TW200932847A - Coating liquid for forming silica-based coating film, method of preparing the same and silica-based insulation film obtained from the coating liquid - Google Patents

Abstract

To provide an application liquid for forming a silica-based coating film, which has high film strength, a relatively low dielectric constant, and excellent surface smoothness and crack resistance, and to provide a preparation method for the application liquid and a silica-based coating film obtained from the application liquid. The application liquid for forming the silica-based coating film comprises a silicon compound, which is obtained by heating a dispersion liquid containing a specific organosilicon compound and silica-based particles containing a basic catalyst component, and at least, performing partial hydrolysis and/or hydrolysis of the organosilicon compound by the basic catalyst component released from the silica-based particles.

Description

200932847 IX. The present invention relates to the formation of a cerium oxide-based film having a high film strength and a low ratio, and having excellent surface flatness and crack resistance, a preparation method thereof, and a self-coating method. The cerium oxide film obtained from the cloth solution. [Prior Art] 0 In recent years, in the manufacturing industry of semiconductor devices, liquid crystal devices, and sensor display devices, more than a semiconductor substrate, a plurality of wiring layers, a component surface, and/or a PN junction portion are formed. On the liquid crystal substrate, a cerium oxide-based coating film as an insulating film is formed as a coating liquid for forming such a cerium oxide-based coating film, for example, containing a general formula of RnSi(OR')4_n (wherein R, R' represent carbon a cerium oxide solution obtained by hydrolyzing polycondensation of an alkyl group represented by an alkyl group, an aryl group or a vinyl group, and having an alkyl group, an aryl group or a vinyl group, and an alkane represented by an integer of 0 to 3, and a reaction product of the alkoxy partial hydrolyzate The cloth liquid (described in 1) and b) contain cerium oxide microparticles and a general formula XnSi 4-n (wherein X is an alkyl group or an aryl group which represents H, F or a carbon number of 1 to 8, and R is An alkoxy decane represented by hydrazine or an alkyl group having 1 to 8 carbon atoms, an aryl group or an integer of 0 to 3, and/or a general formula (wherein X represents H, F or a carbon number of 1) a reactant of a hospital having a base of ～8, an alkyl group of the aryl group 'X', which represents an atom and η is an integer of 0 to 3, or a hydrolyzate thereof The characteristic is that the low dielectric constant oxygen dielectric rate coating liquid is disposed, and the substrate of the display wiring is used for a) the patent (OR) base or the acetylene group of the oxy decane of -8 η, η SiX, 4 -n or ethylene halogenated lanthanide -5 - 200932847 coating liquid for film (described in Patent Document 2). However, the inventors of the present invention repeatedly used the coating liquid and the previously known film forming method (spin coating method and other coating methods) to form substrates and other joint faces of various devices, and repeated tests for forming a ruthenium oxide film. In the case where the film having the above-described characteristics is obtained, in some cases, the cerium oxide fine particles are partially deviated, or the reaction between the cerium oxide fine particles and the partial hydrolyzate and/or the hydrolyzate of the alkoxy decane is insufficient. q The film is not necessarily uniform and has a film having a stable strength (compressive strength and tensile strength), and pinholes and cracks occur on the film depending on the case. Then, the inventors of the present invention have continued to make efforts to solve such problems, and have found that the coating liquid for forming a cerium oxide-based coating film as shown below can be used, and the present invention has been completed. [Patent Document 1] Patent No. 3 1 3 3 5 7 9 [Patent Document 2] Patent No. 3 8 1 3 2 6 8 Q [Explanation] The problem to be solved by the present invention is to solve the above The problem is to provide a Young's modulus of elasticity of 3.OGPa or more, and more specifically, a high-yellow film strength of 5.0 GP a or more and a low specific dielectric ratio, and excellent surface roughness and crack resistance. A coating liquid for a film, a preparation method thereof, and a cerium oxide-based film obtained from the coating liquid, in particular, a cerium oxide-based insulating film. (Means for Solving the Problem) -6-200932847 The coating liquid for forming a cerium oxide-based film of the present invention is characterized by containing an alkoxy decane represented by the following general formula (I), and the following general formula (II) And heating the dispersion of the at least one organic hydrazine compound selected from the halogenated decane and the partial hydrolyzate thereof and the cerium oxide-based fine particles containing the basic catalyst component, at least the aforementioned alkaline liberated by the cerium oxide-based fine particles The catalyst component is a hydrazine compound obtained by partially hydrolyzing and/or hydrolyzing the above organic hydrazine compound. ❹ RnSi(OR,)4-n .........(I)

RnSiX4.„.........(II) (wherein R is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, an alkyl group substituted by fluorine, an aryl group, or a vinyl group. Or a phenyl group, R' is a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms, an aryl group, a vinyl group or a phenyl group, and X is a halogen atom. Further, η is an integer of 0 to 3). It is preferable that the dispersion liquid in the coating liquid for a cerium oxide-based coating film contains a water-alcohol-based dispersion containing water and an alcohol. Q further includes a basic catalyst component and/or an acid in the dispersion liquid. Further, it is preferred that the above-mentioned basic catalyst component is at least one selected from the group consisting of ammonia, ammonium hydroxide, a quaternary ammonium compound, an organic amine, and an amine coupling agent. Further, the acid catalyst component is It is preferable to select at least one of nitric acid, hydrochloric acid, acetic acid, and sulfuric acid. The cerium oxide-based fine particles are an alkoxy decane represented by the following general formula (I), which is hydrolyzed in the presence of the above-mentioned basic catalyst component. The obtained cerium oxide-based fine particles 'and the parts of the basic catalyst component of the previous 200932847 contained in the cerium oxide-based fine particles are adjusted. Better.

RnSi(〇R')4—n (1) (wherein R is a hydrogen atom, a fluorine atom, or a fluorine-substituted alkyl group, an aryl group, a vinyl group or Benzene 3, or an alkyl group having 1 to 8 carbon atoms, an aryl group, and an integer of vinyl i 0 to 3). Further, it is preferable that the cerium oxide-based fine particles are those having a ppm enthalpy. The ruthenium compound is a base catalyst component containing at least the oxygen-releasing agent, and at least a part of the organic sand and/or the hydrolyzed reactant and the cerium oxide-based fine particle are bonded to the cerium oxide micro-fine and fine The inner surface of the hole is preferred. Further, the ruthenium compound is a reaction product containing the above-mentioned basic catalyst component released from the alkaline catalyst component and/or the acidic catalyst component and the particles, and hydrolyzing and/or hydrolyzing the fraction and the cerium oxide. At least a part of the reactant is preferably bonded to the surface of the oxidized portion and the inner surface of the pore. Further, the ruthenium compound is preferably an average molecular weight of from 10,000 to 5,000. Further, the ion concentration contained in the coating liquid is preferably at most the following. The coating liquid for forming a cerium oxide-based film of the present invention has an alkyl group having a number of from 1 to 8, and R' is a hydrogen phenylene group. Further, η is a partial hydrolyzate of the compound of the ruthenium-based fine particles of 200 to 1 1 ,, and the cerium oxide-based microorganoanthoquinone compound-based fine particles contained in the external surface dispersion of the reaction particles, and the front lanthanide The external standard of the microparticles has a method of preparing a cerium oxide-based coating film containing the cerium compound obtained according to the following procedure. (a) The water-alcohol-based dispersion of the cerium oxide-based fine particles obtained by hydrolyzing and polycondensing the alkoxydecane represented by the following general formula (I) in the presence of a basic catalyst component is added to an ultrafiltration device, and the above-mentioned adjustment is carried out. A step of preparing a water-alcohol-based dispersion of cerium oxide-based fine particles in an amount of a basic catalyst component. (b) In the water-alcohol dispersion containing the cerium oxide-based fine particles, the alkoxy decane represented by the following general formula (I), a halogenated decane represented by the following general formula (Π), and a part thereof are mixed and mixed. a step of selecting at least one aqueous dispersion of the organic cerium compound in the hydrolyzate, and (c) heating the mixed liquid at a temperature of 30 to 80 ° C, at least the aforementioned alkaline liberated by the cerium oxide-based fine particles a catalyst component, a step of partially hydrolyzing and/or hydrolyzing the aforementioned organic hydrazine compound R„Si(OR,)4.n (...)

RnSiX4-„ (4) (wherein R is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, an alkyl group substituted by fluorine, an aryl group, or a vinyl group. Or a phenyl group, R' is a hydrogen atom, or an alkyl group having an alkyl group of 1 to 8, an aryl group, a vinyl group or a phenyl group, and X is a halogen atom. Further, η is an integer of 0 to 3). a) The content of the inert catalyst component contained in the obtained cerium oxide-based fine particles is preferably in the range of 200 to 1100 ppm by weight, and the alkali liquid prepared in the above step (b) further contains a base. Preferably, the alkaline catalyst component is selected from ammonia, ammonium hydroxide, a quaternary ammonium compound, an organic amine, and an amine coupling agent. -9 - 200932847 Further, the alkaline catalyst component is selected from the group consisting of ammonia, ammonium hydroxide, a quaternary ammonium compound, an organic amine, and an amine coupling agent. In addition, it is preferable that the acid catalyst component is at least one selected from the group consisting of nitric acid, hydrochloric acid, acetic acid, and sulfuric acid. The cerium oxide-based coating of the present invention is coated on the substrate to form a coating liquid for coating film and dried. , obtained by calcination, with high film strength and low specific dielectric ratio, and excellent surface flatness and crack resistance The cerium oxide-based coating film is characterized in that: the cerium oxide-based coating film contains at least a part of the reactant obtained by partially hydrolyzing and/or hydrolyzing the organic cerium compound to be bonded to the outer surface of the cerium oxide-based fine particle and fine Further, the cerium oxide-based coating film is preferably a film having a Young's modulus of 3.0 GPa or more, and the cerium oxide-based film is a surface roughness thereof. The yttrium oxide-based film having a smooth surface of 5.Onm or less is preferably φ. Further, the yttrium oxide-based film can be suitably used as a yttrium oxide-based insulating film. (Effect of the Invention) Right oxidized dicing according to the present invention When the coating liquid for a film is used, it is possible to form a Young's modulus of 3.OGPa or more, and more specifically 5.0 or more, which has a high film strength and a low specific dielectric ratio, and is excellent in surface flatness and crack resistance. The oxidized sand-based coating film, in particular, the oxidized sand-based insulating film. -10-200932847 In addition, according to the coating liquid of the present invention, even if the surface of the coating film is not subjected to honing treatment or the like, A cerium oxide-based film having a smooth surface (Rms) of 5. Onm or less having a smooth surface is formed on the substrate, particularly a yttrium oxide-based insulating film, and the surface of the obtained yttrium oxide film does not appear on the surface. In addition to the above-described properties, the cerium oxide-based coating film obtained by using the coating liquid of the present invention has excellent adhesion to a film surface formed on a semiconductor substrate or the like, and is excellent in chemical resistance such as alkali resistance. In addition, the coating liquid for forming a cerium oxide-based coating film of the present invention, a preparation method thereof, and the coating method will be specifically described below. The cerium oxide-based coating film is applied to the substrate. The coating liquid for forming a cerium oxide-based coating film of the present invention contains an alkoxy group having the following general formula (I). a decane, at least one organic hydrazine compound selected from the following halogenated decane represented by the general formula (II) and a partial hydrolyzate thereof, and a dispersion of cerium oxide-based fine particles containing a basic catalyst component, at least The ruthenium compound obtained by partially hydrolyzing and/or hydrolyzing the above organic ruthenium compound from the above-mentioned basic catalyst component released from the yttrium oxide-based fine particles.

RnSi(OR,)4_n .........(I) -11 - 200932847

RnSiX4-n (...) (wherein R is a hydrogen atom, a fluorine atom, or a hydrocarbon group having a carbon number of 1 to 8, a fluorine-substituted alkyl group, an aryl group, or a vinyl group. Or phenyl 'R' is a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms, an aryl group, an ethyl group or a phenyl group 'X is a halogen atom. Further, η is an integer of 0 to 3) ° The alkoxydecane may, for example, be methyltrimethoxy sand, methyltriethoxysilane, methyltriisopropoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, or B. Triisopropoxy decane, octyl trimethoxy decane, octyl triethoxy decane, ethyl trimethoxy fluorene, vinyl triethoxy decane, phenyl trimethoxy decane, phenyl tri Ethoxy decane, trimethoxy decane, triethoxy decane, triisopropoxy decane, fluorotrimethoxy decane, fluorotriethoxy decane, dimethyl dimethoxy decane, dimethyl Diethoxydecane, diethyldimethoxydecane, diethyldiethoxydecane, dimethoxydecane, diethoxydecane, difluorodimethoxydecane, difluorodiyl Silane group, trifluoromethyl trimethoxy Silane, trifluoromethyl triethoxy silane-like. Among them, methyltrimethoxydecane, methyltriethoxysilane or a mixture thereof is preferably used. The halogenated decane may, for example, be tetrachlorodecane 'trichlorodecane, methyl trichlorodecane, methyl dichlorodecane, vinyl trichlorodecane, ethyl trichlorodecane, dimethyl dichlorodecane or dimethyl chloride. Baseline, 3,3,3-trifluoropropyltrichloromethane, methylvinyldichlorodecane, n-propyltrichlorosilane, trimethylchlorocholine, methyl-3,3,3 - Trifluoropropyl dichloride sand yard, dimethyl ketone chlorinated base, methyl propyl chlorinated sand, phenyl trichloride sand, third butyl dimethyl chloride based, methyl Phenyl dichloride based sand, heptadecyl fluorene-12- 200932847 based dichlorinated sand yard, diphenyl chlorinated sand yard, etc. Among them, chlorocraceane, methyltrichlorodecane or a mixture thereof is preferably used. The dispersion liquid is preferably a water-alcohol-based dispersion containing water and an alcohol. The alcohol to be used herein may, for example, be methanol, ethanol, propanol, isopropanol or n-butanol. Among them, methanol, ethanol or a mixture thereof is preferably used. Further, it is preferable to further contain a basic catalyst component and/or an acid catalyst component in the dispersion liquid. Among them, it is also desirable to use a component containing the aforementioned acidic catalyst. When the organic ruthenium compound is partially hydrolyzed and/or hydrolyzed in the presence of an acidic catalyst component in the initial stage, the basic catalyst component (the alkaline catalyst component released from the cerium oxide-based fine particles) is further contained. Effect of the effect, etc. The coating liquid of the hydrazine compound obtained by partial hydrolysis and/or hydrolysis forms a film, and a dense cerium oxide-based film can be obtained. The above-mentioned test catalyst component can be exemplified by ammonia, hydrogen peroxide, and quaternary compound. , organic amines and amine coupling agents. Among them, it is preferred to use ammonia, ammonium hydroxide or a quaternary ammonium compound. Further, examples of the acidic catalyst component include nitric acid, hydrochloric acid, acetic acid, sulfuric acid and the like. Among them, nitric acid or hydrochloric acid is preferably used. Further, the basic catalyst component contained in the cerium oxide-based fine particles is the same as the above, and examples thereof include ammonia, ammonium hydroxide, a quaternary ammonium compound, an organic amine, and an amine coupling agent. Among them, it is preferable that the cerium oxide-based fine particles contain ammonia or ammonium hydroxide. When the dispersion containing the alkoxysilane and the cerium oxide-based fine particles is heated, these alkaline catalyst components are easily released from the cerium oxide-based fine particles. Further, the alkaline catalyst component contained in the cerium oxide-based fine particles and the basic catalyst component contained in the dispersion liquid may be the same or different, but it is desirable to use the same as much as possible. The cerium oxide-based fine particles are cerium oxide-based fine particles obtained by hydrolyzing and polycondensing the alkoxy decane represented by the following general formula (I) in the presence of the basic catalytic component, and adjusting the cerium oxide-based fine particles. The amount of the aforementioned basic catalyst component is preferably. Q RnSi(OR,)4-n (I) (wherein R is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group And an aryl group, a vinyl group or a phenyl group, and R' is a hydrogen atom or an alkyl group having an alkyl group of 1 to 8, an aryl group, a vinyl group or a phenyl group. Further, η is an integer of 〇3 to 3). In this case, the content of the basic catalyst component contained in the cerium oxide-based fine particles is preferably in the range of 200 to 1100 ppm by weight, preferably 400 to 8 Å by weight ppm. When the content is less than 200 φ PPm, the partial hydrolysis reaction and the hydrolysis reaction of the organic hydrazine compound (that is, the reaction amount) cannot be sufficiently performed in the vicinity of the outer surface of the cerium oxide-based fine particles and in the vicinity of the inner surface of the pores. When the cerium oxide-based coating film is formed by using the coating liquid obtained by the above treatment, sufficient film strength cannot be obtained. When the content is more than 1,100 ppm by weight, the above partial hydrolysis reaction and hydrolysis reaction cannot be performed, and the resulting coating is carried out. The storage stability of the cloth liquid deteriorates, so it is not good. Further, the above-mentioned adjustment is carried out by adding a water-alcohol-based dispersion containing cerium oxide-based fine particles composed of the hydrolyzate/polycondensate of the alkoxydecane to a filtration apparatus exceeding -14 to 200932847, and performing the method as detailed below. It is better. Further, the oxidized sand-based fine particles are preferably a crumb circumference having an average particle diameter of 5 to 500 nm. When the average particle diameter of the right side is less than 5 nm, the effect as a chelating agent cannot be sufficiently exhibited. Therefore, there is a problem in that the film strength is increased. When the average particle diameter exceeds 500 nm, it is difficult to maintain a uniform dispersion state. Therefore, it is not good. Further, the organic hydrazine compound is obtained by partially hydrolyzing alkoxy decane and/or a halogenated decane, and then mixing with the water-alcohol-based dispersion containing the oxidized sand-based fine particles of the basic catalyst component, and further hydrolyzing. . In this case, it is preferred that the partial hydrolysis of the alkoxydecane and/or the halogenated decane is carried out in the presence of the acidic catalyst component. In the same manner as described above, the above-mentioned organic hydrazine compound is partially hydrolyzed in the presence of an acidic catalyst component, and the use further contains a basic catalyst component (a basic catalyst component released from the cerium oxide-based fine particles, etc.). Effect of the Invention The coating liquid of the hydrazine compound obtained by hydrolysis is formed into a film, and a dense cerium oxide-based film can be obtained. The ratio of the content of the cerium oxide-based fine particles to the organic cerium compound is represented by A in the weight of the cerium oxide-based fine particles, and the weight ratio (A/B) when the weight of the cerium compound (based on Si 〇 2 basis) is represented by B. It is a range of 1/9 to 9/1, preferably 4/6 to 6/4. Here, when the weight it A is 1 / 9 ', the crack resistance of the film finally obtained is deteriorated, and when the weight ratio is more than 9 / 1, the specific dielectric constant of the film is increased, which is not preferable. The ruthenium compound obtained by the treatment of the above-mentioned ruthenium compound containing at least the above-mentioned basic catalyst component released from the oxidized sand-based fine particles, and the above-mentioned organic -15-200932847 sand compound are partially hydrolyzed and/or hydrolyzed, and the aforementioned The cerium oxide-based fine particles 'and at least a part of the reactants are bonded to the outer surface of the oxidized sand-based fine particles and the inner surface of the pores thereof. The alkaline catalyst component emitted from the oxidized sand-based fine particles is such that the organic cerium compound is partially hydrolyzed and/or hydrolyzed in the vicinity of the outer surface of the cerium oxide-based fine particles and the inner surface of the pores. The combination of the reactant and the cerium oxide-based fine particles is sufficiently performed. In the case where the alkaline catalyst component and/or the acidic catalyst component are contained in the dispersion liquid, the alkaline catalyst component and/or the acid catalyst component contained in the dispersion liquid are obtained, and a basic catalyst component emitted from the cerium oxide-based fine particles, a reactant partially hydrolyzed and/or hydrolyzed by the organic cerium compound, and the cerium oxide-based fine particles, and at least a part of the reactant is bonded to the cerium oxide-based fine particles The outer surface and the ruthenium compound on the inner surface of the pores. Further, the ruthenium compound thus obtained is preferably a number average molecular weight of from 500 to 5,000, preferably from 800 to 3,000, based on the converted polystyrene. When the average molecular weight of the number is within the above range, it is possible to provide a coating liquid for forming a cerium oxide-based coating which exhibits excellent stability over time and good coatability. Further, the water-alcohol dispersion containing the ruthenium compound thus obtained can be used as a coating liquid for forming an oxidized sand-based film as it is, but the moisture and the alcohol component contained in the dispersion are contained. 'Use a previously known method, such as distillation in a rotary evaporator, etc.' with propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, etc., selected from -16-200932847, one organic solvent for solvent exchange Use is better. By the solvent exchange, the water and the alcohol contained in the water-alcohol dispersion can be further separated and removed by the alcohol produced by the hydrolysis of the alkoxysilane or the like. Further, if the above operation is carried out using a rotary evaporator, the above-described solvent replacement may be performed almost completely, but in the present invention, it is not necessary to completely perform the above. The amount of the ruthenium compound contained in the coating liquid obtained by the treatment is also different depending on the intended use, and when the ruthenium compound is represented by Si 〇 2, it is desirably adjusted to 2 to 50% by weight based on the weight of the coating liquid. Preferably, it is in the range of 10 to 40% by weight. When the content exceeds 50% by weight, the stability of the coating liquid is deteriorated, and if it is less than 2% by weight, it is difficult to form a uniform film on the substrate. Further, in the present invention, a surfactant, a polyoxyxylene resin or the like as a leveling agent may be added to the liquid composition. Examples of the surfactant include a polyfluorene-based surfactant such as polyoxyalkylene dimethyl polyoxyalkylene, and a fluorine such as a perfluoroalkyl carboxylate or a perfluoroalkyl oxirane adduct. It is a surfactant, etc., and the polyfluorene oxide resin may be a polyether-modified polyanthracene resin, an amine-modified polyanthracene resin, an epoxy-modified polyoxyl resin, or an alkoxy group. Resin, etc. Among them, polyoxyxylene resin is also preferred. Further, the ion concentration contained in the coating liquid for forming a cerium oxide-based coating film is desirably 1.0 mmol/liter or less, preferably 0.6 mmol/liter or less. When the ion concentration is more than 1.0 millimol/liter, when the coating liquid is formed by using the coating liquid, voids, pinholes, and the like are formed in the coating film due to ions contained in the coating liquid. good. -17-200932847 [Preparation method of forming coating liquid for coating film] Next, the method of adjusting the coating liquid for forming a cerium oxide-based coating film of the present invention will be described below. The preparation method of the coating liquid of the present invention is a method for producing a coating liquid for forming a cerium oxide-based coating containing the cerium compound obtained by the following procedure. (a) The water-alcohol-based dispersion of the cerium oxide-based fine particles obtained by hydrolyzing and polycondensing the alkoxydecane represented by the following general formula (I) in the presence of a basic catalyst component is added to an ultrafiltration device, and the above-mentioned adjustment is carried out. The step of preparing the water-alcohol-based dispersion of the oxidized sand-based fine particles by the content of the basic catalyst component. (b) in the water-alcohol-based dispersion containing the cerium oxide-based fine particles, 'mixes and contains the alkoxy decane represented by the following general formula (I), the halogenated decane represented by the following general formula (11) and a step of selecting at least one aqueous dispersion of the organic cerium compound in the partial hydrolyzate, and (c) heating the mixed liquid at a temperature of 30 to 8 (TC), at least Q, the alkali which is released by the cerium oxide-based fine particles a step of partially hydrolyzing and/or hydrolyzing the aforementioned organoquinone compound

RnSi(〇R,) 4. n . . . . . . . . . (1) R&quot;SiX4. n . . . . . . . . . (II) wherein R is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group, a vinyl group or a phenyl group, and R is a hydrogen atom or An alkyl group, an aryl group, a vinyl group or a phenyl group having 1 to 8 carbon atoms, and X represents an atom. Further, η is an integer of 〇3 to 3). The details of each of the above steps are as follows. -18- 200932847 Step (a) lit &amp; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; The method can employ a previously known method. That is, 1) a method in which an aqueous solution of a basic catalyst component (for example, 'ammonia) is added to a water-alcohol dispersion containing the above-mentioned oxoxane, and the obtained hydrolysis/condensation product is aged. And 2) a method in which the cerium oxide-based fine particles obtained in the above 1) are subjected to hot water treatment in a pressure vessel such as a autoclave and matured. However, the average particle diameter of the above cerium oxide-based fine particles is preferably from 5 to 500 nm. However, in the method of the present invention, it is necessary to adjust the content of the aforementioned basic catalyst component contained in the above cerium oxide-based fine particles. If the specific description about this method is as follows. However, the method of the present invention is not limited to the method described herein. (1) First, a water-alcohol-based dispersion containing cerium oxide-based fine particles obtained by the above method is added to an ultrafiltration device, and its capacity is concentrated from about 1/2 to about 1/5 to remove the dispersion. An unreacted product, an intermediate reactant, and the like of the aforementioned alkoxydecane. At this time, a part of water, an alcohol, and a basic catalyst component (for example, ammonia) contained in the dispersion liquid are removed. (2) Next, adding about 1 to 3 times the volume of pure water (using a temperature of 5 to 25 ° C, the same applies hereinafter) to the water-alcohol-based dispersion obtained in the above (1), stirring, and then adding The ultrafiltration device concentrates the content to about 1 /2 to remove a portion of the alkaline catalyst component contained in the dispersion. Further, -19- 200932847, if necessary, the pure water having the same capacity as the obtained water-alcohol-based dispersion is added and stirred, and then added to the ultrafiltration device and the same operation is repeated. By repeating this operation, the alkali catalyst component can be gradually released into the dispersion liquid from the cerium oxide-based fine particles, so that the content of the basic catalyst component contained in the cerium oxide-based fine particles can be adjusted. The number of times of the above-described operation is different depending on the basic catalyst component contained in the cerium oxide-based fine particles and the content thereof, and the properties of the cerium oxide-based fine particles, but it is preferably carried out 2 to 5 times. (3) Next, in the water-alcohol-based dispersion (low alcohol concentration) obtained in the above (1) or (2), an alcohol of the same capacity (using a temperature of 5 to 25 ° C, the same below) is added and stirred. Thereafter, it is added to the ultrafiltration device to concentrate its capacity to about 1/2, and the water contained in the dispersion is exchanged with the alcohol. Further, if necessary, an alcohol having the same capacity as the obtained water-alcohol-based dispersion is added and stirred, and then added to the ultrafiltration device and the same operation is repeated. By repeating this operation for about 2 to 4 times, the concentration of the alcohol contained in the water-alcohol dispersion can be adjusted to about 60 to 90% by weight. Thus, a water-alcohol dispersion suitable for mixing with the aqueous dispersion of the above organic hydrazine compound is obtained. Further, the concentration of the cerium oxide-based fine particles contained in the water-alcohol dispersion is desirably adjusted to about 5 to 20% by weight. In this manner, a water-alcohol-based dispersion containing oxidized chopped fine particles having a content of the above-mentioned basic catalyst component adjusted to a range of from 200 to 1100 ppm by weight is obtained. However, the necessary amount of the above-mentioned basic catalyst component is the type and amount of the organic ruthenium compound used in the step (b) to be described later, or the catalyst component contained in the dispersion obtained by mixing them in -20-200932847. The type and the content thereof vary, and it is desirable to adjust the content of the basic catalyst component contained in the cerium oxide-based fine particles in the above range in consideration of such conditions. Further, the water-alcohol-based dispersion contains the alkaline catalyst component used in the hydrolysis/polycondensation reaction. In other words, the alkaline catalyst component which is not removed by the above-described ultrafiltration operation and the alkaline catalyst component which is released from the cerium oxide-based fine particles after the completion of the operation are used in the dispersion liquid. The partial hydrolysis and/or hydrolysis reaction carried out in the latter step (b) may be contained as it is. The alkoxysilane to be used in the above step is not particularly limited as long as the cerium oxide-based fine particles can be obtained. However, ethyl decanoate or methyl decanoate is preferably used. Further, as the basic catalyst component, at least one selected from the group consisting of ammonia, ammonium hydroxide, a quaternary ammonium compound, an organic amine and an amine-based coupling agent may be used, and ammonia or ammonium hydroxide is also preferably used. Further, the alcohol may be at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol and n-butanol, and methanol or ethanol is also preferably used. Step (b) In this step, the water-alcohol dispersion containing the cerium oxide-based fine particles obtained in the above step (a) and the alkoxy decane having the following general formula (I), the following general formula An aqueous dispersion of at least one organic hydrazine compound selected from (Π) a halogenated decane and a partial hydrolyzate thereof is mixed. In this manner, a water-alcohol dispersion liquid containing the cerium oxide-based fine particles, the organic hydrazine compound -21 - 200932847 or the like is obtained. Here, the alkoxydecane and/or the halogenated decane are mixed as described above, for example, in the presence of an acidic catalyst component, and may be mixed in advance, and the mixing ratio of the cerium oxide-based fine particles to the organic cerium compound may be 0. The weight of the cerium oxide-based fine particles is represented by A, and the weight of the cerium compound (in terms of SiO 2 basis) is represented by B, and the weight ratio (A/B) thereof is 1/9 to 9/1, preferably 4 The range of /6~6/4 is better. The reason is as described above. Further, in this step, the alkaline catalyst component and/or the acidic catalyst component may be further contained in the dispersion liquid. As described above, the water-alcohol-based dispersion obtained in the above step (a) contains a basic catalyst component. However, when the amount of the basic catalyst component contained in the cerium oxide-based fine particles obtained in the above step (a) is less than the desired amount, the alkaline catalyst component may be externally added to the dispersion. Such cases have the following cases. (1) Water-alcohol-based dispersion of cerium oxide-based fine particles which are subjected to hot water treatment in a pressure vessel such as a autoclave and which is subjected to hydrolysis and polycondensation of the alkoxysilane, and which are aged in a pressure vessel such as a autoclave In the case of the liquid, in this case, since the obtained cerium oxide-based fine particles have a dense structure, the basic catalytic component contained in the cerium oxide-based fine particles is somewhat reduced. (2) cerium oxide-based fine particles obtained by hydrolyzing or polycondensing the alkoxy decane, or further oxidizing and oxidizing the cerium-based fine particles in a pressure vessel such as a autoclave for -22-200932847 When the water-alcohol-based dispersion is subjected to ultrafiltration, different operations (for example, excessive number of operations, etc.) are performed, and the obtained cerium oxide-based fine particles and the alkaline catalyst component contained in the water-alcohol dispersion are used. In the case where the content is more lowered than desired, in this case, the aforementioned alkaline catalyst component must be externally supplemented. Further, in order to form a cerium oxide-based coating having a high film strength, it is desirable to add an acidic catalyst component to the water-alcohol-based dispersion as described above. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Effect of the action of the sensory component, etc. The coating liquid of the ruthenium compound obtained by partial hydrolysis and/or hydrolysis forms a film, and a dense yttrium oxide-based film can be obtained. Further, the basic catalyst component and the acidic catalyst component may be selected from the above materials. ❾ Step (C) In this step, the mixed liquid obtained in the above step (b), that is, the water-alcohol dispersion is heated at a temperature of 30 to 80 ° C, at least the aforementioned alkalinity released by the cerium oxide-based fine particles. The organic hydrazine compound is partially hydrolyzed and/or hydrolyzed by a catalyst component. The mixed liquid of the water-alcohol dispersion liquid varies depending on the basic catalyst component contained in the cerium oxide-based fine particles, but is preferably at a temperature of 30 to 80 ° C, preferably 40 to 70 ° C. Heated in. Here, if the temperature is less than 30 ° C, the release rate of the basic catalyst component contained in the cerium oxide-based fine particles is slow, so that the organic hydrazine compound is partially hydrolyzed and/or hydrolyzed. When the temperature is longer than 80 ° C, the diffusion of the basic catalyst component contained in the cerium oxide-based fine particles is rapidly or rapidly generated, so that the stability of the dispersion liquid is deteriorated, which is not preferable. When the mixed liquid is heated, the alkaline catalyst component contained in the cerium oxide-based fine particles is gradually released from the cerium oxide-based fine particles, but the heating operation may be carried out in stages as occasion demands. Thereby, the organic chopping compound is partially hydrolyzed and/or hydrolyzed on the outer surface of the oxidized chopped fine particles and the inner surface of the pores via the alkaline catalyst component released from the cerium oxide microparticles. An antimony compound which is sufficiently bonded to the above-mentioned cerium oxide-based fine particles is obtained. In this case, the organic hydrazine compound is partially hydrolyzed and/or hydrolyzed via the basic catalyst component contained in the mixed solution. However, in the method of the present invention, it is important that at least the cerium oxide-based fine particles are released. The alkaline catalyst component is partially hydrolyzed and/or hydrolyzed. The water-alcohol dispersion obtained by the treatment is a method known from the prior art, for example, a distillation method using a rotary evaporator, etc., so that the water and the alcohol component contained in the dispersion, and propylene glycol monopropyl ether, propylene glycol monomethyl ether, At least one organic solvent selected from propylene glycol monomethyl ether acetate or the like is subjected to solvent replacement. A specific example (an example of using propylene glycol monopropyl ether (PGP) as an organic solvent for solvent replacement) is shown below. However, the invention is not limited to the methods described herein. (i) The water-alcohol dispersion obtained above was placed in a flask of a rotary evaporator, and propylene glycol monopropyl ether was added to the flask. -24- 200932847 (ii) Next, the rotary evaporator is driven at 50 to 90 ° C', preferably 60 to 80. (: Under temperature conditions, at -0. 05~_〇. 1 MPa, preferably. Hey. 08 ~-O. Under the reduced pressure conditions of IMPa, the flask is rotated at a speed of 30 to 120 rPm, preferably 60 to 90 rpm. If so treated, the water and alcohol contained in the water-alcohol dispersion are evaporated, so that they are cooled and discharged outside the system. (iii) The coating liquid for forming a cerium oxide coating film in which the water and the alcohol are replaced with the propylene glycol monopropyl ether solvent can be obtained by the above operation (ϋ) of continuing the necessary time. In addition, the amount of the ruthenium compound contained in the coating liquid for forming a cerium oxide-based coating film can be adjusted to the above-mentioned desired range. Here, the content of the above-mentioned oxime compound varies depending on the intended use, and when the ruthenium compound is represented by SiO 2 , it is adjusted to 2 to 50% by weight, preferably 1 to 40% by weight based on the weight of the coating liquid. The range is good. [Method of Forming Cerium Oxide Film] In the present invention, the above-described method for forming a cerium oxide-based film by using the coating liquid for forming a cerium oxide-based film can be employed. Again, this previously known method is as follows. (1) After the coating liquid for forming a cerium oxide-based coating film is coated on a substrate, the substrate is heat-treated at a temperature of 80 to 350 ° C, and then at a temperature higher than the aforementioned heating temperature of 340 to 4 50 ° C. The method of calcination. (2) After the coating liquid for forming a cerium oxide-based coating film is applied onto a substrate, the substrate is heat-treated at a temperature of 80 to 350 ° C, and further irradiated with an electron beam, ultraviolet light or microwave to be aged. In the present invention, it is desirable that the properties of the coating liquid for forming a cerium oxide-based coating film and the use thereof are appropriately selected from the previously known methods. Hereinafter, the film forming method will be specifically described by taking the method of the above (1) as an example, but the present invention is not limited thereto. The coating step is generally applied to a coating liquid for forming a coating on a substrate, and a coating method such as a spin coating method, a dip coating method, a roll coating method, a slit coating method, or a transfer method is used. In the present invention, The above-described coating liquid for forming a cerium oxide-based coating film can also be applied by such a conventionally known method. In the case where the coating liquid for coating a film is applied onto a semiconductor substrate, the spin coating method is suitable, and the film thickness is uniform and the dust generation property is excellent. Therefore, in the present invention, a coating method by the spin coating method is preferably used, but in the case of being applied to a semiconductor substrate having a large diameter, a transfer method or the like may be employed. Further, in the present invention, the term "application of a coating liquid on a substrate" includes not only directly coating the coating liquid on a substrate such as a tantalum wafer, but also including the coating liquid. The film is applied over the protective film for semiconductor processing and other films. The heating step is performed on the film coated on the substrate in this manner, and is heat-treated at a temperature of 80 to 35 (at a temperature of rc. Here, if the heat treatment is performed at a temperature exceeding 35 Å, the coating film contains the film The organic solvent is rapidly evaporated, and pores and voids having a larger diameter are formed in the film, so that the film strength is lowered by -26-200932847 degrees. Therefore, the heat treatment is desirably set to a temperature of 80 to 3 50 as needed. The range of °C is increased stepwise. For example, at a temperature of 1 5 〇t for 1 minute, at a temperature of 250 °C for 1 minute, and then for 350. (: a temperature of 1 minute, etc.) When the heat treatment is carried out at a temperature of less than 80 ° C, the organic solvent contained in the coating film is almost completely evaporated, and remains in the film as it is. The heat treatment may not be achieved, and unevenness may occur in the film thickness of the formed film. The heat treatment also varies depending on the film thickness of the film, and is preferably 1 to 10 minutes, preferably 2 to 5 minutes. More and 'this plus The treatment can be carried out under a nitrogen atmosphere of an inert gas or under an air atmosphere, so that the treatment can be carried out for a short period of time at a lower temperature of 350 ° C or lower, so that even in an air atmosphere containing a large amount of oxygen The heat treatment does not cause damage to the metal wiring or the like disposed on the semiconductor substrate due to metal oxidation. Moreover, since the possibility of ingesting a trace amount of oxygen in the film is increased, the processing of the calcination step in the subsequent stage is performed. A cerium oxide-based coating film which is crosslinked by a Si-0-Si bond is formed, and a cerium oxide-based coating film having hygroscopicity (water repellency) and high film strength is easily formed. If the heat treatment is applied as described above, the coating is performed. The organic solvent or the like contained in the film is evaporated and detached, and on the other hand, the yttrium oxide-based film component is polymerized and hardened, and the melt viscosity of the polymer is lowered and the reflow property of the film is increased during heating. As a result, the flatness of the obtained film is improved. Further, it is preferable that the heat treatment is performed by placing the substrate obtained in the coating step on a leaf-type hot plate. -27- 200932847 Calcination step Next, the heat-treated film is subjected to an atmosphere of an inert gas, and calcined at a temperature higher than the aforementioned heating temperature of 340 to 450 ° C. The inert gas is desirably used, and it is desired to use nitrogen gas. It is necessary to add oxygen or air to it, and to use an inert gas containing a small amount of oxygen (for example, about 500 to 10,000 ppm by volume of oxygen) (described in International Publication WO 0 1 /48 8 06 A1, etc.). The calcination temperature is also obtained depending on the properties of the ruthenium compound (that is, the ruthenium oxide-based film component) contained in the coating liquid, and the cerium oxide film having moisture absorption resistance (water repellency) and high film strength is obtained. On, it is expected to be selected from a temperature range of 340 to 450 °C. When the temperature of the calcination treatment is less than 3 to 40 ° C, the formation of the cerium oxide-based coating component is difficult to crosslink before the formation of the cerium oxide-based coating component, so that the coating film having sufficient film strength cannot be obtained, and if the temperature of the calcination treatment is When the temperature exceeds 450 ° C, for example, the aluminum wiring and the copper wiring constituting the semiconductor substrate are oxidized or melted to cause fatal damage to the wiring layer. In addition, the calcination treatment may be carried out depending on the type of the coating liquid for forming a coating film and the film thickness of the coating film, and it is preferably 5 to 90 minutes, preferably 10 to 60 minutes. Further, in the same manner as in the case of the above heating step, the calcination treatment is preferably carried out on a hot plate of a leaf type type. The film thickness of the obtained cerium oxide-based film thus treated is also different depending on the substrate on which the film of -28-200932847 is formed and the use thereof, for example, the substrate (sand wafer) in the semiconductor device is usually 100~ 600 nm' is usually 100 to 10 〇 0 nm between the wiring layers of the multilayer wiring. [The cerium oxide-based coating film] The cerium oxide-based coating film of the present invention can be easily formed by using the above-described coating liquid for forming a cerium oxide-based coating film having a Young's modulus of 3.  Above OGPa, in more detail 5. A high film strength of 0 GPa or more and a low specific dielectric ratio, and excellent surface flatness and crack resistance. Further, in the present invention, the cerium oxide-based fine particles used in the formation of the coating liquid for forming a coating film can be formed into a yang by using a cerium oxide-based fine particle which is hydrothermally treated and cured in a pressure vessel such as a hot pot. The modulus of elasticity is 6. 0GPa or more, more detailed 7. A cerium oxide film having a high film strength of 0 GPa or more. Further, since the cerium oxide-based coating of the present invention is also strong in tensile strength, even if the film thickness of the film is increased, cracking of the film does not occur. In the adjustment step of forming the coating liquid for forming a coating film, the reactant of the organic cerium compound partially hydrolyzed and/or hydrolyzed and the oxidizing agent are partially oxidized by the alkaline catalyst component released from the cerium oxide-based fine particles. The outer surface of the lanthanide microparticles is strongly bonded to the inner surface of the pores. When the film is formed as described above, even if the film is shrunk, the yttrium oxide-based fine particles are not separated, so that a ruthenium-based film having high crack resistance can be formed. Further, according to the coating liquid of the present invention, the surface roughness (Rms) of the film can be easily formed to be 5. Oxide sand with a smooth surface below Onm -29- 200932847 is a film. (The surface roughness is a self-sufficient average roughness of 値 measured by an atomic force microscope AF )), and it is not necessary to perform an honing treatment such as flattening the surface of the film formed on the substrate. Further, pinholes and the like do not occur on the surface of the film. In addition, since the cerium oxide-based coating itself is a coating film having excellent water repellency (hygroscopicity), even if it is placed in an air atmosphere containing saturated steam, the specific dielectric constant is not deteriorated (that is, Further, the yttrium oxide-based coating film is excellent in adhesion to a film surface formed on a semiconductor substrate or the like, and is excellent in chemical resistance such as alkali resistance, and is resistant to oxygen plasma resistance and etching processability. It also has excellent characteristics in the suitability of steps. The coating liquid of the present invention which can form such a cerium oxide-based coating film is used on a semiconductor substrate, on a substrate in which a wiring layer of a multilayer wiring structure, a surface of an element, and/or a bonding portion of a layer are provided, or on the substrate. The yttrium oxide-based film is formed between the plurality of wiring layers provided, and is particularly a yttrium oxide-based Q insulating film. Among them, the coating liquid of the present invention is suitably used for the purpose of forming an insulating film having a film thickness of about 1 to 5 μm. [Measurement Method] Next, the measurement method used in the examples of the present invention will be specifically described below. (1) The average particle size of the cerium oxide-based fine particles is a magnified image of yttrium oxide-based fine particles contained in the water-alcohol dispersion (sample) -30-200932847, with a transmission electron microscope (ΤΕΜ) (曰This photograph of Ding Chou 14 photographed by 1"11 company 11-800) was analyzed by 1^26\automatic image processing analyzer (LUZEX-AP manufactured by Nicole Co., Ltd.), and the yttrium oxide microparticles were calculated using the attached analysis software. (2) The content of the basic catalyst component contained in the cerium oxide-based fine particles (a) In order to measure the water-alcohol dispersion (sample) in which the cerium oxide-based fine particles containing the basic catalytic component are dispersed The total amount of the basic catalyst component (for example, the amount of nitrogen) is added by adding an aqueous sodium hydroxide solution to dissolve the cerium oxide-based fine particles, and the alkaline gas generated by the heating is contained with dilute sulfuric acid (H2S04: 0. 05 Mohr / liter) aqueous solution absorption. Next, 2 to 3 drops of methyl red solution were dropped therefrom, and titrated with an aqueous sodium hydroxide solution (NaO Η: 0·1 mol/liter), and the total amount of the alkaline catalyst component contained in the dispersion was measured. (Q 1 ). (b) Next, the water-alcohol dispersion (sample) was centrifuged at a rotation speed of 3000 rpm (centrifugal concentrator: VS200 1 manufactured by Azuwan Co., Ltd., centrifuge KUBOTA 693 0 manufactured by KUBOTA Co., Ltd.), and the dispersion was placed therein. The cerium oxide-containing fine particles are separated. Next, the amount of the basic catalyst component (for example, the amount of ammonia) contained in the obtained dispersion medium is measured in the same manner as in the above (a), and the total amount of the alkaline catalyst component contained in the dispersion medium is measured (Q2). ). (c) The amount of the alkaline catalyst component (Q2) measured in the above (b) is subtracted from the amount of the organic catalyst component (Q1) measured in (a), and the content of the cerium oxide-based fine particles is calculated. The amount of the basic catalyst component (Q). -31 - 200932847 (3) Measurement of the viscosity of the coating liquid for coating film. Transfer 1 ml of the coating liquid as a sample to a tray of a viscometer (made by Toki Sangyo Co., Ltd., VISCONIC ED type), and let the sample touch the rotation. For the child, measure the torque 値 when the rotator is rotated by the known number of revolutions. Next, the viscosity is calculated from the number of revolutions and the measured moment 値. (4) Measurement of the number average molecular weight of the ruthenium compound The measurement was carried out according to the GPC (Gelph Phase Chromatography) method using a molecular weight measuring device (manufactured by Tosoh Corp.: GPC 8020). In other words, 1 ml of the coating liquid as a sample was placed in a solution and passed through a rubber column (manufactured by Tosoh Corporation: TSKgel, manufactured by Tosoh Corporation: G5000Hxl, TSKgel G3 0 00Hxl), according to the volume of fluid force or the like. The molecular component in the sample was separated in size, and the molecular weight distribution was measured based on the reference refractive index difference at each time. Next, the measured molecular weight distribution was compared with a polystyrene distribution having a known molecular weight measured in advance, and the number average molecular weight converted to polystyrene was calculated. (5) Measurement of ion concentration of the coating liquid for forming a coating film: 10 ml of a coating liquid as a sample and 90 ml of purified pure water were mixed', and the mixture was stirred at room temperature for 1 hour, and then the mixture was filtered and filtered. 100 ml of purified pure water was passed through the filter medium and the filtrate was recovered. Next, the cation concentration of metal ions and the like contained in the recovered filtrate is measured by atomic absorption method, and the anion concentration of the basic catalyst component or the like is measured by ion chromatography-32-200932847 (6) Ratio of cerium oxide-based coating film The dielectric constant is applied as a coating liquid on a crucible wafer by spin coating at a rotational speed of 4000 rPm, and dried at a temperature of 120 ° C for 5 minutes, and then at 350 ° C under a nitrogen atmosphere. The film was calcined at a temperature for 30 minutes to form a coating film (yttrium oxide-based film). Next, it was measured by a mercury probe method (SSM495, manufactured by Solid State Measurements, and a frequency of 1 MHz). In other words, the mercury electrode is brought into contact with the coating film, the voltage is changed, and the capacitance of the coating film is measured, and the specific dielectric constant of the coating film is calculated from the obtained capacitance and film thickness (7) The coating of the cerium oxide-based coating film. The coating liquid as the sample was applied by spin coating on a crucible wafer at a rotational speed of 4000 rpm, and dried at a temperature of 12 (TC for 5 minutes, and then at a temperature of 350 ° C under a nitrogen atmosphere). The film was calcined at a temperature for 30 minutes to form a coating film (yttrium oxide-based film). Secondly, the Young's Modulus was measured according to the nanoindenter method (Nanoindenter XP manufactured by MTS Sysbtms Corp.), that is, the pressure of diamond was pressed. The contact area of the pressure applied to the coating film and the pressing strength are measured, and the Young's modulus is calculated. (8) The crack resistance of the cerium oxide-based coating is limited to the thickness of the coating. The solution was applied by spin coating on a crucible wafer at a rotational speed of 300 to -33 to 200932847 700 rpm, and dried at a temperature of 120 ° C, and calcined at a temperature of 350 ° C for 30 minutes under a nitrogen atmosphere. , (yttrium oxide film). Secondly, the obtained coating film is : 50-fold) was observed, confirming whether the cracks. In addition, according to the film thickness measurement method (SURFCOM manufactured by ACCRETECH Co., Ltd., the thickness of the film which does not cause cracks is measured. ^ (9) The surface roughness of the yttrium oxide-based film is applied to the enamel wafer as a sample. The coating was applied at a rpm of rpm and calcined at a temperature of 305 ° C for 30 minutes (a cerium oxide coating film) under a nitrogen atmosphere at a temperature of 12 TC. Next, the coating film was applied. The probe was scanned by Kanchi Labor (manufactured by Bico, Japan), and the surface roughness (Rms) was observed by the intermolecular force between the probe and the coating film. [Examples] Hereinafter, the present invention will be described in detail based on examples. Invention, but limited by the embodiments. Modulation of cerium oxide microparticles [blending example 1] Modulation 99. 9wt% concentration of methanol (Kantong Chemical 5〇8g and pure water 760g of matrix water 1268g dry for 5 minutes to form a coating film microscope (double contact type difference 1 400D), E coating method, to dry The shape of the coating imparting conductivity NCH-10V was formed for 5 minutes, and the invention was calculated not to be made by this product. Join 9 9. 9 -34- 200932847 1604 g of methanol in weight% concentration and 8452 g of ethyl decanoate (manufactured by Tama Chemical Co., Ltd.) and stirred to prepare 245 g of ethyl citrate solution. Next, 1268 g of the above-mentioned matrix water was heated and maintained at a temperature of 65 ° C, and the aforementioned ethyl citrate solution was used in an amount of 24,500 g and 1. A 99% by weight aqueous ammonia solution of 9490 g was added over 5 hours with stirring. After the end of the addition, the temperature was maintained at the above temperature and the aging operation was carried out for 3 hours. A water-methanol dispersion (hereinafter referred to as "water-methanol dispersion") of 4% by weight of cerium oxide microparticles was 35,258 g. Next, the obtained water-methanol dispersion is cooled to room temperature' and added to a water-methanol dispersion of 31,860 g, 2034 g of pure water is added and stirred, and ultrafiltration is used at a temperature of 25 ° C. Filter paper (Asahi Kasei Co., Ltd., ACP-2013), and its weight was concentrated to 18,711 g. In this manner, 1871 g of a water-methanol dispersion (hereinafter referred to as "water monomethyl alcohol refining liquid") containing the ethyl decanoate unreacted product and the intermediate reactant contained in the water-methanol dispersion was removed. Next, in 10395 g of the water-methanol refining liquid obtained above, 99. After 5% by weight of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), 1 3 860 g, and stirring, the above ultrafiltration filter paper was used under a temperature of 25 t, and the weight was concentrated to 10,395 g. Further, 1 3860 g of ethanol was added to the obtained dispersion and stirred, and the weight was again concentrated to 10,395 g using the above-mentioned ultrafiltration filter paper. In this way, the water-methanol dispersion (hereinafter referred to as "water-ethanol dispersion") containing cerium oxide microparticles was replaced by a solvent to replace the water contained in the water-methanol refinement liquid with methanol. -35 - 200932847 2,703 g of ethanol was added to the water-ethanol dispersion, and the concentration of cerium oxide-based fine particles contained in the dispersion was adjusted to 1% by weight, and then a rotary evaporator (Shibata Scientific Co., Ltd.) was used. RE20EU) is concentrated to obtain 19. A sample of 4% by weight of cerium oxide microparticles in water-ethanol dispersion 1A 675 2 g. When the average particle diameter of the cerium oxide-based fine particles contained in the sample 1 A thus obtained was measured, it was about 20 nm. Further, when the total content of ammonia contained in the sample 1A and the ammonia content contained in the cerium oxide-based fine particles were measured by the above method, the results are shown in Table 1. [Combination Example 2] In the same manner as in the mixing example 1, a water-methanol refining solution of 1 8 7 1 1 g was prepared. Next, 10150 g of the water-methanol refining solution prepared above was taken out, 47 g of a 29% by weight aqueous ammonia solution was added thereto, and the mixture was stirred, and then added to a calender (manufactured by a pressure-resistant glass industry, TAS-13 type), and 150 The temperature of °C was treated for 15 hours, and the cerium oxide microparticles contained in the water-methanol refining liquid were aged. Next, 10045 g of a water-methanol refining solution (aging liquid) obtained by cooling to room temperature was taken out, and 13020 g of pure water was added thereto, and after stirring, an ultrafiltration filter paper was used at a temperature of 25 ° C to concentrate the weight to 9998. Gram. Further, 13 020 g of pure water was added and stirred, and again, the above-mentioned ultrafiltration filter paper was used, and the weight was concentrated to 9998 g twice. Thus, from -36 to 200932847, 9998 g of a water-methanol refining liquid containing a part of ammonia contained in the cerium oxide-based fine particles was removed. Next, in the 99.99 g of the water-methanol refining liquid obtained above, 1 3 3 3 1 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred, and then used at a temperature of 25 ° C. The filter paper was filtered and concentrated to a weight of 9998 g. Further, after adding 13331 g of ethanol and stirring, the weight was again concentrated to 999 8 g using the above-mentioned ultrafiltration filter paper. Thus, 9998 g of a water-ethanol dispersion in which water and methanol contained in the water-methanol dispersion were subjected to solvent exchange was obtained. 2600 g of ethanol was added to the water-ethanol dispersion, and the concentration of the cerium oxide-based fine particles contained in the dispersion was adjusted to 1% by weight, and then concentrated using a rotary evaporator (RE2 0EU manufactured by Shibata Scientific Co., Ltd.). , obtained containing 19. A sample of a water-ethanol dispersion of 4% by weight of cerium oxide microparticles 2A 6494 g. When the average particle diameter of the cerium oxide-based fine particles contained in the sample 2A thus obtained was measured, it was about 25 nm. Further, in the same manner as in the case of the mixing example 1, the total content of ammonia contained in the sample 2A and the ammonia content contained in the cerium oxide-based fine particles were measured by the above-described method, as shown in Table 1. [Example 1] The sample 1A prepared in the mixing example 1 and the sample 2A prepared in the mixing example 2 (water-ethanol dispersion containing 19 to 4% by weight of cerium oxide microparticles) were respectively taken out and 6050 g were taken out. Mixed methyltrimethyl-37- 200932847 Oxydecane (MTMS, Shin-Etsu Chemical Co., Ltd.) 0. 449% by weight of nitric acid (1409 g manufactured by Kanto Chemical Co., Ltd.) and slowly heated from room temperature to 50 ° C while maintaining the temperature (50 ° C) and at a speed of 200 rpm The portion of the methyltrimethoxydecane is 7". When the pH of the mixture is measured at this time, the first sample (before heating) is used, and the nitrate which is an acidic catalyst component is added as ρΗ2·1' but with temperature. Rise and become PH7. 8, under the stability. Further, in the case of using the sample 2A described above, initially (under the influence of the addition of nitric acid as an acidic catalyst component, it becomes PH8 as the temperature rises. In this state, ammonia which is a catalyst component contained in the cerium oxide-based fine particles contained in the above-mentioned sample is known, and contributes to the aforementioned methyltrimethoxy hydrolysis reaction and/or hydrolysis reaction. Next, 'the obtained water-ethanol dispersion is supplied to Rotary Science Co., Ltd. to make RE20EU), and the alcohol and the like in the dispersion are mixed with propylene glycol monopropyl ether (PGP, Japanese emulsifier (stock solvent replacement). The content of the compound in the solvent-replaced PGP solution was adjusted to 25% by weight on the basis of Si〇2, and the coating liquid for spray coating 3A (referred to as sample 3A using the sample 1A) and 4A (using the aforementioned Sample 2A or less is referred to as sample 4 A). The sample thus obtained is placed at room temperature for 1 day and 1778 g of the aqueous solution at 150 ° C. Further, J is stirred for 1 5 k and/or 1 A of water, the most acidic. Under the influence of this state before heating), ρΗ2·4, but the definition. In other words, a partial evaporator (made of water containing wood and B) which is a basic decane is used to form a oxidized product, and the following is prepared, and the coating liquid is confirmed by a viscosity of -38 to 200932847. When the preservation stability is maintained, it is known that there is no change. The properties of the obtained coating liquid for forming a cerium oxide-based coating film are shown in Table 2 [Example 2] The sample 1A prepared in the mixing example 1 and the sample 2A adjusted in the mixing example 2 (all water-ethanol dispersions) The 6050 was taken out separately, and 2,668 g of methyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0. 1691 g of nitric acid (manufactured by Kanto Kasei Co., Ltd.) at a concentration of 44% by weight was slowly heated from room temperature to a temperature of 5 °C. Further, the hydrolysis and/or hydrolysis of the methyltrimethoxydecane was carried out while maintaining the temperature at 50 ° C and stirring at a speed of 200 rpm for 15 hours. When the pH of the mixed solution was measured at this time, it was initially (before heating), and under the influence of nitric acid added as an acidic catalyst component, it was PH2. 3, but as the degree rises, it becomes PH7. 5, and stabilized in this state. In other words, it is known that ammonia which is an alkaline catalyst component is released from the cerium oxide-based fine particles contained in the sample, and contributes to partial hydrolysis and/or hydrolysis reaction of the methyltrimethoxydecane. Next, the obtained water-ethanol dispersion is supplied to a rotary evaporator (RE20EU, manufactured by Tian Science Co., Ltd.), and water and alcohol contained in the dispersion are mixed with propylene glycol monopropyl ether (PGP, Japanese emulsifier). ))) Into the solvent replacement. Furthermore, the content of the chelating agent contained in the PGP solution in which the solvent was replaced was adjusted to 25% by weight on the basis of SiO 2 to obtain a coating liquid 5A for forming an oxon-based coating film (manufactured by using the above-mentioned sample 1A). The temperature of the chemical processing unit is determined by the anti-Chai-Bai-39-200932847 'referred to as sample 5A' and 6A (the sample prepared by using the sample 2A, hereinafter referred to as sample 6A). The sample thus obtained was allowed to stand at room temperature for 150 days, and the storage stability of the coating liquid was confirmed by the viscosity change, and it was found that there was no change. The properties of the obtained coating liquid for forming a cerium oxide-based coating film are shown in Table 2. [Example 3] The sample 2A prepared in Preparation Example 2, and phenyltrimethoxydecane (PhTMS, manufactured by Shin-Etsu Chemical Co., Ltd.) and phenyltrichloromethane (PhTCS, Shin-Etsu Chemical Industry Co., Ltd.) were used. In addition to the methyltrimethoxy decane, the coating liquid 7A for forming an oxidized coating film containing a ruthenium compound containing 25 wt% of a reactant based on S i Ο 2 was obtained in the same manner as in the case of Example 1. (The sample prepared by the above-mentioned sample 2A and phenyltrimethoxydecane is hereinafter referred to as sample 7A) and 8A (manufactured by using the sample 2A and phenyltrichloroethane, hereinafter referred to as sample 8a). When the sample thus obtained was allowed to stand at room temperature for 5 days, and the storage stability of the coating liquid was confirmed by the change in viscosity, it was found that there was no change. The properties of the obtained coating liquid for forming a cerium oxide-based coating film are shown in Table 2. [Comparative Example 1] A water-methanol purified liquid of 9988 g was obtained in the same manner as in the mixing example 1 until the water-methanol purified liquid was obtained. Secondly, in order to reduce the ammonia concentration, once again, add 1 3 3 3 1 g of pure water to the water-methanol refining solution of 9 9 9 g and stir it, then use it at a temperature of 25 ° C -40-200932847 The filter paper was filtered and the weight was concentrated to 9998 g. Next, 1 33 3 1 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred, and the weight was concentrated to 9998 g using an ultrafiltration filter paper at a temperature of 25 °C. Further, after adding 13331 g of ethanol and stirring, the weight was again concentrated to 9998 g using the above-mentioned ultrafiltration filter paper. Thus, 9998 g of a water-ethanol dispersion in which water and methanol contained in the water-methanol refining liquid were replaced with a solvent was obtained. To the water-ethanol dispersion, 2,500 g of ethanol was added, and the concentration of the cerium oxide-based fine particles contained in the dispersion was adjusted to 1% by weight, and then concentrated using a rotary evaporator (RE20EU manufactured by Shibata Scientific Co., Ltd.). , obtained containing 19. Water-ethanol dispersion sample of 4% by weight of cerium oxide microparticles 9A 6494 g ° The average particle diameter of the cerium oxide-based fine particles contained in the sample 9A thus obtained was measured to be about 25 nm. Further, in the same manner as in the case of the mixing example 1, the total content of ammonia contained in the sample 9A and the ammonia content contained in the cerium oxide-based fine particles were measured by the above-described method, as shown in Table 1. The partial hydrolysis and/or hydrolysis of the above methyltrimethoxydecane was carried out in the same manner as in the case of Example 1 except that the above sample 9A was used. The pH of the mixed solution when the sample 9A was used was measured as 'first (before heating), and under the influence of the addition of nitric acid as an acidic catalyst component, it was PH2. 2, but as the temperature rises, the force is gradually increased and becomes ρΗ4·1. That is, it is understood that the amount of ammonia released from the cerium oxide-based fine particles by the basic catalyst component type is insufficient to contribute to the partial hydrolysis of the methyltrimethoxydecane and/or the alkaline contact of the hydrolysis reaction. Less media. Next, the obtained water-ethanol dispersion is supplied to a rotary evaporator (RE20EU manufactured by Shibata Scientific Co., Ltd.), and water and ethanol contained in the dispersion are mixed with propylene glycol monopropyl ether (PGP, Japanese emulsifier). ))) Solvent replacement. Furthermore, the content of the ruthenium compound contained in the PGP solution in which the solvent was replaced was adjusted to 25% by weight on the basis of SiO 2 to obtain a coating liquid for forming a cerium oxide-based film 1 〇A (using the sample 9 A described above) Hereinafter, it is referred to as sample 1 OA ). When the sample thus obtained was allowed to stand at room temperature for 150 days, and the storage stability of the coating liquid was confirmed by the change in viscosity, it was found that there was no change. The properties of the obtained coating liquid for forming a cerium oxide-based coating film are shown in Table 2. [Comparative Example 2] A sample of 18,711 g of a water-methanol purified solution was prepared by the same method as in the mixing example 1 except that the water-methanol refining solution was obtained. Next, 10150 g of the water-methanol refining liquid was taken out. In order to increase the ammonia concentration in the sample, 1 90 g of a 29 wt% aqueous ammonia solution was added to the water-methanol refining solution and stirred, and then added to a hot pot ( Pressure glass industry (stock), TAS-13 type), and 150. (: The temperature was treated for 15 hours, and the cerium oxide microparticles contained in the water-methanol refining liquid were aged. Next, '10-45 g of the water-methanol refining solution (aging liquid) obtained by cooling to room temperature was taken out. Gram, and add pure water 丨3〇2 () grams and stir -42- 200932847, use ultrafiltration filter paper at 25 ° C, the weight is concentrated to 9861 grams. Add 13020 grams of pure water and After stirring, the above-mentioned ultrafiltration filter paper was used, and the weight was concentrated to 9861 g twice by repeating the operation. Thus, 9861 g of a water-methanol refining liquid containing a part of ammonia contained in the cerium oxide-based fine particles was obtained. After adding 13147 g of ethanol (Wako Pure Chemical Industries, Ltd.) to the obtained 9861 g of the water-methanol refining solution obtained above, the mixture was stirred, and then filtered at a temperature of 25 ° C using an ultrafiltration filter paper to concentrate the weight thereof. Up to 9 86 1 g. Further, after adding 13147 g of ethanol and stirring, the ultra-filter paper was used again, and the weight thereof was concentrated to 9 86 1 g. Thus, the water-methanol dispersion was obtained in the above-mentioned manner. Containing water and armor 980 g of a water-ethanol dispersion in which the alcohol was subjected to solvent replacement. 2,654 g of ethanol was added to the water-ethanol dispersion, and the concentration of the cerium oxide-based fine particles contained in the dispersion was adjusted to 10% by weight, and then rotated. The evaporator (RE20EU made by Shibata Science Co., Ltd.) was concentrated to obtain 19. A sample of 4% by weight of cerium oxide microparticles in water-ethanol dispersion 11A 6404 g. When the average particle diameter of the cerium oxide-based fine particles contained in the sample 1 1 A thus obtained was measured, it was about 25 nm. Further, in the same manner as in the case of the blending example 1, the total content of ammonia contained in the sample 11A and the ammonia content contained in the cerium oxide-based fine particles were measured by the above-described method, as shown in Table 1. The partial hydrolysis of the methyltrimethoxydecane and/or the determination of the pH of the mixed solution using the sample 11A in the same manner as in the case of Example 1 were carried out in the same manner as in the case of the above-mentioned sample 1 1 A. Initially (before heating), PH8. 3 ' As the temperature rises and increases slightly to pH 8. 5. Thus, although the same amount of nitric acid as the acidic catalyst is mixed, the initial pH is high, and the reason why the enthalpy is almost completely unchanged is because the amount of ammonia contained in the water-ethanol dispersion of the sample 11A is small. Ammonia is also present as a basic catalyst component in the cerium oxide-based fine particles. Thus, the hydrolysis reaction of the above-mentioned methyldimethoxydecane can be predicted to be excessively carried out via excess ammonia (basic catalyst component). Next, 'the obtained water-ethanol dispersion is supplied to a rotary evaporator (RE20EU, manufactured by Shibata Scientific Co., Ltd.), and the water and ethanol contained in the dispersion are mixed with propylene glycol monopropyl ether (PGP, Japanese emulsifier). ))) Solvent replacement. Furthermore, the content of the ruthenium compound contained in the P GP solution in which the solvent was replaced was adjusted to 25% by weight on the basis of Si 〇 2 to obtain a coating liquid for forming a cerium oxide-based film 1 2 A (using the aforementioned sample 1 1 A) The person to be modulated is hereinafter referred to as sample 1 2A). The sample thus obtained was allowed to stand at room temperature for 150 days, and when the storage stability of the coating liquid was observed, it was found that the gelation state was changed. Thus, it has been found that a water-ethanol dispersion containing cerium oxide-based fine particles having an ammonia content of more than llOOppm and a coating liquid prepared by partially hydrolyzing and/or hydrolyzing alkoxysilane or the like have problems in storage stability. The properties of the obtained coating liquid for forming a cerium oxide-based coating film are shown in Table 2. [Comparative Example 3] -44 - 200932847 The above-mentioned sample 2Α and methyltrimethoxydecane (MTMS, Shin-Etsu Chemical Co., Ltd.) prepared by the mixing example 2 were used, and the aforementioned heating temperatures were 20 ° C (room For the formation of a yttrium oxide-based film containing 25% by weight based on Si〇2, in the same manner as in the case of carrying out the method of "I". Coating liquid i3a (modulated at a heating temperature of 20 ° C, hereinafter referred to as sample i3A) and 14 A (manufactured at a heating temperature of 9 〇 ° C, hereinafter referred to as sample i4A)

Ο When the sample thus obtained was allowed to stand at room temperature for a day and the storage stability of the coating liquid was confirmed by the change in viscosity, it was found that the coating liquid 13A did not change. However, it can be seen that the coating liquid 14A changes to a gel state. In the case where the heating temperature of 90 ° C is used, the ammonia (basic catalyst component) contained in the cerium oxide-based fine particles is released to the outside of the particles in a short period of time, and the hydrolysis of the oxalate or the like is rapidly caused. The reaction is such that the preservation stability of the coating liquid is impaired. The properties of the obtained coating liquid for forming a cerium oxide-based coating film are shown in Table 2. [Example 4 and Comparative Example 4] 5 ml of each of the samples 3 A, 4A, 5A, 6A, 7A, 8A, 10A, and 13A prepared in Examples 1 to 3 and Comparative Examples 1 and 3 was used, and previously known. A spin coating method (manufactured by MIKASA Co., Ltd.: 1H-3 60 S) was dropped on a 6-inch ruthenium wafer substrate, and subjected to coating treatment at 4000 rpm for 20 seconds. This operation is repeated to obtain the substrates 3B, 4B, 5B, 6B, 7B, 8B, 10B, and 13B to which the coating treatment is applied. Next, these -45 - 200932847 substrates were placed on a hot plate (EC-1200, manufactured by IUCHI Co., Ltd.) and heat-treated at 120 ° C for 5 minutes under atmospheric atmosphere. In this heat treatment step, since the organic solvent (PGP) or the like contained in the film evaporates, it is discharged outside the system. Further, the substrates were placed on a hot plate, and the treatment environment was changed from a gaseous atmosphere to a nitrogen atmosphere, and calcination was carried out at 350 ° C for 30 minutes. Next, the substrates are cooled to a temperature close to room temperature and then removed from the system. The film thickness of the cerium oxide-based film formed on the obtained substrate was about 500 nm. Next, the specific dielectric constant, the film strength (Young's modulus) and the surface roughness of the cerium oxide-based coating formed on the substrate were measured by the above method. The results of the measurements are shown in Table 3. [Example 5 and Comparative Example 5] 5 ml of each of the samples 3 A, 4A, 5A, 6A, 7A, 8A, 10A, and 13A prepared in Examples 1 to 3 and Comparative Examples 1 and 3 was used, and previously known. A spin coating method (manufactured by MIKASA Co., Ltd.: 1H-360S) was dropped on a 6-inch ruthenium wafer substrate, and subjected to a coating treatment at 200 rpm to 700 rpm for 20 seconds. This operation is repeated to obtain substrates 3C, 4C, 5C, 6C, 7C, 8C, 10C, and 13C to which coating treatment is applied. Next, the substrates were placed on a hot plate (EC-1200, manufactured by IUCHI Co., Ltd.) and heat-treated at 120 °C for 5 minutes in an air atmosphere. In this heat treatment step, the organic solvent (-46-200932847 PGP) contained in the film is evaporated, so that it is discharged outside the system. Further, the substrates were placed on a leaf-type hot plate, and the treatment environment was changed to a nitrogen atmosphere under an air atmosphere, and calcination was carried out at 350 ° C for 30 minutes. Next, the substrates are cooled to a temperature close to room temperature and removed from the system. The critical film thickness at which the cerium oxide-based coating obtained by the calcination was not subjected to cracking was measured by the above method. The measurement results are shown in Table 4» Using the above results (Table 3 and Table 4), using Example i

When the coating liquid samples 3A, 4A, 5A, 6A, 7A, and 8A prepared by D to 3 are obtained, the Young's modulus of elasticity is 6. OGP a or more with high film strength and low specific dielectric ratio. And an excellent yttrium oxide-based film such as surface flatness or crack critical film thickness. On the other hand, in the case of using the coating liquid sample 10A prepared in Comparative Example 1, the critical film thickness of the crack was remarkably lowered, and the film strength was also lowered. The amount of the above-mentioned basic catalyst component contained in the cerium oxide-based fine particles in the water-oxygen alcohol dispersion sample 9A used in the preparation of the coating liquid sample 10A is small, and thus contributes to the aforementioned methyltrimethoxy group. The cerium oxide-based fine particles of the basic catalyst of the partial hydrolysis reaction and/or the hydrolysis reaction of decane are less released, and the partial hydrolysis and/or hydrolysis by the organic hydrazine compound is insufficiently combined with the cerium oxide-based fine particles. Further, in the case of using the coating liquid sample 1 3 A prepared in Comparative Example 3, it was found that the critical film thickness of the crack was remarkably lowered, and the film strength was also lowered. Since the heating temperature is as low as 2 (TC), the alkaline catalyst component contained in the cerium oxide-based fine particles in the water-ethanol dispersion sample 2A used in the coating liquid sample 13A is prepared as described in -47-200932847. The cerium oxide-based fine particles are not sufficiently released, and the partial hydrolysis and/or hydrolysis of the organic cerium compound is insufficiently combined with the cerium oxide-based fine particles. [Table 1] The total amount of ammonia contained in the water-ethanol dispersion sample number sample ( Weight ppm) Amount of nitrogen contained in cerium oxide-based fine particles (ppm by weight) Blending Example 1 1A 420 400 Blending Example 2 2A 700 670 Comparative Example 1 9A 100 90 Comparative Example 2 11A 1400 1200 [Table 2] Coating liquid sample number Viscosity after preparation of water-ethanol dispersion (mPa · s) Viscosity after 150 days (mPa · s) SX Η λι J Example 1 3A 1A 2450 7.2 7.3 4A 2A 2730 7.4 7.4 Example 2 5A 1A 2520 7.5 7.6 6A 2A 2810 7.3 7.3 Example 3 7A 2A 2940 7.7 7.8 8A 2A 2980 7.8 7.9 Comparative Example 1 10A 9A 2010 4.5 4.5 Comparative Example 2 12A 11A 6200 10.2 Measurement Impossible Comparative Example 3 13A 2A 2240 4.4 4.4 14A 2A 5920 9.8 It is impossible -48- 200932847 [Table 3] Coating liquid sample number substrate sample number ratio dielectric ratio film strength (GPa) surface accuracy (nm) Example 4 3Α 3Β 3.9 6.9 4.3 4Α 4Β 3.7 7.8 4.5 5Α 5Β 3.7 6.7 4.1 6Α 6Β 3.5 7.0 4.1 7Α 7Β 3.7 7.3 4.5 8Α 8Β 3.7 7.2 4.4 Comparative Example 4 10Α 10Β 3.8 5.8 4.2 13Α 13Β 3.8 5.9 4.3 Ο [Table 4] Coating liquid sample number Substrate sample number Crack critical film thickness (μ m) Example 5 3A 3C 3.5 4A 4C 4.0 5A 5C 3.2 6A 6C 3.3 7A 7C 4.2 8A 8C 4.3 Comparative Example 5 10A 10C 2.4 13A 13C 2.5 ❹ -49-

Claims (1)

200932847 X. Patent application scope Ο 1. A coating liquid for forming a cerium oxide-based coating film, which comprises an alkoxy decane represented by the following general formula (I), which is represented by the following general formula (II) Heating at least one organic hydrazine compound selected from the halogenated decane and a partial hydrolyzate thereof, and a dispersion of cerium oxide-based fine particles containing a basic catalyst component, and at least the aforementioned alkaline catalyst component released from the cerium oxide-based fine particles The hydrazine compound obtained by partially hydrolyzing and/or hydrolyzing the above organic hydrazine compound, RnSi(OR,)4-n (...) RnSiX4.n (... II) (wherein R is a hydrogen atom, a fluorine atom, or a carbon number of 1 to 8, a fluorine-substituted alkyl group, an aryl group, a vinyl group or a phenyl group, and R is a hydrogen atom, or An alkyl group, an aryl group, a vinyl group or a phenyl group having 1 to 8 carbon atoms, and X is a halogen atom; and η is an integer of 0 to 3). 2. The coating liquid for forming a cerium oxide-based coating film according to the first aspect of the invention, wherein the dispersion liquid is a water-alcohol-based dispersion liquid containing water and an alcohol. The coating liquid for forming a cerium oxide-based coating film according to any one of the above-mentioned claims, wherein the dispersion liquid further contains a basic catalyst component and/or an acidic catalyst component. 4. The coating liquid for forming a cerium oxide-based coating film according to any one of the items 1 to 3, wherein the alkaline catalyst component is ammonia, ammonium hydroxide, a quaternary ammonium compound, or an organic amine. And at least one of the amine coupling agents is selected. 5. The coating of the cerium oxide-based coating film according to the third application of the patent scope is -50- ❹ 200932847 cloth 'liquid' wherein the aforementioned acidic catalyst component is made of nitric acid, hydrochloric acid, Select at least one of the acids. 6. The coating liquid for an oxidized sand-based coating film according to any one of the first to fifth aspects of the present invention, wherein the alkoxy decane represented by the general formula (I) is present in the alkalinity. Hydrolysis. Polycondensation of the obtained cerium oxide microparticles, and adjusting the amount of the basic catalyst component contained in the microparticles, RnSi(〇R,)4.n (...) (1) Wherein 'R is a hydrogen atom, a fluorine atom, or a carbon number!~' A fluorine-substituted alkyl group, an aryl group, a vinyl group or a phenyl group, R, a group, or an alkyl group having 1 to 8 carbon atoms, Base, vinyl or phenyl; 〇~3 integer). The coating liquid for a cerium oxide-based coating film according to any one of the first to sixth aspects of the invention, wherein the cerium oxide-based fine particles are in an amount of from 200 to 11 parts by weight in terms of the basic catalyst component. 8. The coating liquid for a cerium oxide-based coating film according to any one of the above-mentioned items, wherein the cerium compound is an organic cerium compound containing the basic catalyst released from the cerium oxide-based fine particles. Partially hydrolyzed and/or hydrolyzed reactants and lanthanide microparticles, and at least a portion of the foregoing reactants are the outer surface of the bound lanthanide microparticles and the inner surface of the pores. 9. The coating liquid for a cerium oxide-based coating film according to any one of the above-mentioned claims, wherein the cerium compound is the basic catalyst component contained in the dispersion liquid and/or the acetic acid and The formation of the sulfur term is such that the lower catalyst component oxidizes the alkyl group of 8 to represent the hydrogen atom, and the η is formed by the formation of the inclusion term having at least a portion, and the former oxidation to the formation of the oxygen term is By hydrolyzing and/or hydrolyzing the above-mentioned organic hydrazine compound, the above-mentioned basic catalyzed component of the above-mentioned cerium-containing fine particles and the aforementioned cerium-based fine particles are exemplified by the precursor catalyst-51 - 200932847 The reactants and the pre-cerium oxide-based fine particles, and at least a part of the reactants are bonded to the outer surface of the cerium oxide-based fine particles and the inner surface of the pores. The coating liquid for a cerium oxide-based coating film according to any one of the preceding claims, wherein the cerium compound has a number average molecular weight of from 500 to 5,000 on the basis of the converted polyethylene. The coating liquid for a cerium oxide-based coating film according to any one of the preceding claims, wherein the coating liquid contains an ion concentration of 1.0 mmol/L or less. 1 2 - a method for preparing a coating liquid for forming a cerium oxide-based film, comprising: (a) hydrolyzing and polycondensing an alkoxy decane represented by the following general formula (I) in the presence of an alkaline medium component The water-based dispersion of the obtained cerium oxide-based fine particles is added to an ultrafiltration device, and the water-alcohol-based dispersion containing the cerium oxide-based fine particles contained in the alkaline catalyst component is adjusted, and (b) the oxidation is contained in the foregoing The water-alcohol dispersion of the cerium-based fine particles is mixed with the alkoxy decane represented by the following general formula (I), and the halogenated decane represented by the following formula (II) and a partial hydrolyzate thereof are selected to have at least one organic substance. a step of dispersing the aqueous dispersion of the compound, (c) heating the mixture at a temperature of 30 to 80 t: to the above-mentioned organic catalyst compound, which is partially hydrolyzed by the aforementioned oxidized sand microparticles And/or hydrolysis. Step RnSi(OR')4-n .........(I) -52- 200932847 RnSiX4_n ... (II) (wherein 'R Is a hydrogen atom, a fluorine atom, or a carbon number of 88, a fluorine-substituted alkyl group, an aryl group, a vinyl group or a phenyl group. , R, is a table, or an alkyl group having a carbon number of 1 to 8 'aryl 'vinyl or phenyl, 7K halogen atom; further, η is an integer of 0 to 3) The obtained hydrazine compound is treated. 1 3. A method for preparing a cerium oxide-based coating liquid according to the second aspect of the patent application, wherein the content of the basic catalyst component contained in the cerium microparticles before the step (a) is 200 to 1 The range of ppm. 1 4 · If you apply for a patent range! The method for preparing a coating liquid for a cerium oxide-based coating film according to any one of the items 2 to 3, wherein the dispersion liquid prepared by the above-mentioned and the above further contains a basic catalyst or an acidic catalyst component. The method for preparing a coating liquid for a cerium oxide-based coating according to any one of the first to fourth aspects of the invention, wherein the alkali component is ammonia ammonium hydroxide, a quaternary ammonium compound, or an organic At least one of the amine and the mixture is selected. The method for preparing a cerium oxide-based coating liquid according to the invention of claim 14, wherein the acidic catalyst component is at least one selected from the group consisting of nitric acid, acetic acid and sulfuric acid. 17. A cerium oxide-based coating film, which is characterized in that the film forming liquid is coated on the substrate, and the film forming liquid is dried and calcined to have a high film strength and a lower alkane. The hydrogen group X is a shape of the surface of the film which is oxidized by 100 weights&gt; (b ζ 及 / / / 形 形 形 形 形 形 形 形 53 53 53 53 53 53 53 53 53 53 53 53 53 53 - 200932847 rate ' is excellent in surface flatness and crack resistance. 18. The cerium oxide-based coating according to claim 17, wherein the cerium oxide-based coating contains a partial hydrolysis and/or hydrolysis of the organic cerium compound. At least a part of the reactant is a polycondensate of a ruthenium compound which is bonded to the outer surface of the ruthenium oxide-based fine particles and the inner surface of the pores thereof. 1 9. As in any one of the claims 17 to 18 The oxidized cerium-based coating film, wherein the cerium oxide-based coating film has a film strength of Young's modulus 〇 3.0 GPa or more. 20. Oxidation according to any one of claims 17 to 99 Lanthanide film, wherein the aforementioned A cerium oxide-based coating having a smooth surface (Rms) of 5.0 nm or less having a smooth surface. The cerium oxide-based coating according to any one of claims 17 to 20, wherein The yttrium oxide-based coating film is a yttrium oxide-based insulating film. Ο -54 - 200932847 VII. Designation of representative drawings: (1) The representative representative figure of this case is: None (2), the representative symbol of the representative figure is a simple description: None 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4-