group include a phenyl group, a decyl group, a methyl group, a ethyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Dilute base system = for example: ethylene group, acryl group, 3-butyl group, 3_戍 disaccharide base. Specific examples of the compound 1 include, for example, methyltrimethoxy ketone, methyltriethoxy hydroxy, methyltri-n-propoxy fluorite, shishixixue, methyltri-n-butoxide, and =milk-based velvet Diterpene-fluorene-butane-rolled decane, dimethylbutanyl decane, triphenyloxydecane, ethyltrimethoxy 97104568 13 200848451 decane, ethyltriethoxydecane, ethyltri-n-propoxy decane, Ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, ethyl tri-n-butoxy decane, ethyl tri-tert-butoxy decane, ethyl triphenoxy decane, n-propyl: Trimethoxy decane, n-propyl triethoxy decane, n-propyl tri-n-propoxy, decane, n-propyl triisopropoxy decane, n-propyl tri-n-butoxy decane, n-propyl Second butoxy decane, n-propyl tri-t-butoxy decane, n-propyl triphenoxy decane, isopropyl tridecyloxydecane, isopropyl triethoxy decane, isopropyl tri-n-butyl Propoxy decane, isopropyl triisopropoxy decyl, isopropyl tri-n-butoxy decane, isopropyl tri-n-butoxy decane, isopropyl tri-third Butoxy decane, isopropyl triphenoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-butyl tri-n-propoxy decane, n-butyl triisopropoxy decane , n-butyl tri-n-butoxy decane, n-butyl tri-butoxy decane, n-butyl tri-butoxy decane, n-butyl triphenoxy decane, second butyl tridecyloxy Decane, second butyl triethoxy decane, second butyl tri-n-propoxy decane, second butyl, triisopropoxy decane, second butyl tri-n-butoxy decane, second butyl Three \ ^ second butoxy decane, second butyl tri-tert-butoxy decane, second butyl tri phenoxy zebra, third butyl tridecyl oxy-stone, third butyl triethyl Oxydecane, tert-butyltri-n-propoxydecane, tert-butyltriisopropoxy; decane, t-butyltri-n-butoxydecane, tert-butyltris-tert-butoxydecane, Tert-butyltris-tert-butoxydecane, tert-butyltriphenoxydecane, phenyltrimethoxyoxydecane, phenyltriethoxydecane, phenyltri-n-propoxydecane, phenyl Isopropoxydecane, phenyltri-n-butoxydecane, phenyltri-n-butoxydecane, phenyltri-tert-butoxydecane, phenyl tri-97104568 14 200848451 phenoxydecane, dimethyldiene Methoxy decane, dimethyl diethoxy decane, dimethyl di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimercapto 2 Butoxy decane, dimercapto 'di-t-butoxy decane, dinonyldiphenoxydecane, diethyldioxime, hydrazine, diethyldiethoxy oxime, diethyl Di-n-propoxy decane, diethyldiisopropoxy chopping, diethyldi-n-butoxy pulverization, diethyldi-butoxybutane, diethyldi-t-butoxydecane , diethyldiphenoxydecane, di-n-propyldimethoxydecane, di-n-propyldiethoxy decane, di-n-propyldi-n-propoxy decane, di-n-propyldiisopropyloxide Base decane, di-n-propyldi-n-butoxy decane, di-n-propyldi-second butoxy decane, di-n-propyldi-t-butoxy decane, di-n-propyldiphenoxydecane, Isopropyl dimethoxy decane, diisopropyl diethoxy decane, diisopropyl di-n-propoxy decane, diisopropyl diisopropoxy decane, diisopropyl di-n-butoxy Decane, diisopropyldi-2-butoxydecane, diisopropyldibutoxybutane, diisopropyldiphenoxydecane, di-n-butyl-dimethoxydecane, di-n-butyl Diethoxy decane, di-n-butyl di-n-propoxy oxazepine, di-n-butyl diisopropoxy zebra, di-n-butyl di-n-butoxy decane, di-n-butyl bis-second Oxydecane, di-n-butyldi-tert-butoxydecane, di-n-butyldiphenoxydecane, di-tert-butyldimethoxyoxydecane, di-tert-butyldiethoxydecane, dip Dibutyldi-n-propoxy decane, di-second butyl diisopropoxy decane, di-second butyl di-n-butoxy decane, di-second butyl di-butoxy decane, second Butyl di-butoxy decane, di-tert-butyl diphenoxy decane, di-t-butyl dimethoxy decane, di-t-butyl diethoxy decane, di-tert-butyl two 97104568 15 200848451 n-propoxy oxazepine, di-tert-butyl-iso-propoxy oxalate, di-tert-butyl = butyl-based I, di-t-butyldi- 2,2-butoxy, and second: two? Tributoxy decane, di-tert-butyldiphenoxydecane, diphenyldioxy-7, diphenyldiethoxy #烧, diphenyldi-n-propoxy-2-phenyl-isopropyl Oxygen zephyr, diphenyldi-n-butoxy oxalate, diphenyldi-second butoxy decane, diphenyldi-t-butoxybutylidene-based diphenoxylate. These may be used alone or in combination of two or more. The special compound of corpse 2:1 may, for example, be methyltrimethoxy quinone dioxime: tert-butyl sulphate, methyl tri-n-propoxy sulphate, methyl triisoethyltrimethoxy Base stone simmering, ethyl triethoxy sulphur, benzene,: A = money, phenyl triethoxy money, dimethyl dimethoxyethane = bis-diethoxy sulphur, diethyl dimethoxy The base stone Xixuan, the diethyl di-n=yuan, the phenyl dimethoxy zebao, the diphenyl diethoxy shi shi, the 4 series can be used alone or in combination of two or more. 1 1· 2·Compound 2 In the above general formula (2), the monovalent 嫱 π gamma of R 2 is represented by the same group as R and R 1 of the formula (1). + For example, specific examples of the above-mentioned chemical substance 2 include, for example, tetramethoxy money, tetrakis stone garden, tetra-n-propoxy zephyr, tetraisopropoxy zebra, tetra-n-butoxy group, and the like. Examples of the tetrabutoxy (tetra), tetra-t-butoxy-alkaline, and tetraphenoxy 2 bis compounds include tetramethoxy zebra and tetraethyl ketone. These may be used alone or in combination of two types to 97104568. The ones exemplified in R1 are the same base. • In the general formula (3), the compound 3 in which d=0 is exemplified by hexamethoxy-dioxane, hexaethoxydioxane, hexaphenoxydioxane, and 2-pentamethoxy-2. -methyldioxane, 1,1,1,2,2-pentaethoxy-2-methyldioxane, 1,1,1,2,2,5-pentaoxy-2-indenyldioxane, Ll J 2 2-pentamethoxy-2-ethyldioxane, 1,1,1,2,2-pentaethoxy-2-ethylidene, 1,1,1,2, 2- Pentaphenoxy-2-ethyldioxane, lij 2 2 -pentamethoxy-2-phenyldioxane, 1,M,2, 2,5-ethoxy-2-phenylene chopped, 1 1,1'2,2-penta-oxy-2-phenyldicarbonate, 1 1 2 2-tetradecyloxy-1,2-dimercaptodioxane, 1,1,2, 2- Tetraethoxy-!, 2, 2-indenyl group, a chopping, -tetraphenoxy-1,2-diindenyl, 2,1,2,2-tetramethoxy-1,2 -diethyldioxane, lu,2-tetraethoxy-1,2-diethyl-anthracene, 1,1,2,2-tetraphenoxyl,2-diethyldi(, Shi Xizhuo, 1,1,2,2-tetradecyloxy~1,2-diphenyl bismuth, i,i,2,2-tetraethoxy-1,2 a base ^ One second burn, 1,1,2,2-tetraphenoxy-1,2-diphenyldioxane, 1,1,2-trimethoxy-1,2,2-trimethyldioxane, 1 , 1,2-triethoxy-1,2,2-trimethyldioxane, ι,ι,2-triphenyloxy•-1,2,2-dimethyl-cyan, 1,1 ,2-trimethoxy-;[,2,2-triethyl bismuth, 1,1,2-diethoxy_1,2,2-triethyl bismuth, 1,1 ,2-triphenoxy-1,2,2-triethyldioxane, i 1, trimethoxy-1,2,2-triphenyldioxane, 1,1,2-triethoxy- 1,2, triphenyldioxane, 1,1,2-triphenoxy-1,2,2-triphenyldioxane, 1,2-dimethoxy 97104568 17 200848451 -1,1' 2, 2-tetradecyldioxane q'2-diethoxytetramethyl-decane, 1,2-diphenoxy-;, L 2, 2-tetradecyldioxane, I 2_ II曱oxy-1,1,2,2-tetraethyl bismuth, 1>2, diethoxy", ^2-tetraethyl-stone, 1,2-diphenoxy- , I 2, 2 -tetraethyl oxalate, 1,2-monomethoxy-; [, l 2, 2 - tetraphenyl dioxane, l 2 - diethoxy-1, 1, 2 , 2-tetraphenyl dioxane, 1 2_Diphenyl gas group_1, 1,22_tetraphenyldioxane, etc. Among these, it is preferably, for example, hexamethoxydioxane or hexaethoxydioxane: U, 2, 2- Tetramethoxy-1,2-dimercaptodioxane, 1,1,2,2-tetraethoxy-1,2-dimethyldioxane; [,12,2-tetramethoxy- I 〗 〖 笨 矽 矽 矽 、, 1,2 曱 曱 曱 ;; [, kg, 2, 4-tetradecyldioxane, 1,2-ethoxyl-, ι, 2, 2-tetra Dioxadecane, l 2 -dioxyloxy 1,1,2,2-tetraphenyldioxane, 1,2-diethoxy-u, 2, tetraphenyl-cracked, and the like. Further, in the general formula (3), the compound 3 of d = 1 may, for example, be bis(trimethoxydecyl)decane, bis(triethoxydecyl)decane or bis(tri-n-propyl) Oxyalkylene) decane, bis(triisopropoxydecyl)methane, bis(tri-n-butoxydecyl)decane, bis(tri-t-butoxydecyl)decane, bis (two) Tertiary butoxyalkyl)methane, 1,2-bis(trimethoxydecylalkyl) • phenylene, anthracene, 2-bis(triethoxydecyl)ethane, 1,2-double (three N-propoxy: fluorenyl) ethane, 1,2-bis(triisopropoxydecyl)ethane, hydrazine, 2-bis(tri-n-butoxydecyl)ethane, 12-bis (three Second butoxyalkylalkyl)ethane, 1,2-bis(tris-tert-butoxydecyl)ethane, iododimethoxycarbazide-1 -(trimethoxy-stone) )Methyl, 1-(diethoxymethyl 97104568 18 200848451 decyl)-1-(triethoxydecyl)decane, 1-(di-n-propoxymethylcarbazide-(tri-n-propyl) Oxygen-based sulphur-based, 1-(diisopropoxy oxetane -1 -(triisopropoxydecyl)methane, 1-(di-n-butoxymethylcarbazide:alkyl)_1 -(tri-n-butoxydecylalkyl)decane, 1-(second second Butoxy-alkyl-alkyl)-1-(di-di-butoxy-oxanyl)-methyl, 1-(di-t-butoxy-methoxyalkyl)-1 -(tris-tert-butoxyalkyl) ) decane, 1-(dimethoxycarbamoyl)-2-(trimethoxydecyl)ethane, 1 (diethoxymethyl decyl)-2-(diethoxy chopping) Ethyl bromide, 1-(di-n-propoxy oxindole (alkyl)-2-(tri-n-propoxy oxalate)-ethyl bromide, 1-(diisopropoxydecyl)-2- (triisopropoxydecyl)ethane, i-(di-n-butoxymethylcarbenyl)-2-(tri-n-butoxyfluorenyl)ethane, ι-(di-second butoxide Benzyl hydrazino)-2-(tris-2-butoxy decyl)ethane, iota-(di-t-butoxy decyl)-2-(tri-tert-butoxy decyl) ethane , bis(dimethoxycarbinyl)methane, bis(diethoxydecyl)methane, bis(di-n-propoxymethyl decyl)methane, bis ( Isopropoxymethyl sulfonyl)methane, G bis(di-n-butoxymethyl decyl)methane, bis(di-butoxycarbonylmethyl)methane, bis(di-t-butoxymethyl decyl) Methane, bis(dimethoxycarbinyl)ethane, 1,2-bis(diethoxycarbamido)ethane, 1,2-bis(di-n-propoxymethylcarbenyl) Ethane, I?-le-carbyl)ethane, hydrazine, 2-bis(di-n-butoxymethyl decyl)ethane, 1,2 -; bis(a second butoxymethyl decyl) Ethane, 1,2-bis(di-t-butoxycarbenyl)ethane, 1,2-bis(trimethoxydecyl)benzene, anthracene, 2-bis(2-ethoxydecyl)benzene , 丨, 2 - bis(tri-n-propoxy decyl) benzene, hydrazine, 2 bis (triisopropoxy oxymethylene) benzene, U-bis (tri-n-butoxy decyl) 97104568 19 200848451 1,2-bis(tris-2-butoxydecyl)benzene, anthracene, 2-bis(tris-tert-butoxyalkyl)benzene, anthracene, 3-bis(tridecyloxydecyl)benzene,丨, 3 - bis (triethoxy decyl) benzene, hydrazine, 3 - double (three positive Benzene, hydrazine, bis (triisopropoxy decyl) benzene, 1,3-bis(tri-n-butoxy decyl) benzene, hydrazine, 3-bis (three second butoxide) Base alkyl)benzene, 1,3-bis(tris-tert-butoxyalkyl)benzene, anthracene, 4-bis(trimethoxyoxyalkyl)benzene, anthracene, 4-bis(triethoxydecylalkyl) Benzene, anthracene, 4-bis(tri-n-propoxydecyl)benzene, anthracene, 4-bis(triisopropoxydecyl)benzene, anthracene, 4-bis(tri-n-butoxydecyl)benzene , 1,4-bis(tris-2-butoxyalkyl)benzene, anthracene, 4-bis(tris-tert-butoxyalkyl)benzene, and the like. Among the preferred examples are: bis(trimethoxydecylalkyl)decane, bis(diethoxydecyl)decane, 1,2-bis(tridecyloxydecyl)ethane, 1,2 bis(diethoxy sulphide) ethene, 1 (dimethoxy phthalocyanine)-1 - (trimethoxy decyl) decane, 1 - (diethoxy)曱矽alkyl)-1 -(diethoxy oxalate) oxime, 1 (dimethoxy oxime oxime I; base) 1-2 (dimethoxy oxime), E-burning, 1 -(diethoxysulfonyl)-2-(diethoxydecyl)ethane, bis(dimethoxydecylalkyl) oxime, bis(diethoxymethylcarbazide) Strontium, 1,2-bis(dimethoxymethylhydrazine) ethane, 1,2-bis(diethoxydecyl)ethane, hydrazine, 2 bis: (dimethoxy sulphur Burning base) benzene, 1,2-bis(triethoxy sulphur) benzene, 1,3-: bis (dimethoxy sulphur) benzene, 1,3-bis (triethoxy oxime) Base) benzene, 1,4-bis(trimethoxydecyl)benzene, iota, bis(triethoxydecyl)benzene, and the like. The above compound 3 may be used singly or in combination of two or more. 97104568 20 200848451 L 2. (B) Component As described above, the component (B) is a hydrolyzable polycarbene. The component (B) is π, +, . . . Ν 聚 A polycarbodecane compound having the structural unit represented by the following general formula (4) (hereinafter referred to as "compound 4"). [Chemical 2]

(4) f (wherein, R8 is the choice of pendulum white _ shop ν ^ selected from cesium atom, halogen atom, hydroxyl group, alkoxy group, milk base, sulphuric acid base, stone to the lack of #丰八虹暴甲石a group consisting of only an acid group, a trisyl methanesulfonate group, a pyridyl group, an aromatic di-allyl group, and a glycidyl group; r9 means a selected atom, a hydroxyl group, an alkoxy group, a hydrazine group, and an acid group. Burning base, aroma:: C:", acid group, trifluoro group; η" is the same ^ s gas propyl group formed ', ask or mutually different, indicating that selected from halogen atom, hydroxyl group, alkoxy group, a group of a decyloxy group, a fluorene group of a fluorenyl group, an aromatic dipropylamine, a fluoromethyl acid group, a group of carbon; a group of the same m% of an epoxy group; the same or different, indicating a substitution Or unsubstituted methylene, exudyl, dilute base, exudate base finger 〇~ι〇, _ value, and, u ^ square base, xy, z are respectively 卜, 十, 一如如足5<x+y+z<i〇, _ condition.) In the above formula (4), R8~r11# - 4 = atom, chlorine atom, and disulfide: the tooth atom system may be, for example, fluorocarbon Oxyl, ethoxy, propoxy, Oxyl group, etc., thiol group: For example: 丞 丞 κ 〜 R 所 醯 97 97104568 200848451 exemplified by: ethoxylated, propyloxy, etc., r8~r11 Examples of the aromatic group represented by a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a cyclohexyl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, and a bromine group. Phenyl, fluorophenyl, etc. Further, in the above general formula (4), the alkylene group may, for example, be an ethyl group, a propyl group, a butyl group, a hexyl group or a sulfonyl group. Preferably, the carbon number is 2-6, and the stretching bases may be chain-shaped or branched, and more may form a ring, and may also utilize a hydrogen atom such as a gas atom, a chlorine atom, an atom, a moth atom. The halogen atom is substituted, and the alkenyl group represented by r^rh may, for example, be a linear or branched alkenyl group having a carbon number of 2 to 6 (preferably 1 to 4), for example, a vinyl group or a vinyl group. Dilute, butenyl, pentenyl, b-based, methyl-propenyl, 2-methyl-propenyl, methyl-pentenyl, 3-methyl-p-pentenyl Vinyl, B a propylene group, a propyl ethyl butyl group, a 3-ethyl butyl group, etc. The hydrogen atoms in the above-mentioned stretching groups may also be substituted with a _ atom such as a fluorine atom, a (tetra), a (tetra), a ruthenium atom or the like. The m-extended alkynyl group may, for example, be a linear or branched exfoliating group having a carbon number of 2 to 4, for example, a stretching group, a stretching group, a 1-butenyl group. , 卜伸戊块基,卜伸己块基, 2—buttydinyl, 2-exetylene group, benzyl group, 3 methyl group, 3-methyl group Butyl group, etc. The chlorine atom in the extended block group may also be substituted by a tooth atom such as a fluorine atom, a chlorine atom, a hydrazine atom, a filled atom, etc. The aryl group represented by R12 to R14 may, for example, be a benzene extending benzene. The chlorine atom can also be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a molybdenum atom.卞寺 97104568 22 200848451 Furthermore, in the above general formula (4), χ, y, z are 〇~1〇, the value of 〇〇〇, and 5<x+y + z<1 0,000. When x+y + z<uf, there will be a case where the polymer has poor storage stability. On the contrary, when 1〇, 〇〇〇<x+y+z, the obtained polymer will undergo layer separation phenomenon. membrane. Preferably, X, 乂, and z are respectively 〇$x$8〇〇, 〇gy^5〇〇, 〇^d, 〇〇〇, preferably ο

Sx$ 500, 〇^y^3〇〇, 0$zg 500, and even better 〇^χ^ι〇〇, 0$y$50, osdoo 〇

Further, in the above general formula (4), preferably 5 < x + y + z < 5 〇〇, more preferably < 100 〇, preferably 5 < x + y + z < 1, 〇〇〇, more 5 < X + y + z < 250 'Special 5 < x + y + z Compound 4 can be selected from, for example, chloromethyltrichloromethane, methane methyl, gas stone, gas, f-methyl, chlorine , chloro-f-ethyl chlorite, chloromethyl vinyl dichloride, chloromethyl phenyl diethylene, bromomethyl methyl dichloromethane, ethylene dichloride, chloromethyl曱 氯 氯 夕 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Chloromethyltrimethoxydecane, bromomethyltrimethoxydecane, chloromethylmethyldimethoxysulfonium, milk methylethylenedimethoxycarbazide, chlorof-phenyl phenyldimethoxylate Xishao, Mo Methyl-Dimethoxy-I, Mo-methylvinyldimethoxy-naphthene, Bromomethylphenyldimethoxydecane, Chloromethyldimethylmethoxydecane, Milk Armor Divinyl methoxy decane, chloromethyl diphenyl methoxy hydrazine ,? Methyl dimethyl methoxy decane, methylene methyl diisopropyl methoxy oxime, hydrazine methyl triethoxy (tetra), methyl triethoxy stone, chloromethyl methyl ethoxylate Xishou, chloromethylethyl: ethoxylate, chloromethyl B 97104568 23 200848451 = bis ethoxy money, chloromethyl phenyl diethoxy money, bromomethyl methyl - B , methyl methyl diphenyl diethoxy money, bromomethyl benzoquinone B: keshi Xizhuo, chloromethyl dimethyl ethoxylate, chloromethyl diethoxy sulphur, / stinking methyl At least one compound of divinyl ethoxy oxime, chloromethyl triisopropoxy ketone, and methyl triisopropoxy zebra, at least one of the metal and the soil of the soil tester The anti-j' can be obtained by using an alcohol, an organic acid, a reducing agent or the like as needed. (B: The weight average molecular weight of the component is preferably 3 〇〇 1 〇〇, _, especially preferably / 00. If the weight average molecular weight of the component (B) is larger than the range, the raw silk is easily made and the fine is cut. The pores inside the diemulsified (tetra) oxime formed by the polymer tend to become too large, so it is preferable to avoid the use amount of the component (B) and the component (B). The synthesis method +, the first liquid hydrolysis (four) fired compound preferably contains the components (A) and (8). In this case, the mixing ratio of the component (A) to the component (B) is a complete hydrolysis of the component (8). The content of 1 〇 0 is 1 part by weight, preferably (A) is 1 to 1000 parts by weight, more preferably 5 to 2 parts by weight, and even more preferably 5 to 1 part by weight. If (a) component ^ When the 1st rereading is completed, 'there will be no sufficient resistance after the film formation. The other way, if it exceeds 丨_parts by weight, the film may not reach the low dielectric constant of the film. 1· 4. (C) Catalyst (C) The catalyst is contained in the second liquid. (6) The catalyst is preferably at least one of the compounds, the acidic compound, and the metal chelate compound. One type of compound is selected. 1·4·1· Metal Chelate Compound The metal chelate compound which is (C) catalyst can be used as shown in the following general formula (6) • R15eM(〇R16)fe ··· (6) (wherein R15 means a chelating agent; lanthanum means a metal atom; R16 means an alkyl group or an aryl group; f means the valence of the metal M; and e means an integer of 1 to f 〇 Wherein the 'metal ruthenium is preferably at least one metal selected from the group ππβ group metals (aluminum, gallium, indium, antimony) and the Group IVA metal (titanium, zirconium, hafnium), especially titanium, aluminum, and antimony. Further, the alkyl group or the aromatic group shown may, for example, be an alkyl group or an aromatic group represented by Ri in the above general formula (丨).

Specific examples of the metal chelate compound include, for example, triethoxyl mono(ethylidene propyl g) titanium, tri-n-propoxy-mono(ethyl acetonide), triisopropoxy: (Ethyl acetonide) Titanium, Tri-n-butoxy-mono(ethenylacetone) Titanium, Tri-tert-butoxy-mono(ethinylacetone) Titanium, Tri-tert-butoxy-Single Base, g, and titanium, diethoxy, bis(ethyl fluorenyl), n-propoxy, bis (ethyl "acetone" titanium, diisopropoxy bis (acetyl) acetonide , di-n-butoxy bis(acetylidene acetonide) titanium, two second butoxy ί (b, propyl acetonide) titanium, - third butoxy bis (ethinyl acetonide, early ethoxylate) · ginseng (acetonitrile) titanium, mono-n-propoxy-sodium (ethenyl propyl hydrazine) titanium, monoisopropoxy ginseng (acetyl acetonide) titanium, mono-n-butoxy ginseng (B醯 丙酮 ) ) 钛 辈 辈 辈 早 早 早 早 早 早 早 早 早 早 早 早 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 97 Acetylacetone) titanium, diethoxy; early ( Ethyl ethyl acetate acetic acid), tri-n-propoxy-single (ethyl acetoacetate) titanium, triisopropoxy-mono (ethyl acetoacetate) titanium, tri-n-butoxy • mono (ethyl Acetate acetic acid) titanium, tri-tert-butoxy-mono(ethylacetamidineacetic acid) titanium, tri-tert-butoxy-mono(ethylacetamidineacetic acid) titanium, diethoxy-bis (ethyl ethyl)醯Acetic acid) Titanium, di-n-propoxy-oxy-bis(ethyl acetoacetate) titanium, diisopropoxy bis (ethyl acetonitrile) titanium, di-n-butoxy bis (ethyl acetamidine acetate) Titanium, di-butoxide, bis(ethylethyl c-acetate) titanium, di-t-butoxy-bis(ethylacetamidineacetic acid) titanium, monoethoxy-tris(ethylacetamidineacetic acid) Titanium, mono-n-propoxy-parameter (ethyl acetoacetate) titanium, monoisopropoxy ginseng (ethyl acetoacetate) titanium, mono-n-butoxy-tea (ethyl acetoacetate) titanium , mono-second butoxy ginseng (ethyl acetoacetate) titanium, mono-tert-butoxy ginseng (ethyl acetoacetate) titanium, decyl acetonitrile acetic acid) titanium, single (ethyl fluorenyl)甲纲) ginseng (ethyl ethyl acetate) , bis(ethyl decyl acetonide) bis (ethyl acetamidine acetate) titanium, ginseng (acetyl acetonide) G early (ethyl acetoacetate) titanium and other titanium chelating compounds; triethoxy fluorenylacetone) , tri-n-propoxy-mono (ethyl acetoacetate), tri-propyl propyl acetonitrile, zirconium, tri-n-butoxy-mono(ethenylacetone) ^ dibutoxy • single Acetone)|#, three third butoxy group (Ethyl hydrazine & propyl propyl) is wrong, - hexyl hydrazine | - ethyl hydrazine / bis (acetyl ketone) wrong, two positive sheep soil · again ( Ethyl acetonide) bismuth, diiso ketone) zirconium, di-n-butyl sulphide 雔 雔 ( ο ο ο 暴 暴 暴 暴 又 又 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ,二箆二#土m . A ., —Didi-diyl bis(ethyl decyl acetonide) 早, 早乙虱基•参(乙醯 acetone)鍅, 早正丙虱基•芩(乙醯基97104568 26 200848451 Acetone) oxime, monoisopropoxy oxy-x (acetamidacetone), mono-n-butoxy-anhydroacetic acid) hydrazine, mono-second butoxy-glycolate , • butyloxy• ginseng (acetoxime)鍅, 肆 (acetonitrile), ethoxy, mono (ethyl acetamidine acetate), tri-n-propoxy--acetamidine acetate, zirconium, Sanli and Tongqi · Ganzao (ethyl hydrazine) - a propyl milk mono (ethyl ethyl hydrazine acetate) hydrazine, tri-n-oxide mono (ethyl acetate acetic acid) wrong, three second butoxy • single (ethyl acetate) acetate, three third oxygen Base · monoethyl acetate (acetic acid acetate),: p = lactyl • bis(ethyl acetamidineacetate) hydrazine, di-n-propoxy bis (ethyl ethyl hydrazine), diisopropoxy Bis(ethylacetamidineacetic acid) zirconium, di-n-butoxy-bis(ethylacetamidineacetic acid) zirconium, two second butoxy-bis(ethyl b, 酉B酉夂), two third Oxy-bis(ethylacetamidineacetic acid), monoethoxy, ginseng (ethylacetamidineacetic acid), mono-n-propoxy, ginseng (ethyl acetoacetate), monoisopropoxy ((ethylacetamidineacetic acid) hydrazine, mono-n-butoxy-para (ethyl acetoacetate) hydrazine, mono-second butoxy-para (ethyl acetoacetate), mono-butadiene Base ginseng (ethyl acetoacetate) wrong, 肆 (B乙乙ga酉文), singly, succinylacetone, succinate (ethyl acetate), ^, ^ (ethylidene acetonide) bis(ethyl acetamidineacetate), ginseng (ethyl hydrazide) Zirconium chelate compound such as (ethylacetamidineacetic acid) ruthenium; triethoxyl mono(ethyl decyl acetonide) aluminum, tri-n-propoxy oxy-mono(ethenyl propylamine) aluminum, triisopropyl acrylate = Single (acetamidacetone) aluminum, tri-n-butoxy-mono(ethenylacetone) aluminum, two second butoxy-mono(ethylideneacetone) aluminum, three third butoxy group (b) Mercaptoacetone) aluminum, diethoxy bis(acetic acetone) aluminum, di-n-propoxy bis(ethyl decyl acetonide) aluminum, diisopropoxy bis (ethyl fluorenyl propyl) a n-butoxy bis(ethyl decyl acetonide), a second butyloxy group 97104568 27 200848451 bis(ethyl decyl acetonate) aluminum, two third butoxy bis (ethyl decyl acetonide ) aluminum, Monoethoxy, ginseng (acetonitrile) aluminum, mono-n-propoxy-x (acetamidacetone) aluminum, monoisopropoxy ginseng (acetonitrile) aluminum, mono-n-butoxy Ginseng (acetylacetone) Aluminum, mono-second butoxy-glycol (acetonitrile) aluminum, • mono-second butoxy • ginseng (acetoxime), 肆 (醯 醯 propyl g) with the second, Ming Oxygen mono (ethyl acetamidine acetate), tri-n-propoxy-single (ethyl acetoacetate) aluminum, triisopropoxy-mono (ethyl acetoacetate) aluminum, tri-n-butoxy • Single (ethyl acetoacetate) aluminum, three second butoxy • mono (ethyl f acetonitrile) aluminum, tri-tert-butoxy • mono(ethyl acetonitrile) aluminum, diethoxy • bis (ethyl acetamidine acetate) 1 ly, di-n-propoxy bis (ethyl acetonitrile) aluminum, diisopropoxy bis (ethyl acetonitrile) aluminum, di-n-butoxy Bis(ethylacetamidineacetate)aluminum,di-second-butoxy-bis(ethylacetate acetate),di-tert-butoxy-bis(ethyl b-acetate)aluminum, monoethoxyl-parameter Ethylacetamidineacetic acid)aluminum, mono-n-propoxy-oxyl (ethyl ethyl acetonitrile), aluminum, monoisopropoxy, ginseng (ethyl acetoacetate), aluminum, mono-n-butoxy-indenyl Ethyl acetate, aluminum, single-second Base ginseng (ethyl acetoacetate) aluminum, mono-tert-butoxy ginseng (ethyl acetoacetate) aluminum, lanthanum (ethyl acetoacetate) aluminum, mono (ethyl acetonide) ginseng (B Acetylacetate, aluminum, bis(ethylideneacetone) bis(ethylacetamidineacetic acid)aluminum, ginseng (acetamidoacetone): aluminum chelate compound such as mono(ethylacetamethyleneacetate)aluminum, etc. Species or 2 in particular for use such as: (CH3(CH3)HC0)4-tTi(CH3C0CH2C0CH3)t, (CH3(CH3)HC0)4-tTi(CH3C0CH2C00C2H5)t > (C4H9〇)4-tTi(CH3COCH2COCH3 ) t ^ (C4H90)4-tTi(CH3C0CH2C00C2H5)t, (C2H5(CH3)C0)Wri(CH3C0CH2C0CH3)t, 97104568 28 200848451 (C2H5(CH3)C0)4-tTi(CH3C0CH2C00C2H5)t > (CH3(CH3) HC0)4-tZr(CH3C0CH2C0CH3)t > (CH3(CH3)HC0)4-tZr(CH3C0CH2C00C2H5)t, (C4H90)4-tZr(CH3C0CH2C0CH3)t, (C4H90)4tZr(CH3C0CH2C00C2H5)t, (C2H5( CH3)C0)4-tZr(CH3C0CH2C0CH3)t,6(C2H5(CH3)CO)4-tZr(CH3COCH2COOC2H5)t > (CH3(CH3)HC0)3-tAl(CH3C0CH2C0CH3)t ^ , (CH3(CH3) HC0)3-tAl(CH3C0CH2C00C2H5)t > (C4H9〇)3-tAl(CH3COCH2COCH3)t ^ (C4H90)3-tAl(CH3C0CH2C00C2H5)t, C2H5 (CH3) C0) 3-tAl (CH3C0CH2C0CH3) t, (C2H5 (CH3) C0) 3 tAl (CH3C0CH2C00C2H5) t like or two or more species of the metal chelate compound is preferred. The amount of the metal chelating compound is from 0.0001 to 10 parts by weight, preferably from 0.000 to 5 parts by weight, based on 100 parts by weight of the total amount of the hydrolyzable decane compound (in terms of the total hydrolysis condensate). When the ratio of use of the metal chelate compound is less than 0.0001 part by weight, the coating property may be poor. On the other hand, if it exceeds 10 parts by weight, the polymer may not be controlled to grow and gelation may occur. 5〜20摩尔的水,特别添加1~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ 10 moles of water is better. If the amount of water added is less than 0.5 mol, there will be a case where the hydrolysis reaction is not sufficiently carried out, and the coating property and the storage stability are problematic. On the contrary, if it exceeds 20 mol, there will be a hydrolysis and condensation reaction. In the case where polymer precipitation or gelation occurs. In addition, the water is preferably added in a batch or continuous manner. 1.4. 2. Acidic compound The acidic compound which can be used as the (C) catalyst can be exemplified by an organic acid or an inorganic acid, preferably an organic acid. Examples of the organic acid include acetic acid, propionic acid, 97104568 29 200848451 butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, and Diacid, azelaic acid, gallic acid, butyl acid, benzoic acid, peanut oleic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, water yang Acid, benzoic acid, p_amino benzoic acid, P-toluene, benzoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, tartaric acid , citric acid, antibutanic acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, pentanoic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, The hydrolyzate of glutarylene, the hydrolyzate of maleic anhydride, and the hydrolyzate of phthalic anhydride. The first inorganic acid may be, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphorus, or From the viewpoint of less precipitation of the polymer in the condensation reaction and less threat of coagulation, it is preferably an organic acid, particularly a compound having a carboxyl group, and more preferably Acetic acid, ¥ acid, cis acid, malonic acid, acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, j-glycolic acid, glutaric acid, butylene The organic S such as the hydrolyzate of the dianhydride is 4 inches long. These systems may be used alone or in combination of two or more. The amount of the hydrazine acidic compound used is 100 parts by weight based on the total amount of the hydrolyzable decane compound (in terms of the total hydrolysis condensate), and is used in the case of • 0001 1 0 parts by weight, preferably 5 parts by weight. When the acidic compound is used in an amount of 00 parts by weight based on the total amount of the hydrolyzable decane compound, less than 0/0001 parts by weight, the coating property may be poor, and if it exceeds 10 parts by 1 part, the hydrolysis condensation reaction will be The case of gelation occurs when it is rushed. 97104568 30 200848451 In the presence of acidic compounds in the presence of τ, when the hydrolysis is condensed, 'preferably relative to the hydrolyzable dream compound total ffc:= 亍hydrolyzed 〇· 5~20 moles of waves, I heart and mother 1 molar use of added water Less than OB: 1~1 〇 Moer's water is better. If the added material does not ride 5 materials, there will be a case where the hydrolysis reaction is not _ dimorphism and storage stability will occur. On the contrary, J super: 〇 4 ears, there will be in the hydrolysis and condensation reaction. In addition, the water is preferably in a batch or continuous manner;; the addition of the substance, the gel 1·4·3·the test compound ▲ can be used as the basic compound of the (C) catalyst, for example, a sub-amine, a propanolamine Butanolamine, N-methylmethanolamine, N_propylpropylmethanolamine, N-butylmethanolamine, "ethanolamine=ethylamine ethanol, hydrazine-propylethanolamine, hydrazine-butylethanolamine, ethethylethyl Propylamine, Ν-propylpropanolamine, Ν_丁: propyl = butylbutanyl butanolamine, di-St-methylmethanolamine, N,N-diethylmethanolamine, N,N-dipropyl Methanolamine, N-butyl butyl methoxide, N, bis dimethylethanolamine, & n-diamine, n, n-dipropylethanolamine, N,N-dibutylethanolamine ==A, N-Guang-Diethylpropanolamine Rudipropylpropanolamine: Di-n-butyl-propyl-propyl female, N,N-dimethylbutanolamine, NN-dipropylbutanolamine, u-two Butyl butanolamine, diamine, N-ethyldi-folamine, N-propyldimethanolamine, n-butyldi-N-methyldiethanolamine, n-ethyldiethanolamine, (tetra)diethanolamine , butyl diethanolamine, " bispropanolamine, N-ethyldipropanolamine, N_propyl Dipropanolamine, N-butyldipropanolamine, " butylbutanolamine, ^ 97104568 31 200848451 ethyl dibutanolamine, propyl dibutanolamine, N_ butyl butanolamine, N- (Aminomethyl)methanolamine, N-(aminomethyl)ethanolamine, N-(aminomethyl)propanolamine, N-(aminomethyl)butanolamine, N-(aminoethyl) Methanolamine, N-(amine §ethylethyl)ethanolamine, N-(aminoethyl)propanolamine, N-(aminoethyl)butyl, alcoholamine, N-(aminopropyl)methanolamine , N-(Aminopropyl)ethanolamine, N-(Aminopropyl)propanolamine, N-(Aminopropyl)butanolamine, N-(Aminobutyl)methanolamine, N-(Amine Butyl)ethanolamine, N-(aminobutyl)propanolamine, N-(aminobutyl)butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxy Butylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butyl Oxymethylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine, decylamine, ethylamine, propylamine, butylamine, N, N Indoleamine, N,N-diethylamine, N,N-dipropylamine, n,N-dibutylamine, tridecylamine, triethylamine, tripropylamine, dibutylamine, tetraammonium hydroxide, hydrogen hydroxide Ethylammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetradecylethylenediamine, tetraethylethylenediamine, tetrapropylethyldiamine, tetrabutylethylenediamine, mercaptoaminemethylamine , methylaminoethylamine, mercaptoamine propylamine, mercaptoamine butylamine, ethylaminoguanamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, propyl Aminoguanamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminoguanamine, • butylaminoethylamine, butylaminopropylamine, butylamino Butylamine, pyridine, pyridinium; argon, piperazine, pyrrolidine, piperidine, mercaptopyridine, morpholine, decylmorpholine, diazabicyclooctane, diazabicyclononane, diazabicyclolaurite , ammonia, sodium hydroxide, hydroxide, barium hydroxide, barium hydroxide, etc. The basic compound is particularly preferably a nitrogen-containing compound represented by the following general formula (5) (also referred to as "compound 5" under 97104568 32 200848451). (X 丨X2X3X4N)gY (5) In the above general formula (5), χ1, χ2, χ3, χ4__ represent a non-deuterium atom, a carbon number of 20, and preferably a base group, an ethyl group, and a propyl group. 3 is preferably an ethyl group, an aromatic group (most ~: two 4), a quaternary alkyl group (preferably a phenylmethyl group, etc.); a γ system means a tooth atom = a fluorine atom, a chlorine atom, a desert atom, Impeding atoms, etc.), the ionic group of valence (preferably hydroxyl, etc.); g means! An integer of ~4. Specific examples of the π 5 are, for example, tetramethylammonium hydroxide tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, tetra-n-butylammonium hydride, Tetraisobutyl hydride, tetrahydric hydroxide tetradecyl, =: ammonium, tetrahexammonium hydroxide, tetraheptyl ammonium hydroxide, tetrahydric hydroxide -: Μ Μ #四壬钱' A oxidized fourteen burning Ammonium, tetra(thyl) hydroxide, tetra(didecyl)ammonium hydroxide, evolution of four armor, chlorination of four f, evolution of four E money, chlorination of four Ethyl, desertification of four positive Ammonium, chlorinated=propylammonium", stinky tetra-n-butyl, chlorinated tetra-n-butyl, hexadecyl-chloroammonium chloride, evolution of the sixteen-burning base, three gas recording, gas oxidation, N-octadecyltrimethylammonium monobromide, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, chlorinated thallium trimethyl hydrazine, dimercapto dimethyl chlorinated, hard Fatty dimethyl ammonium chloride, tridecyl chlorohydrin, tetrabutylammonium hydrogen sulfate, desertified tributylmethylammonium chloride, trioctylmethylammonium chloride, trilaurate chlorohydrin, hydroxide base Trimethylammonium, desertification Ethylammonium, desertified stilbene dibutylammonium bromide, phenyltriammonium bromide, choline, etc. Among these, particularly preferred are: tetraammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butyl hydroxide Ammonium, 97104568 33 200848451 Tetra-n-butylammonium chloride, tetraethylammonium bromide, tetra-n-propylammonium bromide, tetraammonium bromide, tetraethylammonium bromide, can be used alone, or can be used N-propylammonium. The compound 5 can be used in two or more types. The amount of the test compound used is based on the total amount of the hydrolyzable hydrolyzable group, and the amount of 0.0_5 to 5 in the mouth. Ear, preferably 1 · 5 · Organic solvent The cut polymer of this embodiment is prepared, and the compound is prepared by dissolving the compound in an organic solvent to prepare a first liquid. For example, isopropyl alcohol, n-butanol, isobutanol, the first alcohol solvent, ethylene glycol, propylene glycol, and 1,3-butyl; 2, pentanediol, 2-methyl _2,4-pentanol a to Z'4 2-ethyl*hexanediol, alcohol 'hexa-, 2,4-heptanediol, one product ^yiyizhi, dipropylene glycol, triethylene glycol C 4 夕 is a solvent; ethylene glycol monoterpene, ethylene glycol monoethylan:: B: alcohol early propyl ether, ethylene glycol monobutyl ether and other polyols partial ether soluble: wide ether, isopropyl ether, n-butyl Ether, n-hexyl ether, 2-ethylhexyl ether, epoxy propylene propylene, 4-pentane, 4-methyl 4-pentane, di- 4:, monomethyldioxane, ethylene glycol monomethyl ether, B Ethylene glycol dimethyl ether, ethylene two: ether, ethylene glycol diethyl ether and other ether solvents; propylene, methyl ethyl ketone, chloroacetone, methyl n-butanone, diethyl ketone, methyl isobutyl ketone, Methyl, iso, ethyl n-butyl, methyl n-hexanone, diisobutyl ketone, trimethyl fluorenone, pentanone, cyclohexyl, cycloheptanone, cyclooctane _, 2 _ _, A A solvent such as a cyclohexanone, a 4-pentanedione, a propylpropanoid, or a diacetone alcohol. Further, 97104568 34 200848451 The organic solvent constituting the second solution is preferably the same solvent. ', α and the above-mentioned first liquid constituting the first liquid 6. The ruthenium-containing polymer of the present embodiment has a carbon atom content of 8 to 40 atom% (preferably, according to the synthesis method) 15~4.0 (preferably u~3 5, ~2〇 atom, and the 黯/Mn form of the polymer containing Shi Xi, because the 5 move %8 is better). In this embodiment, and contains a certain amount of carbon Atom, Inri: When the film forming composition of ^^^ is subjected to oxidation = 3±, there is a core oxide film having a lower dielectric constant of the complex L 1 . Here: :=4.0' will have a meeting A problem of a polymer plexus that has an effect on over-sexability, or a low-molecular weight body that hinders a decrease in the value of 1^. The carbon atom content (atomic %) of a polymer containing a smectite is made in: r3 stone The first base based on the component used in the shovel (hydrolyzable smelting compound) is hydrolyzed to form a sterol group, and the thiol group formed is completely, and the thiophene bond is formed by the primate. The elemental composition of the time is obtained, and specifically, it can be obtained from the following formula: The content of carbon atoms (the number of carbon atoms of the atomic organic cerium oxide sol) / (total number of atoms of the organic cerium oxide sol) xl0 () The weight average molecular weight (Mw) of the dream-containing polymer is preferably 1,000 to 2 Å, 〇〇〇, especially 5,000 to 1 50, 00 () is preferred. If the weight average molecular weight of the ruthenium-containing polymer is more than 20,000, the gelation phenomenon will easily occur 'and the pores in the obtained ruthenium dioxide film are easily too large, and thus it is preferable to avoid. If the weight average molecular weight of the ruthenium-containing polymer is less than 97104568 35 200848451 1, 涂布, the coating property and the storage stability are prone to problems. 17·Effect effect j The synthesis method of the cut polymer of the present embodiment, The second liquid containing the first hydrazine, the hydrazine, and the (B) hydrolyzable decane monomer, which are at least one hydrolyzable decane compound, is added to the second liquid, and the hydrolysis is carried out. "Sintering: a step of = = : :" can obtain a ruthenium-containing polymer that suppresses the occurrence of large particles, has a molecular weight change of 1', and has a predetermined carbon content. Therefore, the user's: a polymer containing Shi Xi Shaped by the film forming composition; number and hygroscopicity are small, and mechanical strength Resistance are excellent |., Hanging 2. The composition for film formation composition for forming a film ::: form, containing the lines

And organic solvents. In the organic solvent, the organic solvent used in the composition for forming a two-film film may be an η攸% 糸 糸 agent, a ketone solvent, or a positive solvent: for example, 1 alcohol, ethanol, n-propanol, Isobutanol, second butanol, third butanol, :, 2-methylbutanol, second pentamyl, basket II, hazelnut, alcohol, 2-methylpentanol, first: upper methoxy Butyl alcohol, Zhengjizao X ^ brother knows 2_ethylbutanol, second heptanol, q = octanol, 2-ethylhexanol, second octanol, n-nonanol, 2-methyl -4-heptanol, n-nonanol, second (undecyl) alcohol, trimethyl^ 971〇4568 36 200848451 alcohol, second (tetradecyl) alcohol, cyclohexanol, nonylcyclohexanol , 3,3 heptadecyl) alcohol, sterol, ketone, and other monoalcoholic solvents; , monomethylcyclohexanol, benzyl alcohol, dipropylene glycol, 1,2-propylene glycol, 1 methyl- 2,4-pentanediol, 2,5-hexa-diol, 2,4-pentanediol, 2-alcohol solvent; one-by-one, three-propanol, monoethyl alcohol Ethylene glycol single top, ethylene glycol single shout, B _ =, ethylene glycol monopropyl bond, ethylene glycol based test, two Glycol monomethyl ether, dioxane phenyl ether, ethylene glycol mono-2-ethylenepropene oxime, diethylene glycol top, diethylene glycol B (10), diacid monopropylene glycol monoethylenol mono-_- shout , propylene glycol monochao, single-test, dipropylene glycol mono-British, di-propanol: alcohol single-dial, dipropylene glycol shouting solvent and so on. Two or more kinds of the polyol portion such as the alcohol (IV) are used. - It can be used alone or in combination with a ketone solvent. For example, propyl methyl n-butanone, diethyl ketone, methyl butyl ketone: ketone, methyl acetonide, ketone, kemei, etc. Methyl-n-pentanone, ethyl positive == isobutyl, trimethyl fluorenone, cyclopentanone, ring (tetra), phosphonone, cyclooctane _, 2 _ gang, methyl cyclohexanone, 2, 4 _ 戊二酉 with acetone propyl _, diacetone alcohol, jas f two 兮 舫 舫 丨〆 丨〆 丨〆 乙 乙 乙 乙 乙 1、 1、 1、 1、 1、 1、 1、 1、 1、 1、 1、 1、 1、 The s=:r system may be used alone or in combination of two or more. For example, N,N-dimethyldione, " carbamide, N,N-dimethylformamide, NN face, Νί田 I 7 * , 丨Ν -ethylformamide, acetaminophen < acetylamine decyl dimethyl acetamide, " propyl amide, 97104568 37 200848451 11f: each: _ and other nitrogen-containing solvents. These amide-based solvents may be used singly or in combination of two or more kinds. Examples of the solvent of the early-only ether system include: ethyl scale, isopropanyl, n-butyl 2-(ethyl), ethylene bromide, 1,2-epoxypropanone, and the like: 4: sulfhydryl, etc. Ethylene, Erqi, etc., and its acetylene, sulfhydryl monodecyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, and ethylene , ethylene glycol mono-n-hexane, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monoterpene ether, diethylene glycol diterpene, Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-ethanol-n-butyl, diethylene glycol mono-n-hexane, ethoxy diethylene glycol, tetraethylene glycol di-n-butyl Ether, propylene glycol monoterpene ether, propylene glycol monoethyl ketone, propylene glycol monopropyl propylene glycol, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropanol monoethyl ether, tripropylene glycol monoterpene ether, tetrahydrofuran, 2-mercaptotetrahydrofuran, two An ether-based solvent such as phenyl ether or anisole. The ether-based solvent may be used singly or in combination of two or more kinds. Examples of the vinegar-based solvent include diethyl carbonate and propylene carbonate. Acetate acetate, ethyl acetate, 7-butyrolactone, 7-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, dibutyl acetate, n-amyl acetate , second amyl acetate, 3-methoxybutyl acetate, decyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate,曱-cyclohexyl acetate, n-decyl acetate, methyl acetate, ethyl acetate, ethyl acetate, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, acetic acid Ethylene glycol monoethyl ether, diethylene glycol diacetate mono-n-butyl bond, propylene glycol mono-decyl ether acetate, propylene glycol acetate single 97104568 38 200848451 Ethyl propylene glycol monopropylene, propylene glycol glycol mono W, dipropylene glycol monoacetate , B:: bismuth, acetic acid dipropionate decyloxy triethylene glycol ester, ethyl propionate::: acetate, vinegar vinegar, oxalic acid, diethyl oxalate, oxalic acid di-n-butyl, known, propionic acid isotonic acid Butai vinegar, lactic acid n- vinegar, malonic acid: 酉:: vinegar diacetate, (iv) diethyl vinegar and other i-based solvents. These ": , dimethyl citrate, seed, can also be used at the same time to use ^ 4 system 〉 gluten system can be used alone 1 Γ [: family = solvent can be, for example, n-pental, iso- simmer, sinter, = , Zhenggeng Shao, Yi Geng Shao, 2,2,4_Sanmethylpentyl, Zhengxinyuan, Alidi Dimethoate: aliphatic fumarate solvents such as methylcyclohexane. These lipids are based on cereals. One type may be used alone or two or more types may be used at the same time. One:: The solvent may, for example, be benzene, toluene, diphenylbenzene, hydrazine, Jit ethylbenzene, n-propylbenzene, cumene, diethyl Benzene, iso-di' 々 broad-isopropyl basic, n-pentyl naphthalene, trimethylbenzene and other aromatics can be combined. The δ hai and other aromatic hydrocarbon-based solvent systems can be used separately, also: 5 days to use 2 The above-mentioned solvent is, for example, a halogen-containing solvent such as dichloromethane or a difluoride-like, chlorobenzene or dichlorobenzene. . The composition for forming a film of $ & is preferably a linear solvent having a boiling point of less than 1 C, particularly preferably an alcohol solvent, a ketone solvent, or a solvent of s, and the "Hai system alone One type may be used or two or more types may be used at the same time. The organic solvent may be the same solvent as that used for the synthesis of the polymer containing the sulphate, or may be substituted with the solvent to the desired organic solvent after the synthesis of the polymer containing the sulphate. The total solid content concentration of the film-forming composition of the present invention is preferably from 0.014568 39 200848451 to from 0: 1 to 20% by mass, and can be appropriately adjusted in accordance with the purpose of use. By setting the total solid content concentration of the film-forming composition of the embodiment of the present invention to 0.1 to 20% by mass, the film thickness of the coating film can be set to an appropriate range, and the storage stability can be exhibited. Further, the adjustment of the total solid content concentration can be carried out by using concentration and dilution with an organic solvent. 2·2·Other Additives In the film-forming composition of the present embodiment, components such as an organic polymer and a surfactant may be added. (2 · 2 · 1) The organic polymer organic polymer may, for example, be a polymer having a sugar chain structure, a vinyl guanamine polymer, a (meth)acrylic polymer, or an aromatic vinyl compound polymer. Dendrimer, polyimine, poly-aramid, poly-aromatic: poly-polyamine, poly-zinaki, polysaki, gas-based polymer, polymer with polyepoxy structure, etc. The polymerization system having a polyepoxy-fired structure may, for example, be a polyformic acid structure, a ruthenium-oxygen-oxygen-fired structure, a polyglycidyl-fired structure, a polytetramethylene oxide butane structure, etc. # w , specifically, for example : polyoxymethylene alkyl ether, polyoxyethylene alkyl ether ♦ oxyethylene benzoic acid Benzene, polyoxyethylene sterol scale, polyoxyethylene lanolin derivative, sulphur-based condensate Ethylene oxide derivative, polyoxyethylene polylactic acid propylene block copolymer, polyoxyethylene oxypropylene sulphide light, etc.; polyoxyethylene glycerin fatty acid, polyoxyethylene sorbitan Alcoholic liver fat, polyoxyethylene sorbitan fatty acid §, polyoxyethylene fatty acid burning (tetra) amine sulfate, etc. Polyethylene glycol fatty acid ester, ethylene two 97104568 200848451 alcohol fatty acid ester, fatty acid monoglycolic anhydride fatty acid 3, propane II 14 (four): glyceryl fatty acid ester, sorbose compound. An ether vinegar type such as a fatty acid vinegar such as a compound having the following structure of an intercalated polyoxyethylene polyoxypropylene smear copolymer: Bovine case - (X'(Y,)m-(X,)n- (wherein, lanthanide Refers to -CH2CH2〇-shows Fu·v, and 4b Γ shows the base; ! means the number of the second 90 = ((5) 〇 - refers to the value of 90 ~ 90.), the value of ^ 10~99; η Preferred examples among the above are, for example, a polyoxypropylene-promoting copolymer, a polyoxyethylene pit, a polyoxyethylene diglyceride fatty acid vinegar, a polyoxyethylene, a mountain, a breast milk, a base, and a polyoxygen. Ethyl sorbitan fatty acid ester and the like may be used alone or in combination with the above-mentioned available amount. 200 parts by weight. ί has been used in 100 parts by weight, usually 2 · 2 · 2 · surfactants == = agent system can be, for example, a non-ionic interface, etc., especially such as u agent, two Surfactant ^ ® agent, polyoxonated surfactant, polydecane 糸 surfactant, 蜊 为 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , / Tongue agent, polyfluorene-based surfactant is preferred. The surfactant used in the use of 旦 #上" 丨王片J苟佳里 is relative to the obtained lanthanide polymer 1〇〇97104568 200848451 ^ 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 0000 The formation of the insulating film) includes a step of applying the film-forming composition onto a substrate, a step of forming the main film, and a step of applying a curing treatment to the coating film. The substrate to which the film-forming composition is applied may, for example, be a Si-containing layer such as Si, Si 2 or (SiM SiC or SiCN. A method of applying a film-forming composition to the group + may be used, for example. Coating means such as spin coating, dipping method, roll coating method, spray coating method, etc. After coating the substrate with the film-forming composition, the solvent is removed to form a coating film. The thickness of the film is 〇〇5~25#m, and the thickness of the second application is 涂.Bu 5. 〇# m coating film. Then, the obtained coating film is hardened. The treatment can form a cerium oxide film. The curing treatment is performed by a high-energy line irradiation plasma treatment such as heating, electron beam or ultraviolet ray, and a combination thereof, preferably by heat treatment or high-energy line irradiation. When hardening by heating, the coating film is heated to 80 to 450 ° C in an inactive environment or under reduced pressure (preferably 30 (TC to 450 〇.) heating at this time, the method can be used, for example: heating Plate, oven, high temperature furnace, etc., and heating ring; environment can be in an inactive environment, or under reduced pressure Further, in order to control the curing rate of the coating film, it may be subjected to stepwise heating or optionally in an environment such as nitrogen, air, oxygen, or reduced pressure, if necessary. Manufacture of ceramide film. 97104568 42 200848451 4. Cerium oxide film The present invention - the oxidized cerium oxide according to the embodiment is particularly suitable for use in, for example, (3), system because it belongs to a low dielectric system and has excellent surface flatness. An interlayer insulating film for a semiconductor element such as LSI, D_, SDRAM, RDRAM, or D_RDRAM, and is applicable to, for example, a surface stop film, a surface coating protective film for a semiconductor element, an intermediate layer of a semiconductor fabrication step using a multilayer photoresist, The interlayer insulating film of the multilayer wiring board, the protective film for the liquid crystal display element, the insulating film, etc. The magnet dioxide film of the present embodiment can be used for a semiconductor device including a copper damascene process. The oxygen cut film system dielectric f number is preferably from 2.5 to 15.0 GPa, more preferably from 3.0 to 12 0 GPa, and the film density is most from 0.1 to 1.3 g/crn3, particularly preferably from 0.8 to 1.27 g/cm3. According to the condition ', the organic cerium oxide film of the present invention is excellent in mechanical properties, chemical resistance, and low dielectric constant, etc. ^ 5. Embodiments Hereinafter, the present invention is implemented. The present invention is not limited to the following examples. In addition, the "parts" and "%" in the examples and comparative examples are respectively referred to as "parts by weight" and unless otherwise stated. "% by mass." Stomach ^ 5. 1. Evaluation method Various evaluations were carried out as follows. In addition, a polymer film (cerium oxide film) formed by the following method was used for the elastic modulus and the drug resistance. The composition obtained in each of the examples and the comparative example 97104568 43 200848451 was applied to the Shixi wafer by spin coating, and then the substrate was dried at 90 ° C for 3 minutes on a hot plate. In a nitrogen atmosphere, the film was dried at 200 ° C for 3 minutes, and the substrate was fired in a nitrogen atmosphere at 400 ° C for 6 minutes to obtain a film thickness of 5 〇〇 # m polymer film. And using the polymer film for the above Kind of assessment. 5· 1· 1. Dielectric constant measurement, Δ k On a pair of n-type Nissin wafers having a resistivity of 0·1 Ω·cm or less, p is applied by spin coating to form a film-forming composition. And drying on a hot plate at 90 ° C for 3 minutes, followed by nitrogen in a nitrogen atmosphere. (: 3 minutes of dry distillation was carried out, and the film was fired under a reduced pressure of 50 mTorr (vacuum atmosphere) in a vertical high-temperature furnace of 42 ° C for 1 hour to obtain a film. On the obtained film, an aluminum electrode pattern was formed by a steaming method. For the sample, a sample for measuring the dielectric constant was prepared. For this sample, a temperature of 1 kHz was used, and an HP16451B electrode and an HP4284A dielectric analyzer LCR meter manufactured by Agilent Co., Ltd. were used, and the room temperature was measured according to the CV method (24. With 2〇(rc) (the dielectric constant of the film. △k is at room temperature (_, side Hit a@RT), and the dielectric constant (10) measured under 2GG C, dry nitrogen environment〇〇 The difference between the daytimes (^k = k@RT-k@2〇(rc). Using this Ak, it is mainly possible to estimate the amount of increase in dielectric constant caused by moisture absorption. Usually, if Ak reaches: 〇 ·15 or more, it is an organic cerium oxide film with high hygroscopicity. 5·1·2· Evaluation of the elastic modulus of the film (Y〇ung rati〇), and the elastic modulus of the film is measured by the continuous rigidity measurement method. 1·3·Resistance 97104568 44 200848451 An 8-inch wafer of ruthenium dioxide film is formed at room temperature in a 2% dilute hydrofluorok K solution. After 1 minute of collapse, the film thickness of the cerium oxide film before and after the immersion was observed. If the residual film rate as defined below was 99% or more, the drug resistance was judged to be good. Residual film rate (%) = ( Film thickness after impregnation) + (film thickness before impregnation) xl00 A: Residual film rate of 99% or more B: Residual film rate less than 99% 5. 5 · 4 · Weight average molecular weight Mw , the number average molecular weight, the molecular weight distribution, the weight average molecular weight (M w) and the number average molecular weight (Μη) of the Mw/Mn hydrolysis condensate, which were subjected to a molecular sieve chromatography method according to the following conditions: concentration 1 Omm〇1 / L of LiBr-IhPO4 in 2-methoxyethanol solution, using solvent as solvent, and dissolving the hydrolysis condensate 〇lg in i〇〇cc iiOiMol/DaiBr-hPO4) 2-methoxyethanol In the solution, the standard sample was prepared by using WAK0 Co., Ltd., and polyethylene oxide was used. t: Using Tosoh Co., Ltd., high-speed Gpc device HLC-8120GPC). Column: used by Tosoh Co., Ltd. tSK—gel, pER AWM-H (length 15 cm), three sets of devices in series. Measurement temperature: 40 ° C Flow rate: 0. 6 ml / mi n· 97104568 45 200848451 Detector: Detected by RI built in Tosoh Co., Ltd., high-speed GPC device (model HLC-8120GPC). Further, the dispersion of molecular weight distribution is calculated by Mw/Mn. Small ' indicates that the molecular weight distribution is closer to the normal distribution. 5·2·Production of film-forming composition 5·2· 1. Synthesis Example 1 In a quartz three-necked flask equipped with a condenser, a solution (2): 1〇% p tetrapropylammonium hydroxide aqueous solution 69.93 g Ultrapure water I22.96g, and ethanol 235.73g, and dissolved. Next, the solution (1): 46.20 g of methyltrimethoxydecane and tetraethoxydecane 3 (h28g, having a structure represented by the following formula (7), wherein η means a value of 1 or more) A mixed solution of carbon hexane (Mw=8 〇〇) 7.96 g and 192.87 g of ethanol was filled in a dropping funnel, and the solution was stirred at 60 ° C while the solution was dropped for 3 hours. Thereafter, stirring was continued for 3 hours at 60° C. After cooling the reaction mixture to room temperature, propylene glycol monopropyl ether 669·57 g and 20% aqueous acetic acid solution (30·43 g were added. The reaction solution was concentrated under reduced pressure. The film formation composition 1 was obtained until the solid concentration reached 10%. [Chemical 3]

••...(7) 5 · 2 · 2.Comparative Synthesis Example 1 In the flask, the solution was weighed (1): the methyl group was made of quartz with a condenser. 97104568 46 200848451 Dimethoxydecane 46·20g, tetraethyl Oxydecane 3〇·28g, polycarbane (Mw=8〇〇) 7·96g, and 192·87g of ethanol, which are not structured according to the following formula (7), are dissolved. Next, a mixed solution of 69.93 g of a solution (2): 1% hydrazine oxidized tetrapropylammonium chloride solution, 122.96 g of ultrapure water, and 235.73 g of ethanol was placed in a dropping funnel. While the solution (1) was stirred at 60 ° C, the solution (2) was dropped over 3 hours, and stirring was continued for 3 hours at 60 °C. After cooling the reaction solution to room temperature, 669.57 g of propylene glycol monopropyl ether and 43 g of a 20% aqueous acetic acid solution were added. The reaction mixture was concentrated under reduced pressure until the solid portion concentration was 1% to obtain the composition 2 for film formation. 5 · 2 · 3. Comparative Synthesis Example 2 In a quartz three-necked flask equipped with a condenser, a solution (1) was obtained: methyl trimethoxy decane 46·20 g, tetraethoxy decane 30·28 g, and Polycarbane (Mw = 800) 7 · 96 g of the structure represented by the following formula (7), and 192. 87 g of ethanol were dissolved. Next, a solution (2): a mixed solution of 10% tetrapropylene hydroxide (69.93 g of an aqueous solution, 122.96 g of ultrapure water, and 235 g of ethanol) was prepared. The solution (1) was further dried at 60 ° C. After stirring, the solution (2) was added all at once, and stirring was continued for 6 hours at 60 ° C. After cooling the reaction solution to room temperature, propylene glycol monopropyl ether 6 6 9 · 5 7 g, and 20% were added. Acetic acid; 30. 43 g of an aqueous solution. The reaction solution was concentrated under reduced pressure until a solid concentration of the component was 10% to obtain a film-forming composition 3. 5·2· 4. Synthesis Example 2 Having a condenser In a quartz three-necked flask, the solution (2) was obtained by dissolving 264.37 g of r-butyrolactone and 0.37 g of oxalic acid in ion exchange water 97104568 47 200848451 and then dissolving. Then, 'solution (1): methyl triethoxy = lg, tetramethoxy money 47.36g, and having a structure represented by the following formula (8) (wherein the external reading refers to the composition ratio of each unit), the carbon stone Xi Hyun (Mw = l_) 26.15g, The solution dissolved in methyl isobutyl _ 216 is filled in the dropping funnel. The solution (2) is mixed under the muscle (4), and the solution (1) is over 2 After the hour is dripped, the mixture is continuously stirred for 3 hours under the diaphragm. Then add propylene glycol monoethylate test (4), and the reaction solution is cooled to room temperature, and then concentrated under reduced pressure until the solid concentration reaches 10%. The film formation composition 4 was obtained. [Chemical 4]

..... (8) 5· 2· 5·Comparative Synthesis Example 3 ί; In a quartz three-necked flask equipped with a condenser, weighed a solution (1): decyl diethoxy decane 57 · 51 g, Tetramethoxy decane 47·36 g, polycarbane (Mw: 1 〇〇〇) 26·15 g having a structure represented by the above formula (8), and decyl isobutyl ketone 216·30 g were dissolved. Next, the solution (2) was prepared: a solution of 264.37 g of succinyl lactone and oxalic acid 0·37 δ dissolved in 87.74 g of ion-exchanged water. While the solution (1) was stirred under 55, the solution (2) was added all at once, and stirring was continued at 55 for 5 hours. Further, propylene glycol monoethyl ether 105 (K23 g was added, and the reaction liquid was cooled to room temperature, and then concentrated under reduced pressure until the solid concentration reached i 〇% to obtain a film-form 97104568 48 200848451 composition 5. 2. Synthesis Example 3 In the three-necked flask containing the condensed stone, 'addition solution (2) · propanol monoethyl ether 85.2 lg, ion exchange water 132 · 82 g, and tetrakis (ethyl acetonate) titanium O.Ollg, and stirred at 5 (TC). Next, the solution (1): dimethyldimethoxydecane 26·62 g, methyltrimethoxysulfate 75.37 g, tetradecyloxydecane 50 54g, a solution having a structure represented by the following formula (9) (wherein η means a value of 1 or more), a solution of polycarbazide (Mw=840) 42·64 g, and propylene glycol monoethyl ether 242·52 g, The solution was filled in a dropping funnel, and while the solution (2) was dropped at a temperature of 50 ° C, the solution (1) was dropped for 2 hours, and then reacted at 5 ° C for 2 hours to add a propylene glycol single. Ether 1021·74g, and the reaction solution was cooled to the temperature. The reaction solution was concentrated under reduced pressure until the solid concentration reached 10%. Stop 'to obtain a film forming composition 6. [Formula 5]

Ch3

Si - CH2 och3 ..... (9) 5 · 2 · 7. Comparative Synthesis Example 4 In a quartz three-necked flask equipped with a condenser, the solution (1): dimercapto-methoxydecane 26· 62 g, decyltrimethoxydecane 75·37 g 'tetradecyloxydecane 50.54 g, polycarbane 97104568 49 having a structure represented by the above formula (9) 200848451 (Mw=840) 42.64 g, and propylene glycol monoethyl ether 242 A 52 g solution was stirred at 50 C. Next, solution (2): 85.21 g of propylene glycol monoethyl ether, 132 82 g of ion-exchanged water, and titanium (meth)acetone 0·01 lg were mixed and filled in a dropping funnel. While the solution (1) was stirred at /50 ° C C, the solution (2) was dropped over 2 hours, and then reacted at 50 C for 2 hours, and propylene glycol monoethyl ether 1021·71 g was added, and the reaction was carried out. The solution was cooled to room temperature. The reaction solution was concentrated under reduced pressure until the solid portion concentration was 1%, to obtain a film forming composition. 5· 2· 8· Synthesis of J 4 In a quartz three-necked flask equipped with a cold state, weigh the solution (2) • 72.25 g of tetrapropylammonium hydroxide aqueous solution, ultra pure water I27.05 g, and ethanol 228·64 g And dissolve. Next, a mixed solution of the solution (1): methyltrimethoxydecane 51·34 g, tetraethoxydecane 33·65 g, and ethanol 187·〇7 g was placed in a dropping funnel. While the solution (2) was stirred at 6 Torr, the solution (1) was dropped for 3 hours and then at 6 Torr. 〇: Stir for 3 hours. After cooling the reaction mixture to room temperature, 669.57 g of propylene glycol monopropyl ether and 3144 g of a 20% aqueous acetic acid solution were added. The reaction solution was concentrated under reduced pressure until a solid concentration of 1% was obtained to obtain a composition for forming a film. 5 · 2 · 9 ·Comparative Synthesis Example 5 In a quartz three-necked flask equipped with a cold descent, weighed the solution (1): decyltrimethoxydecane 51.34 g, tetraethoxydecane 33.65 g, and ethanol 187. 07g, and dissolved. Next, a mixed solution of the solution (2): 1% by weight of tetrapropylammonium hydroxide = 97104568 50 200848451 solution 72·25 g, ultrapure water 127·05 g, and ethanol 228·64 g was placed in a dropping funnel. While the solution (1) was stirred at 60 ° C, the solution (2) was dropped over 3 hours, and then the mixture was continuously stirred at 60 ° C for 3 hours. After cooling the reaction solution to room temperature, propylene glycol monopropyl ether 669.62 g and a 20% aqueous acetic acid solution of 31·44 g were added. The reaction solution was concentrated under reduced pressure until the solid concentration reached 1 〇% to obtain a film-forming composition 9. [Table 1] Composition Mw Μη Mw/Mn 1 54,000 22,000 2. 45 2 ] 126,000 34,000 3. 71 3 88, 〇〇〇 28,000 3. 14 4 12,000 6, 100 1. 97 5 14, 〇〇〇 4, 700 2. 98 6 15, 〇〇〇 7, 300 2. 05 7 16,000 5, 400 2.96 8 60,000 "27, 000 2. 22 9 98, 〇〇〇 31,000 3. 16 5 · 3 · Film formation (implementation Examples 1 to 5 and Comparative Examples u) I The composition obtained in each of the synthesis examples was applied by spin coating on an 8-inch wafer, and then heated in the atmosphere at 8 {rc for 5 minutes. Then, under nitrogen, heat is applied to the TC for 5 minutes. The film is colored in a uniform manner according to the method of each example. The evaluation results of the composition and the film are shown in Table 2. The cross-linking treatment method is heat-treated or ultraviolet-irradiated. The order of heat treatment and ultraviolet irradiation is as follows. 5·3·1·heat treatment^. The obtained film is subjected to vacuum for 1 hour at 425. Heating. 97104568 51 200848451 5· 3. 2. Ultraviolet irradiation in the treatment chamber of oxygen partial pressure O.OlkPa, on the heating plate, while heating the coating film Outside ultraviolet source having a wavelength based white 25〇ηιη ultraviolet wavelengths below. Further, since the ultraviolet light UV is white lines, and thus will not be implemented by an effective method of measuring illuminance.

Comparative Example Example 5 ΖComparative Example 5·4·Results Investigations (1) Example 2 and Comparative Example 2 The crosslinking treatment belonging to the coating film is an example in which the firing is carried out by thermal baking. Although the amount of each reagent used in the production of the film-forming composition is the same, the second liquid containing water and the catalyst, and the second (four) containing the hydrolyzable compound of the reaction raw material in the disk, the reaction method is not obtained according to the example i. The film is a second liquid (solution (2)) (four) which will contain a water disk catalyst. In the case where the mixing is carried out under c, the third liquid containing the hydrolyzable monomer and the hydrolyzable polycarbohydrate (solution (1)) is dropped in the second liquid, the wire name is sick, the public line is The film thus produced, and thus, the film obtained by the method of obtaining a superior polymer drug property. ; low hygroscopicity (Δ k low), and resistance / use of the "formation composition" used in the liquid is obtained, the obtained film will belong to the same level of mediation under the _ 匕Comparative Example 2 was used but the hygroscopicity was high (4) high). The composition of the first h 1 of the leeches _ belongs to a person who will contain all of the ", :: liquids added to the first liquid at a time. In addition, the method of the second embodiment is like the formation of the sputum. Instead, the coating film using the purple coloring material is hard from the viewpoint of film hygroscopicity, and the same junction will appear. Therefore, according to Example 3, the 盥 丨 丄 丄 丄 丄#下Γ The first liquid (solution (1)) is used for mixing, and the second liquid (solution (7)) is dropped. The film η with low hygroscopicity and excellent drug resistance belongs to, and is compared with the case of Example 6'. It is known that the ruthenium produced by using the composition of the second film and the film forming composition, and the use thereof;;: (solution (9) dripped in the first liquid (solution (1)) = made with the composition of the liquid 2 The membrane has a high hygroscopicity. Further, in the formation of the boat, the examples 5 and 7 all belong to the group synthesized by the calcined decane compound: the anti-Early bad. This phenomenon indicates that the polymer constitutes # The octopus's endurance will be important in terms of the improvement of drug resistance. The other two::: 夕 烷 - 事 'examples, will contain hydrolyzed conjugate Eryi 97104568 53 200848451 The side drops are contained in water and the catalyst is low. On the other hand, because the film is more absorbent than the film obtained in the first

Age / 丨", 夺 弟 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 , 幸 添加 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸 幸The reaction method will be effective, and the hygroscopic improvement is improved. This #4 is determined by the molecular weight of each of the ruthenium forming compositions in Table 1 and is: ° 'The right side will contain water and catalyst. The second crucible is heated, and the solution is (1) k square in the middle of the liquid cooling solution (2); the first liquid of the second = raw bi-combustion compound is low. Compared with the Mw/Mn value according to other methods, it is obtained. The gamma correlation of the hydrolysis condensate can reduce the dielectric constant of the polymer as a whole, and the film can be excellent. "In this regard, the present invention can also be said to have Ο Degrees of superior electricity often: ^ Ming obtained the dioxide dream film, mechanical strong interlayer insulation 臈. : quite suitable for use as a semiconductor component, etc. 97104568 54

Claims (1)

200848451 X. Patent application scope: 1 · A method for synthesizing a polymer containing Shixi, comprising: selecting at least one selected from the group consisting of (A) a hydrolyzable decane monomer and (B) a hydrolyzable polycarbane. The first liquid of the hydrolyzable decane compound is added to the second liquid containing water and a catalyst to hydrolyze and condense the hydrolyzable decane compound. 2. The method for synthesizing a ruthenium-containing polymer according to the first aspect of the invention, wherein the temperature of the second liquid is 40 ° C or higher when the first liquid is added to the second liquid. 3. The method for synthesizing a ruthenium-containing polymer according to the first aspect of the invention, wherein the (A) hydrolyzable decane mono-system is selected from the group consisting of the following general formulas (1) to (3); Decane compound: RaSi(〇R1)4-a (1) (wherein R is a hydrogen atom, a fluorine atom or a valence organic group; R1 is an i-valent organic group; a is a 1 An integer of ~3); Si(0R2)4 (2) 〇 (wherein R2 means a monovalent organic group); R3b(R40)3-bSi-(R7)d-Si(〇R5)3- cR6c (3) [wherein, R3 to R6 are the same or different from each other and represent an i-valent organic group; b and c represent the same or mutually different 〇~2 values; R7 represents an oxygen atom; a group represented by phenyl or -(CH2)m- (wherein m is an integer of 1 to 6); d means: hydrazine or 1]. 4. The method for synthesizing a ruthenium-containing polymer according to claim i, wherein the (B) hydrolyzable polycarbane has a polycarbon having a structural unit represented by the following general formula (4); : 97104568 55 200848451 [Chem. 6] (4) (wherein, R8 is selected from the group consisting of aminoproline, rhein, rhodamine, anthracene, alkoxy, Τ 30 夂 |, turbulent mesylate, propyl, propylene a group consisting of a group consisting of a glycidyl group and a group of epoxy propyl groups; only 9 series: atom, alkoxy group, alkoxy group, decyloxy group 4 group, group, rn": broad-based propyl group and epoxy propyl group The group, :, is 'identical or mutually different, indicating 2 (four) selected from * atom, hydroxyl group, foxy group, decyloxy group, Wei group, methyl group, tris (tetra) acid group, carbon = 〜6: The group consisting of an aromatic group, an allyl group, and an epoxy group is the same or different from each other, and represents a substituted or unsubstituted methylene group, a stretching group, an alkenyl group, a stretching group, and a stretching group. Base; y, y, z respectively represent the value of 〇~1〇, 〇〇〇, and satisfy the condition of 5<x+y+z<10 000). 5. The method for synthesizing a ruthenium-containing polymer according to the first aspect of the invention, wherein the hydrolyzable decane compound is the (A) hydrolyzable decane monomer and the (B) hydrolyzable polycarbosilane; The (B) hydrolyzable polycarbosilane complete hydrolysis condensate is used in an amount of 1 part by weight, and the (A) hydrolyzable decane monomer is 1 to 1 part by weight. 6. The method for synthesizing a ruthenium-containing polymer according to the first aspect of the invention, wherein the catalyst is at least one selected from the group consisting of a basic compound, an acidic compound, and a metal chelate compound. 97104568 56 200848451 7 - A method for synthesizing a polymer containing a compound of the seventh aspect of the invention, wherein the basic compound is a compound represented by the following general formula (5): ^ (XTX3X4N)gY ··· ···(5) mu (wherein X, X2, X3, X4 means an independent hydrogen atom, an alkyl group of a carbon number, a hydroxyalkyl group, an aryl group or an aralkyl group; γ means a turning atom or a work ~ valent anionic group; g means an integer of 1 to 4). 8. The method for synthesizing a ruthenium containing polymer according to item 6 of the patent application 'wherein' the above acidic compound is an organic acid. 9. The method for synthesizing a ruthenium-containing polymer according to claim 6, wherein the metal chelating compound is a general metal chelating compound: (8) R15eM(0R16)fe (6) 〔 In the formula, R15 means a chelating agent; hydrazine means a metal atom; Ru is a 2 to 5 alkyl group; or a carbon number 6 to 2 aryl group; f means a metal μ divalent; and e means 1 to f Integer]. Atom 10. A polymer containing ruthenium, which is synthesized according to the method of any of the patent applications. ^1 ^9 n. A film-forming composition containing the patented winter stone 々 :: 3⁄4 A » The collection of 10 brothers and the organic solvent. A method for forming a cerium oxide-based film, comprising the steps of: coating a film-forming composition of the eleventh aspect of the invention on a base: a coating; and performing a hardening on the coating film; The formation of a cerium oxide film is obtained according to the method for forming a patented oxidized cerium film. (5) Brother 12 items 97104568 57 200848451 VII. Designated representative drawings: (1) The representative representative of the case is: None (2) The symbolic symbol of the representative figure is simple: • No. 8. If there is a chemical formula in this case, please reveal the most Chemical formula showing the characteristics of the invention: RaSKORVa ······(1) Si(0R2)4 (2) R3b(R40)3-bSi-(R7)d~Si(0R5)3-〇R6c ...... (3) 97104568 4