CN103193477A - Dielectric film forming composition, dielectric film forming method and dielectric film - Google Patents
Dielectric film forming composition, dielectric film forming method and dielectric film Download PDFInfo
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Abstract
The invention provides a dielectric film forming composition, a dielectric film forming method and a dielectric film formed through the method, wherein the dielectric film forming composition includes no substances causing the environmental pollution, can be used for making the dielectric film suitable for a film capacitor through a simple method, and has an excellent stability and a good film coating property. The liquid dielectric film forming composition is used for forming a film of a compound metal oxide having a general formula of Ca(4-3x)Cu3xTi4O12 (x is not lower than 0.5 and not greater than 1.1), and is characterized in that the composition is formed by an organic metal compound solution formed through dissolving raw materials forming the compound metal oxide in an organic solvent according to a ratio providing the metal atom ratio in the general formula, and the organic solvent treats carboxylic acid having a general formula of CnH2n+1COOH (n is an integer in a range of 2-6) and having a straight chain or one or more than two side chains as a main component.
Description
Technical field
The present invention relates to a kind of not comprising the bigger material of the load of environment and the dielectric film that is suitable for film capacitor be formed with the formation method of composition, dielectric film and the dielectric film that forms by this method.
Background technology
In the past, form as dielectric film and to use composition, for example use barium titanate series composition or lead is ferroelectric materials such as composite perofskite based material always.
On the other hand, in recent years, movement of environmental protection in the world is constantly under the surging situation, and the expectation exploitation does not comprise dielectric film to the novelty of the bigger Ba of the load of environment or Pb and forms and use composition.
In addition, when the dielectric film that comprises Ba, Pb etc. when manufacturing forms and to use composition, for the consideration to environmental protection, therefore the specific installations such as treatment facility that need handle the waste liquid that produces in manufacturing process also require to develop the dielectric film that does not comprise these materials and form and use composition aspect manufacturing cost.
Form as the above-mentioned dielectric film that does not comprise the novelty of the bigger material of the load of environment and use composition, delivered following research contents, namely utilize and used the sol-gel liquid in Ca source, Cu source and Ti source, from this sol-gel liquid making CaCu
3Ti
4O
12(hereinafter referred to as CCTO) film, and the research (for example with reference to non-patent literature 1) that the characteristic of resulting CCTO film is investigated.In this non-patent literature 1, each element source is dissolved in prepares sol-gel liquid in the organic solvent, make the CCTO film by the spin-coating method that utilizes this sol-gel liquid, utilized 2 ethyl hexanoic acid as the organic solvent that in the preparation of sol-gel liquid, uses.
In addition, consider than resistance characteristic from it that CCTO can also be used as gas sensor material (for example referring to Patent Document 1).In this patent documentation 1, each element source is dissolved in the organic solvent, further add acetic acid and prepare sol-gel liquid as the catalyzer that is used for sol gel reaction, make the nanofiber that is constituted by CCTO by the electrical spinning method that utilizes this sol-gel liquid, and it is carried out the incompatible gas sensor of having made of thermo-compressed.
Patent documentation 1: No. 4523582 communique of Japanese Patent (claim 2, paragraph [0027], [0069], [0070])
Non-patent literature 1:A.Dixit et al., " Dielectric Properties of Sol-gel-derived Calcium Copper Titanate and Calcium Barium Copper Titanate Thin Films ", Defence Science Journal, Vol.57, No.1, January2007, pp.55-60
But, the CCTO film that is shown in the above-mentioned non-patent literature 1 in the past has good dielectric property as dielectric materials, but in the sol-gel liquid that 2 ethyl hexanoic acid is prepared as organic solvent, there is following shortcoming, namely when film forming, produce and film inhomogeneous (striped), can not get the shortcoming of level and smooth film and so on.
And, the nanofiber that is made of CCTO that is shown in the above-mentioned patent documentation 1 in the past has the highly sensitive characteristic as the gas sensor material, but utilize acetic acid as Preparation of Catalyst its precursor be sol-gel solution, acetic acid makes the deterioration of filming property, and it is inhomogeneous that film coated surface is produced, therefore the keeping quality of sol-gel solution is also relatively poor, causes generating precipitation, therefore can not be referred to as to be fit to obtain the sol-gel liquid of level and smooth film.
Summary of the invention
The object of the present invention is to provide and a kind ofly do not comprise the bigger material of the load of environment and can enough simple methods make the dielectric film that is suitable for film capacitor and excellent storage stability, the good dielectric film of filming property form with the formation method of composition, dielectric film and the dielectric film that forms by this method.
The 1st viewpoint of the present invention, namely a kind of dielectric film forms and uses composition, is general formula for being used to form: Ca
(4-3x)Cu
3xTi
4O
12The aqueous dielectric film of the film of the complex metal oxides form shown in (0.5≤x in the formula≤1.1) forms uses composition, by constituting with the organometallic compound solution that the ratio that the atoms metal ratio shown in the above-mentioned general formula is provided is dissolved in organic solvent for the raw material that constitutes complex metal oxides, described organic solvent is to have general formula: C
nH
2n+1Straight chain shown in the COOH (wherein n is 2～6 integer) or the carboxylic acid of 1 or 2 above side chain are principal constituent.
The 2nd viewpoint of the present invention, namely based on the invention of the 1st viewpoint, wherein, the raw material that is used for the above-mentioned complex metal oxides of formation further is that organic group is by the compound of its Sauerstoffatom or nitrogen-atoms and metallic element bonding.
The 3rd viewpoint of the present invention, namely based on the invention of the 1st or the 2nd viewpoint, wherein, be used for constituting the raw material of above-mentioned complex metal oxides further for being selected from metal alkoxide, metal two alcohol complexs, metal trivalent alcohol complex compound, metal carboxylate, metal beta-diketon complex compound, metal beta-diketon ester complex compound, metal β-imino-ketone complex compound and more than a kind or 2 kinds of metal amino complex compound.
The 4th viewpoint of the present invention, namely based on the invention of the 1st to the 3rd viewpoint, wherein, with respect to 1 mole of the total amount in the above-mentioned composition, further contain the stablizer more than a kind or 2 kinds that further is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, oxygen acid, glycol, trivalent alcohol, high carboxylic acid, alkanolamine and the polyamine with the ratio below 3 moles.
The 5th viewpoint of the present invention, namely based on the invention of the 1st to the 4th viewpoint, wherein, carboxylic acid as the principal constituent of above-mentioned organic solvent further is propionic acid, butanic acid, isopropylformic acid, positive valeric acid, isovaleric acid, 2-Methyl Butyric Acid, trimethylacetic acid, n-caproic acid, 2 Ethylbutanoic acid, 2, the 2-acid dimethyl, 3, the 3-acid dimethyl, 2, the 3-acid dimethyl, 3 methylvaleric acid, the 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, the 4-methylhexanoic acid, the 5-methylhexanoic acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 4-ethyl valeric acid, 2,2-dimethyl valeric acid, 3,3-dimethyl valeric acid, 4,4-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2,4-dimethyl valeric acid, 3,4-dimethyl valeric acid, 2,2,3-trimethylammonium butyric acid or 2,3,3-trimethylammonium butyric acid.
The 6th viewpoint of the present invention, namely based on the invention of the 1st to the 5th viewpoint, wherein, at least a in Ca source or the Cu source further is acetate.
The 7th viewpoint of the present invention, namely based on the invention of the 1st to the 5th viewpoint, wherein, at least a in Ca source or the Cu source further is naphthenate.
The 8th viewpoint of the present invention, namely based on the invention of the 1st to the 7th viewpoint, wherein, the Ti source further is tetraisopropoxy titanium.
The 9th viewpoint of the present invention, it is a kind of formation method of dielectric film, wherein, to form based on the dielectric film of the 1st to the 8th viewpoint and coat on the heat resistant substrate with composition, carry out once in air, in the oxidizing atmosphere or the operation that heats in the containing water vapor atmosphere or repeat this operation up to the film that obtains desired thickness, at least in the end adding in the operation, pine for or heat and then burn till this film with the temperature more than the crystallized temperature.
The 10th viewpoint of the present invention, the i.e. dielectric film that forms by the method based on the 9th viewpoint.
The 11st viewpoint of the present invention, it is a kind of combined electronical assembly with film capacitor, laminate film electrical condenser, integrated passive devices (IPD, Integrated Passive Device), DRAM storer electrical condenser, cascade capacitor, transistorized gate insulator or LC noise filter element based on the dielectric film of the 10th viewpoint.
In the 1st viewpoint of the present invention, a kind of dielectric film forms and uses composition, is general formula for being used to form: Ca
(4-3x)Cu
3xTi
4O
12The aqueous dielectric film of the film of the complex metal oxides form shown in (0.5≤x in the formula≤1.1) forms uses composition, it is characterized in that, by constituting with the organometallic compound solution that the ratio that the atoms metal ratio shown in the above-mentioned general formula is provided is dissolved in organic solvent for the raw material that constitutes complex metal oxides, described organic solvent is to have general formula: C
nH
2n+1Straight chain shown in the COOH (wherein n is 2～6 integer) or the carboxylic acid of 1 or 2 above side chain are principal constituent.Be above-mentioned general formula: Ca
(4-3x)Cu
3xTi
4O
12The CCTO film formation of the complex metal oxides form shown in (0.5≤x in the formula≤1.1) does not comprise with liquid composition makes the dielectric film that is suitable for film capacitor to the load of environment bigger material and the enough simple methods of energy.And, by with above-mentioned general formula: C
nH
2n+1Carboxylic acid shown in the COOH (wherein n is 2～6 integer) is as organic solvent, and filming in the time of can preventing from forming dielectric film is inhomogeneous, and, even the film formation of taking care of for a long time before film forms can not generate precipitation with composition yet.
Embodiment
Below explanation is used for implementing mode of the present invention.
It is not comprise the bigger material of the load of environment and be used to form the liquid composition of the dielectric film that is suitable for film capacitor that dielectric film of the present invention forms with composition.The dielectric film that utilizes said composition to form is general formula: Ca
(4-3x)Cu
3xTi
4O
12Complex metal oxides form shown in (0.5≤x in the formula≤1.1).By with general formula: Ca
(4-3x)Cu
3xTi
4O
12X be located in the above-mentioned scope, the dielectric film of formation can obtain higher relative permittivity.In addition, if general formula: Ca
(4-3x)Cu
3xTi
4O
12X less than 0.5 or x surpass 1.1, the unfavorable condition that the relative permittivity of the dielectric film that forms diminishes then takes place.Said composition is made of with the organometallic compound solution that the mode of ratio that the atoms metal ratio that provides shown in the above-mentioned general formula is provided is dissolved in organic solvent the raw material that is used for constituting complex metal oxides.
Complex metal oxide raw material is best to be the compound that organic group passes through each metallic element bonding of its Sauerstoffatom or nitrogen-atoms and Ca, Cu and Ti.For example, can enumerate be selected from metal alkoxide, metal two alcohol complexs, metal trivalent alcohol complex compound, metal carboxylate, metal beta-diketon complex compound, metal beta-diketon ester complex compound, metal β-imino-ketone complex compound and the metal amino complex compound more than a kind or 2 kinds.Especially Zui Jia compound is metal alkoxide, its partial hydrolystate and organic alkoxide.Wherein, as Ca compound, Cu compound, acetate, naphthenate, methyl cellosolve be can enumerate, acetate, naphthenate most preferably are.And, as the Ti compound, can enumerate tetraisopropoxy titanium.Metal alkoxide can directly use, and also can use its partial hydrolystate in order to promote to decompose.
Form and use composition in order to prepare dielectric film of the present invention, with these raw materials with the ratio solvent that is equivalent to desirable dielectric film and forms in organic solvent, be prepared into and be fit to the concentration that is coated with.
At this, the organic solvent that dielectric film forms with composition uses to have general formula: C
nH
2n+1Straight chain shown in the COOH (wherein n is 2～6 integer) or the carboxylic acid of 1 or 2 above side chain are the organic solvent of principal constituent.Constitute or with the organic solvent of above-mentioned carboxylic acid as principal constituent by using by above-mentioned carboxylic acid, can prevent when utilizing in the past composition to come film forming, produce, film inhomogeneously during coating, can obtain level and smooth film.And, constitute or with the organic solvent of above-mentioned carboxylic acid as principal constituent, the storage stability of organometallic compound solution also improves by using by above-mentioned carboxylic acid.
In addition, when using general formula: C
nH
2n+1When the n of COOH was 1 carboxylic acid (acetic acid), the deterioration of filming property produced inhomogeneously in film coated surface, and the keeping quality of composition is also relatively poor, causes generating precipitation.When using general formula: C
nH
2n+1When the n of COOH was carboxylic acid more than 7, following unfavorable condition took place too, i.e. filming property deterioration, and be that keeping quality also worsens in a part of carboxylic acid in the carboxylic acid more than 7 at n, cause generating precipitation.
Carboxylic acid as the principal constituent of organic solvent, can enumerate propionic acid, butanic acid, isopropylformic acid, positive valeric acid, isovaleric acid, 2-Methyl Butyric Acid, trimethylacetic acid, n-caproic acid, 2 Ethylbutanoic acid, 2, the 2-acid dimethyl, 3, the 3-acid dimethyl, 2, the 3-acid dimethyl, 3 methylvaleric acid, the 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, the 4-methylhexanoic acid, the 5-methylhexanoic acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 4-ethyl valeric acid, 2,2-dimethyl valeric acid, 3,3-dimethyl valeric acid, 4,4-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2,4-dimethyl valeric acid, 3,4-dimethyl valeric acid, 2,2,3-trimethylammonium butyric acid or 2,3,3-trimethylammonium butyric acid.
In addition, dielectric film formation preferably is made as about 0.1～20 quality % in metal oxide conversion amount with the total concentration of the organometallic compound in the organometallic compound solution of composition.
In this organometallic compound solution, can add in (stablizer molecule number)/(atoms metal number) about 0.2～3 as required, beta-diketon class (methyl ethyl diketone for example, 2,2-dimethyl-6,6,7,7,8,8,8-seven fluoro-3,5-acetyl caproyl (Heptafluorobutanoyl pivaloylmethane), dipivaloylmethane(DPVM), trifluoroacetylacetone, benzoyl acetone etc.), beta-keto acid class (acetoacetic acid for example, propionyl acetic acid, benzoylacetic acid etc.), 'beta '-ketoester class (the methyl of above-mentioned ketone acid for example, propyl group, lower alkyl esters classes such as butyl), oxygen acid class (lactic acid for example, oxyacetic acid, the Alpha-hydroxy butyric acid, Whitfield's ointment etc.), the lower alkyl esters class of above-mentioned oxygen acid, hydroxyl ketone (diacetone alcohol for example, 3-oxobutanol etc.), glycol, trivalent alcohol, alkanol amine (diethanolamine for example, trolamine, monoethanolamine) and polyamine etc. as stablizer.
Among the present invention, preferably carry out filtration treatment etc. by the organometallic compound solution to above-mentioned preparation and remove particle, and the number of the particle of particle diameter 0.5 μ m above (particularly more than the 0.3 μ m, especially more than the 0.2 μ m) is made as 50 of every 1mL solution/below the mL.
If being the number of the above particle of 0.5 μ m, the particle diameter in the organometallic compound solution surpasses 50/mL, then prolonged preservation bad stability.Particle diameter in this organometallic compound solution is that the number of the above particle of 0.5 μ m is more few more good, especially preferred 30/below the mL.
There is no particular limitation with the method for the organometallic compound solution after the mode Processing of Preparation that becomes above-mentioned particle number, for example, can enumerate following method.The 1st method: using commercially available aperture is the membrane filter of 0.2 μ m and the filtration method that pushes with syringe.The 2nd method: making up commercially available aperture is the membrane filter of 0.05 μ m and the pressure filtration method of pressurized tank.The 3rd method: make up the strainer that uses in above-mentioned the 2nd method and the circulating filtration method of solution circulated groove.
In any method all because of the particle catch rate difference of solution squeeze pressure based on strainer.Usually the more low catch rate of known pressure more uprises, and especially, in order to realize the particle number more than the particle diameter 0.5 μ m is made as condition below 50 in the 1st method, the 2nd method, preferably makes solution pass through strainer very lentamente with low pressure.
The dielectric film of the application of the invention forms and uses composition, can form the CCTO dielectric film that is the complex metal oxides form simply.
Form the CCTO dielectric film in order to use dielectric film of the present invention to form with composition, by coating methods such as spin-coating method, dip coating, LSMCD (liquid source atomizing electroless plating Liquid Source Misted Chemical Deposition) methods above-mentioned composition is coated on the heat resistant substrate, carried out drying (temporarily burning till) and formally burn till.
As the object lesson of employed heat resistant substrate, can enumerate in the substrate skin section and use single crystalline Si, polycrystalline Si, Pt, Pt (the superiors)/Ti, Pt (the superiors)/Ta, Ru, RuO
2, Ru (the superiors)/RuO
2, RuO
2(the superiors)/Ru, Ir, IrO
2, Ir (the superiors)/IrO
2, Pt (the superiors)/Ir, Pt (the superiors)/IrO
2, SrRuO
3Or (La
xSr
(1-x)) CoO
3Deng the substrate of perovskite typed electroconductive oxide etc., but be not limited to these.
In addition, when repeating repeatedly to be coated with 1 coating obtain desired thickness the time, formally burning till after the drying process.At this, the thickness of the dielectric film that desired thickness obtains after referring to formally burn till, the thickness of the dielectric film after formally burning till is the scope of 50～1000nm.
And, burn till temporarily and make organometallic compound thermolysis or hydrolysis change into composite oxides when removing solvent to carry out, so in air, in the oxygen atmosphere or carry out in the containing water vapor atmosphere.Even if airborne heating also can fully be guaranteed the moisture that hydrolysis is required according to airborne moisture.This heating can be implemented by 2 stages that are used for removing the low-temperature heat of solvent and being used for the heat of decomposition organometallic compound.
Formally burn till is for burning till with the temperature more than the crystallized temperature burn till the film that obtains and make the operation of its crystallization temporarily, can obtaining dielectric film thus.Firing atmosphere the best of this crystallization step is O
2, N
2, Ar, N
2O or H
2Deng or their mixed gas etc.
Burn till temporarily and carrying out under 150～550 ℃ about 5～10 minutes, formally burn till and carrying out about 1～60 minute under 600～800 ℃.Formally burn till and to handle (RTA processing) with rapid heating and carry out.When formally burning till with the RTA processing, its heat-up rate is preferably 10～100 ℃/second.
The dielectric film of the present invention of Xing Chenging does not comprise the material bigger to the load of environment like this, as the fundamental characteristics excellence of electrical condenser, is suitable for film capacitor or laminate film electrical condenser.And dielectric film of the present invention is also excellent as the fundamental characteristics of IPD.
And dielectric film of the present invention can be used as the constituent material in the combined electronical assemblies such as IPD, DRAM storer electrical condenser, cascade capacitor, transistorized gate insulator or LC noise filter element.
[embodiment]
Below together describe embodiments of the invention in detail with comparative example.
＜embodiment 1 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.
Use this film to form and use solution, carry out formation based on the film of CSD method by following method.That is, be coated with for 3 seconds by spin-coating method with 500rpm, afterwards under 3000rpm, the condition in 20 seconds with solution coat on substrate.Substrate has used 6 inches silicon substrate (Pt/TiO that form the Pt film with sputtering method on the surface
2/ SiO
2/ Si (100) substrate).Then, utilize hot-plate to heat down at 350 ℃ burnt till in 5 minutes temporarily.Repeating 5 times is somebody's turn to do after coating, the interim firing process, in 100% oxygen atmosphere by heat-up rate be 10 ℃/second, to keep temperature be 700 ℃ and hold-time to be that 1 minute RTA (rapid heating processings) burns till, and is the dielectric film of 300nm at substrate formation thickness.
＜embodiment 2 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.
Use this film to form and use solution, carry out formation based on the film of CSD method by following method.That is, be coated with for 3 seconds by spin-coating method with 500rpm, afterwards under 3000rpm, the condition in 20 seconds with solution coat on substrate.Substrate has used 6 inches silicon substrate (Pt/TiO that form the Pt film with sputtering method on the surface
2/ SiO
2/ Si (100) substrate).Then, utilize hot-plate to heat down at 350 ℃ burnt till in 5 minutes temporarily.Repeating 5 times is somebody's turn to do after coating, the interim firing process, in dry air atmosphere by heat-up rate be 10 ℃/second, to keep temperature be 700 ℃ and hold-time to be that 1 minute RTA (rapid heating processings) burns till, and is the dielectric film of 300nm at substrate formation thickness.
＜embodiment 3 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 4 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 5 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 6 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 7 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 8 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 9 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the propionic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 10 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the butanic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 11 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the isopropylformic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 12 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the positive valeric acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 13 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the isovaleric acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 14 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2-Methyl Butyric Acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 15 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the trimethylacetic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 16 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the n-caproic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 17 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as 2 of organic solvent, the 2-acid dimethyl.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 18 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 3 methylvaleric acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 19 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 4-methylvaleric acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 20 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the naphthenic acid ketone in copper source, as the tetraisopropoxy titanium in titanium source and as the positive enanthic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 21 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the naphthenic acid ketone in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 methyl caproic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 22 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium naphthenate, as the naphthenic acid ketone in copper source, as the tetraisopropoxy titanium in titanium source and as the 5-methylhexanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 23 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2-ethyl valeric acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 24 〉
At first, shown in the following tabulation 1, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 4-ethyl valeric acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 25 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the naphthenic acid ketone in copper source, as the tetraisopropoxy titanium in titanium source and as 2 of organic solvent, 2-dimethyl valeric acid.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 26 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as 2 of organic solvent, 4-dimethyl valeric acid.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 27 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the naphthenic acid ketone in copper source, as the tetraisopropoxy titanium in titanium source and as 4 of organic solvent, 4-dimethyl valeric acid.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 28 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source dimethoxy-ethanol calcium, as the dimethoxy-ethanol ketone in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2/2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.67) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 29 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source dimethoxy-ethanol calcium, as the dimethoxy-ethanol ketone in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 30 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source dimethoxy-ethanol calcium, as the dimethoxy-ethanol ketone in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.7/3.3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜embodiment 31 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), be the carboxylic acid mixed solvent of equivalent as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as organic solvent propionic acid and 2 Ethylbutanoic acid are mixed into the molar ratio computing.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜embodiment 32 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, be the carboxylic acid-alcohol mixed solvent of equivalent as the naphthenic acid ketone in copper source, as the tetraisopropoxy titanium in titanium source and as organic solvent 2 Ethylbutanoic acid and propyl carbinol are mixed into the molar ratio computing.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 1 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 2 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 3 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 4 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 5 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 6 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 7 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 8 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 Ethylbutanoic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 9 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the propionic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 10 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the butanic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 11 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the isopropylformic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 12 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the positive valeric acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 13 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the isovaleric acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 14 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2-Methyl Butyric Acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 15 〉
At first, shown in the following tabulation 2, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the trimethylacetic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 16 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the n-caproic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 17 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as 2 of organic solvent, the 2-acid dimethyl.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 18 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 3 methylvaleric acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 19 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 4-methylvaleric acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 20 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the positive enanthic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 21 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 methyl caproic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 22 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the 5-methylhexanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 23 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2-ethyl valeric acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 24 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 4-ethyl valeric acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 25 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as 2 of organic solvent, 2-dimethyl valeric acid.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=0.4/3.6/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1.2) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 26 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as 2 of organic solvent, 4-dimethyl valeric acid.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 27 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as 4 of organic solvent, 4-dimethyl valeric acid.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=2.8/1.2/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=0.4) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 28 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the acetic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 29 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the acetic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 30 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the n-caprylic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 31 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the n-caprylic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 32 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the n-caprylic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 33 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the n-caprylic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 34 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the pelargonic acid of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 35 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium naphthenate, as the copper naphthenate in copper source, as the tetraisopropoxy titanium in titanium source and as the pelargonic acid of organic solvent.And, prepare diethanolamine as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 2 in addition and form dielectric film at substrate.
＜comparative example 36 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the 2 ethyl hexanoic acid of organic solvent.Secondly, add calcium source, copper source and titanium source, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
＜comparative example 37 〉
At first, shown in the following tabulation 3, prepare respectively as the calcium source calcium acetate (monohydrate), as the neutralized verdigris (monohydrate) in copper source, as the tetraisopropoxy titanium in titanium source and as the p-Xylol of organic solvent.And, prepare methyl ethyl diketone as the stablizer that is used for stabilizing solution.Secondly, add calcium source, Tong Yuan, titanium source and stablizer, become Ca/Cu/Ti=1/3/4 (general formula: Ca with each metal ratio
(4-3x)Cu
3xTi
4O
12X=1) mode, under nitrogen atmosphere, in the organic solvent, be heated into 150 ℃ and reflux, obtain thus forming and using composition with the convert film of counting 10 quality % concentration of oxide compound.Carry out in the same manner with embodiment 1 in addition and form dielectric film at substrate.
[table 1]
[table 2]
[table 3]
＜comparison test and evaluation 〉
At the substrate that is formed with the dielectric film that in embodiment 1～32 and comparative example 1～37, obtains, use metal mask to make the Pt upper electrode of 250 μ m from the teeth outwards with sputtering method, between the Pt lower electrode under the dielectric film, in the scope inner evaluation C-V of-5～5V characteristic (the voltage interdependence of electrostatic capacity), go out relative permittivity ε r according to the maximum value calculation of electrostatic capacity with the 1kHz frequency.In addition, the mensuration of relevant C-V characteristic, the 4284A precision LCR meter that uses Hewlett-Packard Corporation to make measures under the condition of Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, 23 ℃ of Delay time 0.2sec, Temperature, Hygrometry 50 ± 10%.
And, at the dielectric film that in embodiment 1～32 and comparative example 1～37, obtains, have or not striped (it is inhomogeneous to film) with the range estimation judgement.With this as the evaluation of filming property.
And the part that the film that will obtain in embodiment 1～32 and comparative example 1～37 forms with composition is sealed in the reagent bottle, in keeping 5 ℃ refrigerating chamber after the keeping 3 months, has or not with the range estimation judgement and to precipitate.With this as estimation of stability.
These be the results are shown in down in the tabulation 4～table 6.In addition, in the filming property evaluation in table 4～table 6, be used as during the film surface smoothing of the whole base plate after covering is burnt till that not produce crawling even and be made as " well ", the film surface that covers the whole base plate after burning till island, striated etc. and film air spots occur and is used as when sliding and produces crawling and spare and be made as " bad ".And, in the estimation of stability, be not made as " well " when producing precipitation in the reagent bottle after the refrigeration keeping, be made as when producing precipitation " bad ".
[table 4]
[table 5]
[table 6]
As from table 4～table 6 as can be known, with general formula: Ca
(4-3x)Cu
3xTi
4O
12Shown x is 0.4 the cooperation that Ca is more and Cu is less or general formula: Ca
(4-3x)Cu
3xTi
4O
12Shown x is that the dielectric film of the comparative example 1～27 of the less and cooperation that Cu is more of 1.2 Ca is compared, at general formula: Ca
(4-3x)Cu
3xTi
4O
12Shown x is in the dielectric film of 0.67～1.1 embodiment 1～32 and comparative example 28～37, has obtained the result that electrostatic capacity is higher and relative permittivity is higher.From this results verification to, general formula: Ca
(4-3x)Cu
3xTi
4O
12There is the scope that shows good dielectric property among the shown x.
Yet, in embodiment 1～32 and the comparative example 28～37, with acetic acid as the comparative example 28 of organic solvent, 29 and with n-caprylic acid or pelargonic acid, 2 ethyl hexanoic acid, p-Xylol as in the comparative example 30～37 of organic solvent, produced when forming dielectric film film inhomogeneous.And, with acetic acid as the comparative example 28,29 of organic solvent, with n-caprylic acid as the comparative example 30～32 of organic solvent and with p-Xylol as in the comparative example 37 of organic solvent, the film of taking care of for a long time before film forms forms with the generation of having found precipitation after the composition.On the other hand, among the embodiment 1～32, both do not produced film inhomogeneous, and, take care of film for a long time and form with also generating precipitation after the composition.From this results verification to, have also excellent compound of the good and storage stability of filming property in the organic solvent that in the CCTO film forms with composition, uses, can pass through general formula of the present invention: C
nH
2n+1The filming when carboxylic acid shown in the COOH (wherein n is 2～6 integer) prevents from forming dielectric film as organic solvent is inhomogeneous, and, even the film formation of taking care of for a long time before film forms can not generate precipitation with composition yet.
And, in the dielectric film of embodiment 1～32, if be conceived to use methyl cellosolve as the dielectric film of the embodiment 28～30 in calcium source and copper source, find that then electrostatic capacity and relative permittivity all are worse than a little except using acetate or naphthenate as the tendency of the dielectric film of the embodiment 1～8 that makes with roughly the same condition calcium source and the copper source.From this results verification to, if with acetate or naphthenate as calcium source and Tong Yuan, then can make the dielectric film that electrostatic capacity is higher and relative permittivity is higher.
And, in the dielectric film of embodiment 1～32, use the dielectric film of embodiment 31 of the mixed solvent of 2 kinds of carboxylic acids as organic solvent, as organic solvent use the dielectric film of carboxylic acid and the embodiment 32 of ethanol mixed solvent obtain with except use single solvent as organic solvent with electrostatic capacity and the relative permittivity of the dielectric film same degree of the embodiment 1～9 of roughly the same condition manufacturing, from this results verification to, be not limited to the organic solvent that the single solvent by the carboxylic acid shown in the above-mentioned general formula constitutes, even for mixing mixed solvent or the carboxylic acid shown in the above-mentioned general formula and the mixed solvent of other solvents of the carboxylic acid shown in the multiple above-mentioned general formula, as long as the carboxylic acid shown in the above-mentioned general formula can be as the principal constituent of organic solvent, filming in the time of also can preventing from forming dielectric film is inhomogeneous, and, even the film formation of taking care of for a long time before film forms can not generate precipitation with composition yet.
Utilizability on the industry
Dielectric film of the present invention forms with the formation method of composition, dielectric film and passes through the dielectric film that this method forms, it does not comprise the material bigger to the load of environment, and as the fundamental characteristics excellence of electrical condenser, can be used in the purposes of film capacitor or laminate film electrical condenser.In addition, its fundamental characteristics as IPD is also excellent, can be used in combined electronical assemblies such as IPD, DRAM storer electrical condenser, cascade capacitor, transistorized gate insulator or LC noise filter element.
Claims (11)
1. a dielectric film forms and uses composition, it is characterized in that, is general formula for being used to form: Ca
(4-3x)Cu
3xTi
4O
12The aqueous dielectric film of the film of shown complex metal oxides form forms uses composition, in the formula, and 0.5≤x≤1.1,
By constituting with the organometallic compound solution that the ratio that the atoms metal ratio shown in the above-mentioned general formula is provided is dissolved in organic solvent for the raw material that constitutes described complex metal oxides, described organic solvent is to have general formula: C
nH
2n+1The carboxylic acid of the straight chain shown in the COOH or 1 or 2 above side chain is principal constituent, and wherein, n is 2～6 integer.
2. dielectric film as claimed in claim 1 forms and uses composition, wherein,
The raw material that is used for the described complex metal oxides of formation is the compound that organic group passes through its Sauerstoffatom or nitrogen-atoms and metallic element bonding.
3. dielectric film as claimed in claim 1 or 2 forms and uses composition, wherein,
The raw material that is used for the described complex metal oxides of formation is to be selected from metal alkoxide, metal two alcohol complexs, metal trivalent alcohol complex compound, metal carboxylate, metal beta-diketon complex compound, metal beta-diketon ester complex compound, metal β-imino-ketone complex compound and more than a kind or 2 kinds of metal amino complex compound.
4. dielectric film as claimed in claim 1 forms and uses composition, wherein,
With respect to 1 mole of the total amount in the described composition, further contain the stablizer more than a kind or 2 kinds that is selected from beta-diketon, beta-keto acid, 'beta '-ketoester, oxygen acid, glycol, trivalent alcohol, high carboxylic acid, alkanolamine and the polyamine with the ratio below 3 moles.
5. dielectric film as claimed in claim 1 forms and uses composition, wherein,
Carboxylic acid as the principal constituent of described organic solvent is propionic acid, butanic acid, isopropylformic acid, positive valeric acid, isovaleric acid, 2-Methyl Butyric Acid, trimethylacetic acid, n-caproic acid, 2 Ethylbutanoic acid, 2, the 2-acid dimethyl, 3, the 3-acid dimethyl, 2, the 3-acid dimethyl, 3 methylvaleric acid, the 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, the 4-methylhexanoic acid, the 5-methylhexanoic acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 4-ethyl valeric acid, 2,2-dimethyl valeric acid, 3,3-dimethyl valeric acid, 4,4-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2,4-dimethyl valeric acid, 3,4-dimethyl valeric acid, 2,2,3-trimethylammonium butyric acid or 2,3,3-trimethylammonium butyric acid.
6. dielectric film as claimed in claim 1 forms and uses composition, wherein,
At least a in Ca source or the Cu source is acetate.
7. dielectric film as claimed in claim 1 forms and uses composition, wherein,
At least a in Ca source or the Cu source is naphthenate.
8. dielectric film as claimed in claim 1 forms and uses composition, wherein,
The Ti source is tetraisopropoxy titanium.
9. the formation method of a dielectric film is characterized in that,
Each described dielectric film formation in the claim 1 to 8 is coated on the heat resistant substrate with composition, carry out once in air, in the oxidizing atmosphere or the operation that heats in the containing water vapor atmosphere or repeat this operation up to the film that obtains desired thickness, at least in the end adding in the operation, pine for or heat and then burn till this film with the temperature more than the crystallized temperature.
10. dielectric film, this dielectric film forms by the described method of claim 9.
11. combined electronical assembly with film capacitor, laminate film electrical condenser, integrated passive devices, DRAM storer electrical condenser, cascade capacitor, transistorized gate insulator or LC noise filter element of the described dielectric film of claim 10.
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