CN103193477B - Dielectric film forms the formation method and dielectric film of using composition, dielectric film - Google Patents

Dielectric film forms the formation method and dielectric film of using composition, dielectric film Download PDF

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CN103193477B
CN103193477B CN201210003035.1A CN201210003035A CN103193477B CN 103193477 B CN103193477 B CN 103193477B CN 201210003035 A CN201210003035 A CN 201210003035A CN 103193477 B CN103193477 B CN 103193477B
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acid
source
dielectric film
organic solvent
film
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CN103193477A (en
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藤井顺
樱井英章
曽山信幸
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Mitsubishi Materials Corp
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Abstract

The invention provides and a kind ofly do not comprise the larger material of the load of environment and can make by simple method the dielectric film that is suitable for film capacitor and the formation method of the good dielectric film formation composition of excellent storage stability, film, dielectric film and the dielectric film that formed by the method.A kind of aqueous dielectric film formation composition, for the formation of being general formula: Ca (4-3x)cu 3xti 4o 12the film of the complex metal oxides form shown in (in formula 0.5≤x≤1.1), it is characterized in that, be made up of with the organo-metallic solutions providing the ratio of the ratio of the atoms metal shown in above-mentioned general formula and be dissolved in organic solvent the raw material for forming this complex metal oxides, described organic solvent is to have general formula: C nh 2n+1the carboxylic acid of the straight chain shown in COOH (wherein n be 2 ~ 6 integer) or more than 1 or 2 side chain is principal constituent.

Description

Dielectric film forms the formation method and dielectric film of using composition, dielectric film
Technical field
The present invention relates to a kind of not comprising the larger material of the load of environment and the dielectric film being suitable for the dielectric film formation composition of film capacitor, the formation method of dielectric film and being formed by the method.
Background technology
In the past, as dielectric film formation composition, use the such as ferroelectric material such as barium titanate series composition or lead system composite perofskite based material always.
On the other hand, in recent years, when movement of environmental protection is in the world constantly surging, expect that exploitation does not comprise the dielectric film formation composition of the novelty to larger Ba or Pb of the load of environment.
In addition, when manufacture comprises the dielectric film formation composition of Ba, Pb etc., for the consideration to environmental protection, need specific installations such as the treatment facilities that the waste liquid produced in manufacturing process processes, therefore also require to develop the dielectric film formation composition not comprising these materials in manufacturing cost.
As the above-mentioned dielectric film formation composition not comprising novelty to the larger material of the load of environment, deliver following research contents, namely utilized the sol-gel liquid in the Ca source that employs, Cu source and Ti source, make CaCu from this sol-gel liquid 3ti 4o 12(hereinafter referred to as CCTO) film, and to the research (such as with reference to non-patent literature 1) that the characteristic of obtained CCTO film is investigated.In this non-patent literature 1, each element source being dissolved in organic solvent and preparing sol-gel liquid, by utilizing the spin-coating method of this sol-gel liquid to make CCTO film, make use of 2 ethyl hexanoic acid as the organic solvent used in the preparation of sol-gel liquid.
In addition, consider from its ratio resistance characteristic, CCTO can also be used as gas sensor material (such as referenced patent document 1).In this patent documentation 1, each element source is dissolved in organic solvent, add acetic acid further as the catalyzer for sol gel reaction and prepare sol-gel liquid, by utilizing the electrical spinning method of this sol-gel liquid to make the nanofiber be made up of CCTO, and it is carried out to thermo-compressed is incompatible has manufactured gas sensor.
Patent documentation 1: Japanese Patent No. 4523582 publication (claim 2, paragraph [0027], [0069], [0070])
Non-patent literature 1:A.Dixitetal., " DielectricPropertiesofSol-gel-derivedCalciumCopperTitana teandCalciumBariumCopperTitanateThinFilms ", DefenceScienceJournal, Vol.57, No.1, January2007, pp.55-60
But, the CCTO film be shown in 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 produce film uneven (striped) when film forming, can not get the shortcoming of level and smooth film and so on.
And, the nanofiber be made up of CCTO be shown in above-mentioned patent documentation 1 in the past has highly sensitive characteristic as gas sensor material, but utilized acetic acid as catalyst preparing its precursor and sol-gel solution, acetic acid makes film worsen, and it is uneven to make film coated surface produce, therefore the keeping quality of sol-gel solution is also poor, causes generating precipitation, therefore can not be referred to as the sol-gel liquid being applicable to obtaining 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 larger material of the load of environment and can make by simple method the dielectric film that is suitable for film capacitor and the formation method of the good dielectric film formation composition of excellent storage stability, film, dielectric film and the dielectric film that formed by the method.
1st viewpoint of the present invention, i.e. a kind of dielectric film formation composition, for for the formation of in general formula: Ca (4-3x)cu 3xti 4o 12the aqueous dielectric film formation composition of the film of the complex metal oxides form shown in (in formula 0.5≤x≤1.1), be made up of with the organo-metallic solutions providing the ratio of the ratio of the atoms metal shown in above-mentioned general formula and be dissolved in organic solvent the raw material for forming complex metal oxides, described organic solvent is to have general formula: C nh 2n+1the carboxylic acid of the straight chain shown in COOH (wherein n be 2 ~ 6 integer) or more than 1 or 2 side chain is principal constituent.
2nd viewpoint of the present invention, namely based on the invention of the 1st viewpoint, wherein, for form above-mentioned complex metal oxides raw material further for organic group is by the compound of its Sauerstoffatom or nitrogen-atoms and metallic element bonding.
3rd viewpoint of the present invention, namely based on the invention of the 1st or the 2nd viewpoint, wherein, the raw material for forming above-mentioned complex metal oxides is one kind or two or more for what be selected from metal alkoxide, metal two alcohol complex, metal trivalent alcohol complex compound, metal carboxylate, metal p-diketonates complex compound, metal p-diketonates ester complex compound, metal β-imino-ketone complex compound and metal amino complex compound further.
4th viewpoint of the present invention, namely based on the invention of the 1st to the 3rd viewpoint, wherein, relative to the total amount in above-mentioned composition 1 mole, with the ratio of less than 3 moles further containing the one kind or two or more stablizer be selected from further in beta-diketon, beta-keto acid, 'beta '-ketoester, oxygen acid, glycol, trivalent alcohol, high carboxylic acid, alkanolamine and polyamine.
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 is propionic acid further, butanic acid, isopropylformic acid, positive valeric acid, isovaleric acid, 2-Methyl Butyric Acid, trimethylacetic acid, n-caproic acid, 2 Ethylbutanoic acid, 2, 2-acid dimethyl, 3, 3-acid dimethyl, 2, 3-acid dimethyl, 3 methylvaleric acid, 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-ethylpentanoic, 3-ethylpentanoic, 4-ethylpentanoic, 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.
6th viewpoint of the present invention, namely based on the invention of the 1st to the 5th viewpoint, wherein, at least one in Ca source or Cu source is acetate further.
7th viewpoint of the present invention, namely based on the invention of the 1st to the 5th viewpoint, wherein, at least one in Ca source or Cu source is naphthenate further.
8th viewpoint of the present invention, namely based on the invention of the 1st to the 7th viewpoint, wherein, Ti source is tetraisopropoxy titanium further.
9th viewpoint of the present invention, a kind of i.e. formation method of dielectric film, wherein, dielectric film formation composition based on the 1st to the 8th viewpoint is coated on heat resistant substrate, carry out once in atmosphere, in oxidizing atmosphere or the operation heated in containing water vapor atmosphere or repeat this operation until obtain the film of desired thickness, adding at least in the end in operation hankers or burn till this film with temperature more than crystallized temperature after heating.
10th viewpoint of the present invention, the dielectric film namely by being formed based on the method for the 9th viewpoint.
11st viewpoint of the present invention, i.e. a kind of film capacitor, laminate film electrical condenser, integrated passive devices (IPD, IntegratedPassiveDevice), DRAM storer electricity container, cascade capacitor, the gate insulator of transistor or combined electronical assembly of LC noise filter element with dielectric film based on the 10th viewpoint.
In the 1st viewpoint of the present invention, a kind of dielectric film formation composition, for for the formation of in general formula: Ca (4-3x)cu 3xti 4o 12the aqueous dielectric film formation composition of the film of the complex metal oxides form shown in (in formula 0.5≤x≤1.1), it is characterized in that, be made up of with the organo-metallic solutions providing the ratio of the ratio of the atoms metal shown in above-mentioned general formula and be dissolved in organic solvent the raw material for forming complex metal oxides, described organic solvent is to have general formula: C nh 2n+1the carboxylic acid of the straight chain shown in COOH (wherein n be 2 ~ 6 integer) or more than 1 or 2 side chain is principal constituent.In above-mentioned general formula: Ca (4-3x)cu 3xti 4o 12the CCTO film formation liquid composition of the complex metal oxides form shown in (in formula 0.5≤x≤1.1) does not comprise the larger material of the load of environment and can make by simple method the dielectric film being suitable for film capacitor.Further, by by above-mentioned general formula: C nh 2n+1carboxylic acid shown in COOH (wherein n be 2 ~ 6 integer) is used as organic solvent, and film when forming dielectric film can be prevented uneven, and, even if long-term keeping film formed before film-forming composition also can not generate precipitation.
Embodiment
Below illustrate for implementing mode of the present invention.
Dielectric film formation composition of the present invention is not comprise the larger material of the load of environment and for the formation of the liquid composition of dielectric film being suitable for film capacitor.The dielectric film utilizing said composition to be formed is general formula: Ca (4-3x)cu 3xti 4o 12complex metal oxides form shown in (in formula 0.5≤x≤1.1).By by general formula: Ca (4-3x)cu 3xti 4o 12x be located in 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 more than 1.1, then the unfavorable condition that the relative permittivity of dielectric film occurring to be formed diminishes.The organo-metallic solutions that said composition is dissolved in organic solvent in the mode becoming the ratio providing the ratio of the atoms metal shown in above-mentioned general formula by the raw material for forming complex metal oxides is formed.
The best compound passing through each metallic element bonding of its Sauerstoffatom or nitrogen-atoms and Ca, Cu and Ti for organic group of complex metal oxide raw material.Such as, be selected from metal alkoxide, metal two alcohol complex, metal trivalent alcohol complex compound, metal carboxylate, metal p-diketonates complex compound, metal p-diketonates ester complex compound, metal β-imino-ketone complex compound and metal amino complex compound one kind or two or more can be enumerated.Especially best compound is metal alkoxide, its partial hydrolystate and organic alkoxide.Wherein, as Ca compound, Cu compound, acetate, naphthenate, methyl cellosolve can be enumerated, most preferably be acetate, naphthenate.Further, as Ti compound, tetraisopropoxy titanium can be enumerated.Metal alkoxide can directly use, and also can use its partial hydrolystate to promote to decompose.
In order to prepare dielectric film formation composition of the present invention, by these raw materials to be equivalent to the ratio solvent of desired dielectric film composition in organic solvent, be prepared into the concentration being applicable to coating.
At this, the organic solvent of dielectric film formation composition uses to have general formula: C nh 2n+1the carboxylic acid of the straight chain shown in COOH (wherein n be 2 ~ 6 integer) or more than 1 or 2 side chain is the organic solvent of principal constituent.State by using to be made up of or more above-mentioned carboxylic acid the organic solvent that carboxylic acid is principal constituent, can prevent to produce when utilizing composition in the past to carry out film forming, coating time film uneven, level and smooth film can be obtained.Further, state by using to be made up of or more above-mentioned carboxylic acid the organic solvent that carboxylic acid is principal constituent, the storage stability of organo-metallic solutions also improves.
In addition, as use general formula: C nh 2n+1when the n of COOH is carboxylic acid (acetic acid) of 1, film worsens, and produce uneven, and the keeping quality of composition is also poor in film coated surface, causes generating precipitation.As use general formula: C nh 2n+1when the n of COOH is the carboxylic acid of more than 7, following unfavorable condition occurs too, namely film worsens, and is that in a part of carboxylic acid in the carboxylic acid of more than 7, keeping quality also worsens at n, causes generating precipitation.
As the carboxylic acid of the principal constituent of organic solvent, propionic acid can be enumerated, butanic acid, isopropylformic acid, positive valeric acid, isovaleric acid, 2-Methyl Butyric Acid, trimethylacetic acid, n-caproic acid, 2 Ethylbutanoic acid, 2, 2-acid dimethyl, 3, 3-acid dimethyl, 2, 3-acid dimethyl, 3 methylvaleric acid, 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-ethylpentanoic, 3-ethylpentanoic, 4-ethylpentanoic, 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, the total concentration of the organometallic compound in the organo-metallic solutions of dielectric film formation composition is preferably set to about 0.1 ~ 20 quality % with metal oxide conversion gauge.
In this organo-metallic solutions, can add in (stablizer molecule number)/(metal raw subnumber) about 0.2 ~ 3 as required, beta-diketon class (such as methyl ethyl diketone, 2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8-seven fluoro-3, 5-acetyl caproyl (Heptafluorobutanoylpivaloylmethane), dipivaloylmethane(DPVM), trifluoroacetylacetone, benzoyl acetone etc.), beta-keto acid class (such as acetoacetic acid, propionyl acetic acid, benzoylacetic acid etc.), 'beta '-ketoester class (the such as methyl of above-mentioned ketone acid, propyl group, the lower alkyl esters classes such as butyl), oxygen acid class (such as lactic acid, oxyacetic acid, alpha-hydroxybutyric acid, Whitfield's ointment etc.), the lower alkyl esters class of above-mentioned oxygen acid, hydroxyl ketone (such as diacetone alcohol, 3-Hydroxybutanone etc.), glycol, trivalent alcohol, alkanol amine (such as diethanolamine, trolamine, monoethanolamine) and polyamine etc. as stablizer.
In the present invention, particle is removed preferably by carrying out filtration treatment etc. to the organo-metallic solutions of above-mentioned preparation, and the number of the particle of particle diameter more than 0.5 μm (particularly more than 0.3 μm, especially more than 0.2 μm) is set to every 1mL solution 50/below mL.
If the particle diameter in organo-metallic solutions be the number of the particle of more than 0.5 μm more than 50/mL, then long-term storing stability be deteriorated.Particle diameter in this organo-metallic solutions is that the number of the particle of more than 0.5 μm is more few better, especially preferably 30/below mL.
There is no particular limitation for the method for the organo-metallic solutions after preparing with the mode process becoming above-mentioned particle number, such as, can enumerate following method.1st method: use commercially available aperture be 0.2 μm membrane filter and with syringe extruding filtration method.2nd method: combining commercially available aperture is the membrane filter of 0.05 μm and the compression filtration of pressurized tank.3rd method: the circulating filtration method combining strainer and the solution circulated groove used in above-mentioned 2nd method.
All different based on the particle catch rate of strainer because of Solution extrusion pressure in any one method.The lower catch rate of usual known pressure more uprises, and especially, in order to realize the condition particle number of particle diameter more than 0.5 μm being set to less than 50 in the 1st method, the 2nd method, preferably makes solution slowly pass through strainer with low pressure.
The dielectric film formation composition of the application of the invention, can form the CCTO dielectric film in complex metal oxides form simply.
In order to use dielectric film formation composition of the present invention to form CCTO dielectric film, by coating methods such as spin-coating method, dip coating, LSMCD (liquid source misted chemical deposition LiquidSourceMistedChemicalDeposition) methods, above-mentioned composition is coated on heat resistant substrate, carry out drying (temporarily burning till) and formally burn till.
As the object lesson of used heat resistant substrate, can enumerate and use single crystalline Si, polycrystalline Si, Pt, Pt (the superiors)/Ti, Pt (the superiors)/Ta, Ru, RuO in substrate skin section 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 desired thickness cannot be obtained with 1 coating, repeat repeatedly to be coated with, formally burn till after drying process.At this, the thickness of the dielectric film that desired thickness obtains after referring to and formally burning till, the thickness of the dielectric film after formally burning till is the scope of 50 ~ 1000nm.
Further, burn till to make organometallic compound thermolysis or hydrolysis become composite oxides to carry out the while of removing solvent temporarily, thus in atmosphere, in oxygen atmosphere or carry out in containing water vapor atmosphere.Even if the heating in air also can according to the moisture in air fully guarantee be hydrolyzed needed for moisture.This heating can be implemented by the low-temperature heat for removing solvent with for 2 stages of the heat of decomposing organometallic compound.
Formally burn till is for burning till the film that obtains in burning till with temperature more than crystallized temperature and make the operation of its crystallization, can obtain dielectric film thus temporarily.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 carry out about 5 ~ 10 minutes at 150 ~ 550 DEG C, formally burn till and carry out about 1 ~ 60 minute at 600 ~ 800 DEG C.Formally burn till and can carry out with rapid heating process (RTA process).When formally burning till with RTA process, its heat-up rate is preferably 10 ~ 100 DEG C/sec.
The dielectric film of the present invention of such formation does not comprise the material larger to the load of environment, and the fundamental characteristics as electrical condenser is excellent, 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.
Further, dielectric film of the present invention can be used as the constituent material in the combined electronical assembly such as gate insulator or LC noise filter element of IPD, DRAM storer electricity container, cascade capacitor, transistor.
[embodiment]
Together embodiments of the invention are described in detail below with comparative example.
< embodiment 1>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.
Use this film formation solution, carried out the formation of the film based on 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 by solution coat on substrate.Substrate employs the 6 inches of silicon substrate (Pt/TiO forming Pt film with sputtering method on surface 2/ SiO 2/ Si (100) substrate).Then, utilize hot-plate to heat at 350 DEG C within 5 minutes, to come to burn till temporarily.After repeating 5 these coatings, interim firing process, be 10 DEG C/sec by heat-up rate, keep temperature to be 700 DEG C and the hold-time is that the RTA (rapid heating process) of 1 minute burns till in 100% oxygen atmosphere, substrate is formed the dielectric film that thickness is 300nm.
< embodiment 2>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.
Use this film formation solution, carried out the formation of the film based on 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 by solution coat on substrate.Substrate employs the 6 inches of silicon substrate (Pt/TiO forming Pt film with sputtering method on surface 2/ SiO 2/ Si (100) substrate).Then, utilize hot-plate to heat at 350 DEG C within 5 minutes, to come to burn till temporarily.After repeating 5 these coatings, interim firing process, be 10 DEG C/sec by heat-up rate, keep temperature to be 700 DEG C and the hold-time is that the RTA (rapid heating process) of 1 minute burns till in dry air atmosphere, substrate is formed the dielectric film that thickness is 300nm.
< embodiment 3>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 4>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 5>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 6>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 7>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 8>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 9>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the propionic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 10>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the butanic acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 11>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the isopropylformic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 12>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the positive valeric acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 13>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the isovaleric acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 14>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2-Methyl Butyric Acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 15>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the trimethylacetic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 16>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the n-caproic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 17>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and 2, the 2-acid dimethyls as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 18>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 3 methylvaleric acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 19>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 4-methylvaleric acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 20>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the naphthenic acid ketone as copper source, the tetraisopropoxy titanium as titanium source and the positive enanthic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 21>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the naphthenic acid ketone as copper source, the tetraisopropoxy titanium as titanium source and the 2 methyl caproic acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 22>
First, shown in following list 1, prepare the calcium naphthenate as calcium source, the naphthenic acid ketone as copper source, the tetraisopropoxy titanium as titanium source and the 5-methylhexanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 23>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2-ethylpentanoic as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 24>
First, shown in following list 1, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 4-ethylpentanoic as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 25>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the naphthenic acid ketone as copper source, the tetraisopropoxy titanium as titanium source and 2, the 2-dimethyl valeric acids as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 26>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and 2, the 4-dimethyl valeric acids as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 27>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the naphthenic acid ketone as copper source, the tetraisopropoxy titanium as titanium source and 4, the 4-dimethyl valeric acids as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 28>
First, shown in following list 2, prepare the dimethoxy-ethanol calcium as calcium source, the dimethoxy-ethanol ketone as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 29>
First, shown in following list 2, prepare the dimethoxy-ethanol calcium as calcium source, the dimethoxy-ethanol ketone as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 30>
First, shown in following list 2, prepare the dimethoxy-ethanol calcium as calcium source, the dimethoxy-ethanol ketone as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< embodiment 31>
First, shown in following list 2, prepare respectively the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, as the tetraisopropoxy titanium in titanium source and be the carboxylic acid mixed solvent of equivalent as organic solvent propionic acid and 2 Ethylbutanoic acid are mixed into molar ratio computing.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< embodiment 32>
First, shown in following list 2, prepare respectively the calcium naphthenate as calcium source, the naphthenic acid ketone as copper source, as the tetraisopropoxy titanium in titanium source and be the carboxylic acid-alcohol mixed solvent of equivalent as organic solvent 2 Ethylbutanoic acid and propyl carbinol are mixed into molar ratio computing.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 1>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 2>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 3>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 4>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 5>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 6>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 7>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 8>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 Ethylbutanoic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 9>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the propionic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 10>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the butanic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 11>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the isopropylformic acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 12>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the positive valeric acid as organic solvent respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 13>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the isovaleric acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 14>
First, shown in following list 2, prepare the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2-Methyl Butyric Acid as organic solvent respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 15>
First, shown in following list 2, prepare the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the trimethylacetic acid as organic solvent respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 16>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the n-caproic acid as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 17>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and 2, the 2-acid dimethyls as organic solvent are prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 18>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 3 methylvaleric acid as organic solvent is prepared respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 19>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 4-methylvaleric acid as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 20>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the positive enanthic acid as organic solvent is prepared respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 21>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 2 methyl caproic acid as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 22>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the 5-methylhexanoic acid as organic solvent is prepared respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 23>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2-ethylpentanoic as organic solvent is prepared respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 24>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 4-ethylpentanoic as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 25>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and 2, the 2-dimethyl valeric acids as organic solvent are prepared respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 26>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and 2, the 4-dimethyl valeric acids as organic solvent are prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 27>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and 4, the 4-dimethyl valeric acids as organic solvent are prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 28>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the acetic acid as organic solvent is prepared respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 29>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the acetic acid as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 30>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the n-caprylic acid as organic solvent is prepared respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 31>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the n-caprylic acid as organic solvent is prepared respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 32>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the n-caprylic acid as organic solvent is prepared respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 33>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the n-caprylic acid as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 34>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the pelargonic acid as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 35>
First, as shown in Listing 3, the calcium naphthenate as calcium source, the copper naphthenate as copper source, the tetraisopropoxy titanium as titanium source and the pelargonic acid as organic solvent is prepared respectively.Further, diethanolamine is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 2 and form dielectric film on substrate.
< comparative example 36>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the 2 ethyl hexanoic acid as organic solvent is prepared respectively.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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
< comparative example 37>
First, as shown in Listing 3, the calcium acetate (monohydrate) as calcium source, the neutralized verdigris (monohydrate) as copper source, the tetraisopropoxy titanium as titanium source and the p-Xylol as organic solvent is prepared respectively.Further, methyl ethyl diketone is prepared as the stablizer 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, be heated into 150 DEG C in organic solvent and reflux, obtaining thus converts with oxide compound counts the film-forming composition of 10 quality % concentration.Carry out in addition identically with embodiment 1 and form dielectric film on substrate.
[table 1]
[table 2]
[table 3]
< comparison test and evaluation >
For the substrate being formed with the dielectric film obtained in embodiment 1 ~ 32 and comparative example 1 ~ 37, metal mask is used to make the Pt upper electrode of 250 μm of from the teeth outwards with sputtering method, between Pt lower electrode immediately below dielectric film, with the scope inner evaluation C-V characteristic (the voltage interdependence of electrostatic capacity) of 1kHz frequency at-5 ~ 5V, go out relative permittivity ε r according to the maximum value calculation of electrostatic capacity.In addition, about the mensuration of C-V characteristic, use the 4284AprecisionLCRmeter that Hewlett-Packard Corporation manufactures, Biasstep0.1V, Frequency1kHz, Oscillationlevel30mV, Delaytime0.2sec, Temperature23 DEG C, measure under the condition of Hygrometry50 ± 10%.
Further, for the dielectric film obtained in embodiment 1 ~ 32 and comparative example 1 ~ 37, striped (film is uneven) is determined whether to estimate.This is evaluated as film.
Further, a part for the film-forming composition obtained in embodiment 1 ~ 32 and comparative example 1 ~ 37 is sealed in reagent bottle, in the refrigerating chamber of maintenance 5 DEG C after keeping 3 months, determines whether precipitate to estimate.Using this as estimation of stability.
These results are shown in lower list 4 ~ table 6.In addition, during film in table 4 ~ table 6 is evaluated, be used as when covering the film surface smoothing of whole substrate after burning till that not produce crawling even and be set to " well ", the film surface covering the whole substrate after burning till there is island, striated etc. and film air spots is sliding time to be used as generation crawling even and be set to " bad ".Further, in estimation of stability, be set to " well " when not producing precipitation in the reagent bottle after refrigeration keeping, be set to " bad " when producing precipitation.
[table 4]
[table 5]
[table 6]
As from table 4 ~ table 6, with general formula: Ca (4-3x)cu 3xti 4o 12shown x is Ca more and the cooperation that Cu is less or general formula: the Ca of 0.4 (4-3x)cu 3xti 4o 12shown x be 1.2 the less and dielectric film that the is comparative example 1 ~ 27 of the cooperation that Cu is more of Ca compare, at general formula: Ca (4-3x)cu 3xti 4o 12shown x be 0.67 ~ 1.1 embodiment 1 ~ 32 and comparative example 28 ~ 37 dielectric film in, obtain the higher and result that relative permittivity is higher of electrostatic capacity.From this results verification to, general formula: Ca (4-3x)cu 3xti 4o 12the scope of the good dielectric property of display is there is in shown x.
But, in embodiment 1 ~ 32 and comparative example 28 ~ 37, acetic acid is used as the comparative example 28,29 of organic solvent and n-caprylic acid or pelargonic acid, 2 ethyl hexanoic acid, p-Xylol are used as, in the comparative example 30 ~ 37 of organic solvent, to create film uneven when forming dielectric film.And, acetic acid is used as organic solvent comparative example 28,29, n-caprylic acid is used as organic solvent comparative example 30 ~ 32 and p-Xylol is used as in the comparative example 37 of organic solvent, found the generation precipitated after the film-forming composition before long-term keeping film is formed.On the other hand, in embodiment 1 ~ 32, both do not produce film uneven, and, do not generate precipitation after long-term keeping film-forming composition yet.From this results verification to, there is the good and compound that storage stability is also excellent of film in the organic solvent used in CCTO film-forming composition, can by by general formula of the present invention: C nh 2n+1carboxylic acid shown in COOH (wherein n be 2 ~ 6 integer) is used as organic solvent and prevents film when forming dielectric film uneven, and, even if long-term keeping film formed before film-forming composition also can not generate precipitation.
And, in the dielectric film of embodiment 1 ~ 32, the dielectric film of the embodiment 28 ~ 30 using methyl cellosolve as calcium source and copper source if be conceived to, then find that electrostatic capacity and relative permittivity are worse than all a little except using acetate or naphthenate as the tendency of the dielectric film of the embodiment 1 ~ 8 manufactured with roughly the same condition except calcium source and copper source.From this results verification to, if acetate or naphthenate are used as calcium source and Tong Yuan, then can make the higher and dielectric film that relative permittivity is higher of electrostatic capacity.
And, in the dielectric film of embodiment 1 ~ 32, the dielectric film of the embodiment 31 of the mixed solvent of 2 kinds of carboxylic acids is used as organic solvent, carboxylic acid and the dielectric film of the embodiment 32 of the mixed solvent of ethanol is used to obtain and the electrostatic capacity of the dielectric film same degree except using the embodiment 1 ~ 9 manufactured with roughly the same condition except single solvent as organic solvent and relative permittivity as organic solvent, from this results verification to, be not limited to the organic solvent be made up of the single solvent of the carboxylic acid shown in above-mentioned general formula, even if be the mixed solvent of the mixed solvent of carboxylic acid shown in the multiple above-mentioned general formula of mixing or the carboxylic acid shown in above-mentioned general formula and other solvents, as long as the carboxylic acid shown in above-mentioned general formula can be used as the principal constituent of organic solvent, also film when forming dielectric film can be prevented uneven, and, even if the film-forming composition before long-term keeping film is formed also can not generate precipitation.
Utilizability in industry
The formation method of dielectric film formation composition of the present invention, dielectric film and the dielectric film formed by the method, it does not comprise the material larger to the load of environment, and excellent as the fundamental characteristics of electrical condenser, the purposes of film capacitor or laminate film electrical condenser can be used in.In addition, its fundamental characteristics as IPD is also excellent, can be used in the combined electronical assembly such as gate insulator or LC noise filter element of IPD, DRAM storer electricity container, cascade capacitor, transistor.

Claims (12)

1. a dielectric film formation composition, is characterized in that, for for the formation of in general formula: Ca (4-3x)cu 3xti 4o 12the aqueous dielectric film formation composition of the film of shown complex metal oxides form, in formula, 0.5≤x≤1.1,
Be made up of with the organo-metallic solutions providing the ratio of the ratio of the atoms metal shown in above-mentioned general formula and be dissolved in organic solvent the raw material for forming described complex metal oxides, described organic solvent is to have general formula: C nh 2n+1the carboxylic acid of the straight chain shown in COOH or more than 1 or 2 side chain is principal constituent, and wherein, n is the integer of 2 ~ 6.
2. dielectric film formation composition as claimed in claim 1, wherein,
For to form the raw material of described complex metal oxides be organic group by the compound of its Sauerstoffatom or nitrogen-atoms and metallic element bonding.
3. dielectric film formation composition as claimed in claim 1 or 2, wherein,
Be that it is one kind or two or more to be selected from metal alkoxide, metal two alcohol complex, metal trivalent alcohol complex compound, metal carboxylate, metal p-diketonates complex compound, metal p-diketonates ester complex compound, metal β-imino-ketone complex compound and metal amino complex compound for forming the raw material of described complex metal oxides.
4. dielectric film formation composition as claimed in claim 1, wherein,
Relative to the total amount in described composition 1 mole, with the ratio of less than 3 moles further containing the one kind or two or more stablizer be selected from beta-diketon, beta-keto acid, 'beta '-ketoester, oxygen acid, glycol, trivalent alcohol, high carboxylic acid, alkanolamine and polyamine.
5. dielectric film formation composition as claimed in claim 1, 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, 2-acid dimethyl, 3, 3-acid dimethyl, 2, 3-acid dimethyl, 3 methylvaleric acid, 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-ethylpentanoic, 3-ethylpentanoic, 4-ethylpentanoic, 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 formation composition as claimed in claim 1, wherein,
At least one in Ca source or Cu source is acetate.
7. dielectric film formation composition as claimed in claim 1, wherein,
At least one in Ca source or Cu source is naphthenate.
8. dielectric film formation composition as claimed in claim 1, wherein,
Ti source is tetraisopropoxy titanium.
9. a formation method for dielectric film, is characterized in that,
Dielectric film formation composition according to any one of claim 1 to 8 is coated on heat resistant substrate, carry out once in atmosphere, in oxidizing atmosphere or the operation heated in containing water vapor atmosphere or repeat this operation until obtain the film of desired thickness, adding at least in the end in operation hankers or burn till this film with temperature more than crystallized temperature after heating.
10. a dielectric film, this dielectric film is formed by method according to claim 9.
11. 1 kinds of film capacitors with dielectric film according to claim 10, laminate film electrical condenser, integrated passive devices, DRAM storer electricity container, cascade capacitor, the gate insulator of transistor or combined electronical assemblies of LC noise filter element.
The manufacture method of 12. 1 kinds of dielectric film formation compositions, is characterized in that, the method for its dielectric film formation composition according to any one of manufacturing claims 1 to 8,
By being used for forming the material dissolution of described complex metal oxides in described organic solvent, heating and refluxing.
CN201210003035.1A 2012-01-06 2012-01-06 Dielectric film forms the formation method and dielectric film of using composition, dielectric film Expired - Fee Related CN103193477B (en)

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