CN102219507B - Composition for forming ferroelectric film, forming method of ferroelectric film and ferroelectric film - Google Patents
Composition for forming ferroelectric film, forming method of ferroelectric film and ferroelectric film Download PDFInfo
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- CN102219507B CN102219507B CN201110093553.2A CN201110093553A CN102219507B CN 102219507 B CN102219507 B CN 102219507B CN 201110093553 A CN201110093553 A CN 201110093553A CN 102219507 B CN102219507 B CN 102219507B
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Abstract
The invention provides a composition for forming a ferroelectric film suitably applied in a high capacity density film capacitor, a forming method of the ferroelectric film and the ferroelectric film. The composition for forming ferroelectric films such as PLZT ferroelectric films is characterized in that the composition is a liquid composition for forming films adopting a mixed composite metal oxide form. The mixed composite metal oxide comprises a composite metal oxide B of Bi in a mixing way in a mixed metal oxide A as illustrated in the general formula (PbxLay) (ZrzTi (1-z))O3, wherein, 0.9<x<1.3, 0<=y<=0.1,0<=z<0.9, and is composed of an organic metal compound solution. In the organic metal compound solution, each raw material is dissolved in an organic solvent with a metal atom ratio as illustrated in the above-mentioned general formula. Furthermore, the material forming the composite metal oxide B is a compound formed by the bonding of a positive caprylic acid base and a metal element through the oxygen atom of the positive caprylic acid base.
Description
Technical field
The ferroelectric thin film that the present invention relates to a kind of film capacitor that is suitable for high capacity density forms with the formation method of composition, ferroelectric thin film and the ferroelectric thin film forming by the method.
Background technology
As the manufacture method of this ferroelectric thin film, the general known following method that has: use the alkoxide of each composition metal or acylate are dissolved in to the mixed solution in polar solvent, and be coated on metal substrate, be dried and formation film, and the temperature being heated to more than crystallized temperature carries out sintering, thus dielectric film is carried out to film forming (for example, with reference to patent documentation 1,2).
But, in the time making film, there is the large effect of stress being caused by the constraint of substrate, thereby have the such problem of sufficient relative dielectric constant (for example, with reference to non-patent literature 1) that can not get.
Therefore, carried out improving by adding trace element the trial (for example, with reference to non-patent literature 2) of relative dielectric constant all the time.
And by filming, static capacity uprises in theory, so also carried out improving by filming the trial of static capacity always.
And, also carry out the Bi that adulterates and improved the trial (for example, with reference to patent documentation 3) of dielectric voltage withstand characteristic in PZT.But Bi only enumerates as doped chemical in above-mentioned patent documentation 3, in fact there is not the implementation column of having adulterated.And, also do not carry out the mensuration of relative dielectric constant.
Patent documentation 1: the clear 60-236404 communique of Japanese Patent Publication (page hurdle, lower-left, the 11st row～4th, the 3rd page of hurdle, bottom right the 10th row, hurdle, 10th row～same page lower-left, the 5th page of hurdle, upper right the 17th row)
Patent documentation 2: Japanese Patent Publication 7-252664 communique (claim 2,3,7,8, paragraph [0001], [0035], [0117], [0118])
Patent documentation 3: Japanese Patent Publication 8-153854 communique (claim 3)
Non-patent literature 1: セ ラ ミ Star Network ス, 42,175-180 (2007) (p.175 verso the 20th row～22nd row)
Non-patent literature 2:S.B.Majumder, D.C.Agrawal, Y.N.Mohopatra, and R.S.Katiyar, " Effect of Cerium Doping on the Microstructure and ElectricalProperties of Sol-Gel Derived Pb1.05 (Zr0.53-dCedTi0.47) O3 (d=10at%) ThinFilms ", Materials Science and Engineering, B98,2003, pp.25-32 (Fig.2)
But, if improve static capacity and attenuate the thickness of formed ferroelectric thin film, leakage current density uprises, also insulation breakdown likely, so cannot give full play to the performance as capacitor.And the not talkative trial of also having carried out improving by adding trace element fully relative dielectric constant.
Summary of the invention
The object of the present invention is to provide a kind of can formation with the formation method of composition, ferroelectric thin film and the ferroelectric thin film forming by the method with the ferroelectric thin film that simple method more significantly improves film capacitor relative dielectric constant, that be suitable for high capacity density than ferroelectric thin film in the past.
The 1st viewpoint of the present invention, be used to form the ferroelectric thin film formation composition of a kind of ferroelectric thin film being selected from PLZT, PZT and PT, it is characterized in that, said composition is to be used to form the fluid composition of taking the film that mixes composite metal oxide form, and described mixing composite metal oxide is at general formula: (Pb
xla
y) (Zr
zti
(1-z)) O
3(0.9 < x < 1.3 in formula, 0≤y < 0.1, 0≤z < 0.9) shown in composite metal oxide A in, mix the composite metal oxide B that contains Bi, and formed by organo-metallic compound solution, in described organo-metallic compound solution, for forming the raw material of composite metal oxide A and being dissolved in organic solvent for the raw material that forms composite metal oxide B with the ratio that the metallic atom ratio shown in above-mentioned general formula is provided, be that caprylic acid base is by the compound of its oxygen atom and metallic element bonding for forming the raw material of composite metal oxide B.
The 2nd viewpoint of the present invention, i.e. the ferroelectric thin film formation composition of the invention based on the 1st viewpoint, is characterized in that, further passes through the compound of its oxygen atom or nitrogen-atoms and metallic element bonding for forming the raw material of composite metal oxide A for organic group.
The 3rd viewpoint of the present invention, the ferroelectric thin film formation composition of the i.e. invention based on the 2nd viewpoint, it is characterized in that, be to be further selected from the one kind or two or more of metal alkoxide, metal two alcohol complexs, metal trihydroxy alcohol complex compound, metal carboxylate, metal beta-diketon complex compound, metal beta-diketo-ester complex compound, metal β-imino group ketone complex compound and metal amino complex compound for forming the raw material of composite metal oxide A.
The 4th viewpoint of the present invention, the i.e. ferroelectric thin film formation composition based on the 1st invention to the 3rd viewpoint, it is characterized in that, ratio with respect to 1 mole of total metal content in composition with 0.2～3 mole further contains stabilizer, and described stabilizer is to be selected from one kind or two or more in beta-diketon, beta-keto acid, 'beta '-ketoester, oxyacid, glycol, trihydroxy alcohol, high carboxylic acid, alkanolamine and polyamine.
The 5th viewpoint of the present invention,, based on the 1st invention to the 4th viewpoint, is characterized in that, the mol ratio B/A of B and A is further 0 < B/A < 0.2.
The 6th viewpoint of the present invention, the invention based on the 5th viewpoint, is characterized in that, the mol ratio B/A of B and A is further 0.005≤B/A≤0.1.
The 7th viewpoint of the present invention, it is the formation method of ferroelectric thin film, it is characterized in that, ferroelectric thin film formation based on the 1st to the 6th viewpoint is coated on heat resistant substrate with composition, carry out once in air, in oxidizing atmosphere or the operation heating in moisture vapor atmosphere or repeat this operation until obtain the film of desired thickness, at least adding in final operation hanker or heat after with this film of temperature sintering more than crystallized temperature.
The 8th viewpoint of the present invention, the ferroelectric thin film forming by the method based on the 7th viewpoint.
The 9th viewpoint of the present invention, there is film capacitor (Condenser), capacitor, the integrated passive devices (IPD, Integrated Passive Device) of the ferroelectric thin film based on the 8th viewpoint, the composite electronic component of DRAM capacitor, cascade capacitor, transistorized gate insulator, nonvolatile memory, thermoelectric type infrared-ray detecting element, piezoelectric element, electrooptic cell, actuator, resonator, ultrasonic motor or LC noise filter element for memory.
The 10th viewpoint of the present invention, the i.e. composite electronic component based on the 9th film capacitor with ferroelectric thin film corresponding with more than 100MHz frequency band viewpoint, capacitor, IPD, DRAM capacitor, cascade capacitor, transistorized gate insulator, nonvolatile memory, thermoelectric type infrared-ray detecting element, piezoelectric element, electrooptic cell, actuator, resonator, ultrasonic motor or LC noise filter element for memory.
Invention effect
Ferroelectric thin film formation of the present invention has following advantage with composition: in organo-metallic compound solution, be used in and form the raw material of composite metal oxide A and be dissolved in organic solvent for the raw material that forms composite metal oxide B with the ratio of being scheduled to, so that take general formula: (Pb
xla
y) (Zr
zti
(1-z)) O
3(0.9 < x < 1.3 in formula, 0≤y <, 0.1,0≤z < 0.9) shown in composite metal oxide A in mix the mixing composite metal oxide form of composite metal oxide B that contains Bi.And be that caprylic acid base is by the compound of its oxygen atom and metallic element bonding for forming the raw material of composite metal oxide B.By using said composition to form ferroelectric thin film, can obtain more significantly improving relative dielectric constant and being suitable for the ferroelectric thin film of the film capacitor of high capacity density than ferroelectric thin film in the past by simple method.
Embodiment
Below explanation is used for implementing form of the present invention.
It is to be used to form the composition that is selected from a kind of ferroelectric thin film in PLZT, PZT and PT with composition that ferroelectric thin film of the present invention forms.The ferroelectric thin film that uses said composition to form, takes at general formula: (Pb
xla
y) (Zr
zti
(1-z)) O
3(0.9 < x < 1.3 in formula, 0≤y <, 0.1,0≤z < 0.9) shown in composite metal oxide A in mix the mixing composite metal oxide form of composite metal oxide B that contains Bi.In addition, in above-mentioned formula, in the time of y ≠ 0 and z ≠ 0, be PLZT, in the time of y=0 and z ≠ 0, be PZT, in the time of y=0 and z=0, be PT.Said composition is made up of organo-metallic compound solution, in described organo-metallic compound solution, be dissolved in organic solvent with the raw material for forming composite metal oxide B in the mode that becomes the ratio as the metallic atom ratio as shown in above-mentioned general formula is provided for forming the raw material of composite metal oxide A.
Composite metal oxide A is the compound that organic group passes through each metallic element bonding of its oxygen atom or nitrogen-atoms and Pb, La, Zr and Ti by raw material the best.For example, can enumerate one kind or two or more in the group that metal alkoxide, metal two alcohol complexs, metal trihydroxy alcohol complex compound, metal carboxylate, metal beta-diketon complex compound, metal beta-diketo-ester complex compound, metal β-imino group ketone complex compound and metal amino complex compound form.Especially best compound is metal alkoxide, its partial hydrolystate and acylate.Wherein, can enumerate acetate (lead acetate: Pb (OAc) as Pb compound, La compound
2, lanthanum acetate: La (OAc)
3), diisopropoxy lead: Pb (OiPr)
2, three isopropoxy lanthanum: La (OiPr)
3deng.Can enumerate purity titanium tetraethoxide: Ti (OEt) as Ti compound
4, tetraisopropoxy titanium: Ti (OiPr)
4, four titanium n-butoxide: Ti (OnBu)
4, four isobutoxy titanium: Ti (OiBu)
4, four tert-butoxy titanium: Ti (OtBu)
4, dimethoxy diisopropoxy titanium: Ti (OMe)
2(OiPr)
2deng alkoxide.Be preferably the alcohol salt same with above-mentioned Ti Compound Phase as Zr compound.Metal alkoxide can directly use, and also can use in order to promote to decompose its partial hydrolystate.
Composite metal oxide B is that caprylic acid base is by the compound of its oxygen atom and Bi element bonding by raw material the best.Particularly, can enumerate caprylic acid bismuth.
In order to prepare ferroelectric thin film formation composition of the present invention, by these raw materials with the ratio solvent that is equivalent to required ferroelectric thin film composition in suitable solvent, be prepared into the concentration that is applicable to coating.
The mol ratio B/A of B and A is adjusted in the scope of 0 < B/A < 0.2.As in above-mentioned scope, can more significantly improve relative dielectric constant than ferroelectric thin film in the past.In addition, as less than lower limit or exceed higher limit, obtain not having when not adding bismuth the result of much difference, be not suitable for the film capacitor of high capacity density.Wherein, especially preferred 0.005≤B/A≤0.1.
Ferroelectric thin film formation can suitably determine according to used raw material with the solvent of composition as used herein, generally can use carboxylic acid, alcohol, ester, ketone (such as acetone, methyl ethyl ketone), ethers (such as dimethyl ether, Anaesthetie Ether), naphthenic (such as cyclohexane, cyclohexanol), fragrant family (such as benzene,toluene,xylene) and other oxolanes etc., or can use these mixed solvents of more than two kinds.
As carboxylic acid, concrete n-butyric acie, alpha-methyl butyric acid, isovaleric acid, the 2 Ethylbutanoic acid, 2 of preferably using, 2-acid dimethyl, 3,3-acid dimethyl, 2,3-acid dimethyl, 3 methylvaleric acid, 4-methylvaleric acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 2,2-dimethyl valeric acid, 3,3-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2 ethyl hexanoic acid and 3-thylhexoic acid.
And as best ethyl acetate, propyl acetate, n-butyl acetate, 2-butyl acetate, tert-butyl acetate, isobutyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid tert-pentyl ester and the isoamyl acetate of using of ester, preferably use 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, isobutanol, 1-amylalcohol, 2-amylalcohol, 2-methyl-2-amylalcohol and 2-methyl cellosolve as alcohol.
In addition, ferroelectric thin film formation is preferably made as 0.1～20 quality % left and right by the total concentration of the organo-metallic compound in the organo-metallic compound solution of composition in metal oxide conversion amount.
In this organo-metallic compound solution, can add as required in (stabilizer molecular number)/(metallic atom number) 0.2～3 left and right, beta-diketon class (for example acetyl propyl ester, 2, 2-dimethyl-6, 6, 7, 7, 8, 8, 8-seven fluoro-3, 5-acetyl caproyl (Heptafluorobutanoyl pivaloylmethane), dipivaloylmethane, trifluoroacetylacetone (TFA), benzoyl acetone etc.), beta-keto acid class (for example acetoacetic acid, propionyl acetic acid, benzoylacetic acid etc.), 'beta '-ketoester class (the methyl of for example above-mentioned ketone acid, propyl group, the lower alkyl esters classes such as butyl), oxyacid class (for example lactic acid, glycolic acid, alpha-hydroxybutyric acid, salicylic acid etc.), the lower alkyl esters class of above-mentioned oxyacid, hydroxyl ketone (for example diacetone alcohol, 3-Hydroxybutanone etc.), glycol, trihydroxy alcohol, high carboxylic acid, alkanol amine (for example diethanol amine, triethanolamine, monoethanolamine) and polyamine etc. as stabilizer.
In the present invention, preferably carry out filtration treatment etc. by the organo-metallic 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 0.3 μ m, especially more than 0.2 μ m) is made as 50 of every 1mL solution/below mL.
If particle diameter is that the number of particle more than 0.5 μ m exceedes 50/mL, long-term storing stability variation in organo-metallic compound solution.Particle diameter in this organo-metallic compound solution is that the number of particle more than 0.5 μ m is more few better, especially preferably 30/below mL.
Process the method for the organo-metallic compound solution after preparation there is no particular limitation to become the mode of 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 the filtration method with syringe extruding.The 2nd method: combine membrane filter that commercially available aperture is 0.05 μ m and the pressure filtration method of pressurized canister.The 3rd method: combine the filter that uses in above-mentioned the 2nd method and the circulating filtration method of solution circulation groove.
In any method all because of the particle catch rate difference of solution squeeze pressure based on filter.Conventionally the lower catch rate of known pressure more uprises, and especially, in the 1st method, the 2nd method, in order to realize, particle number more than particle diameter 0.5 μ m is made as to the condition below 50, preferably makes solution pass through very lentamente filter with low pressure.
The ferroelectric thin film formation composition of the application of the invention, can form the ferroelectric thin film of taking to mix the mixing composite metal oxide form of the composite metal oxide B that contains Bi in the a kind of composite metal oxide A being selected from PLZT, PZT and PT simply.
In order to form ferroelectric thin film with ferroelectric thin film formation composition of the present invention, by rubbing methods such as spin-coating method, dip coating, LSMCD (liquid source misted chemical deposition Liquid Source Misted ChemicalDeposition) methods, above-mentioned composition is coated on heat resistant substrate, is dried (interim sintering) and formal sintering.
As the object lesson of used heat resistant substrate, can enumerate in 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 Ca-Ti ore type electroconductive oxide etc., be not limited in these.
In addition, when cannot be with 1 coating obtain required thickness time, repeat to be repeatedly coated with, carry out formal sintering after drying process.At this, required thickness refers to the thickness of the ferroelectric thin film obtaining after formal sintering, in the time of film capacitor for high capacity density, and the scope that the thickness of the ferroelectric thin film after formal sintering is 50～500nm.
And interim sintering makes organo-metallic compound thermal decomposition or hydrolysis become composite oxides to carry out for except desolventizing time, so in air, in oxygen atmosphere or carry out in moisture vapor atmosphere.Even if airborne heating also can fully guarantee to be hydrolyzed required moisture according to airborne moisture.This heating can be by for implementing except the low-temperature heat of desolventizing with for 2 stages of the high-temperature heating that decomposes organo-metallic compound.
Formal sintering is the film obtaining at interim sintering for the temperature sintering with more than crystallized temperature the operation that makes its crystallization, can obtain thus ferroelectric thin film.Sintering atmosphere the best of this crystallization step is O
2, N
2, Ar, N
2o or H
2deng or their mist etc.
Interim sintering carried out about 5～10 minutes at 150～550 DEG C, and formal sintering carries out about 1～60 minute at 450～800 DEG C.Formal sintering can carry out with Fast Heating processing (RTA processing).While carrying out formal sintering with RTA processing, its programming rate is preferably 10～100 DEG C/sec.
The ferroelectric thin film of the present invention forming so has more significantly improved relative dielectric constant than ferroelectric thin film in the past, as the fundamental characteristics excellence of capacitor, and the best film capacitor for high capacity density.And the fundamental characteristics as IPD of ferroelectric thin film of the present invention is also excellent.
And ferroelectric thin film of the present invention can be used as the constituent material in the composite electronic component of film capacitor, capacitor, IPD, DRAM capacitor, cascade capacitor, transistorized gate insulator, nonvolatile memory, thermoelectric type infrared-ray detecting element, piezoelectric element, electrooptic cell, actuator, resonator, ultrasonic motor or LC noise filter element for memory.Wherein, especially can also be used in the parts corresponding with more than 100MHz frequency band.
[embodiment]
Together describe implementation column of the present invention in detail with comparative example below.
< embodiment 1>
First, add four n-butoxy zirconiums and the acetylacetone,2,4-pentanedione as stabilizer in reaction vessel, the temperature with 150 DEG C under blanket of nitrogen refluxes.Add wherein tetraisopropoxy titanium and the acetylacetone,2,4-pentanedione as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/Zr/Ti=110/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 0.5mol% outward with additional percentage (cutting), obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 2>
To adding caprylic acid bismuth that additional percentage counts 1.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 1 in addition and on substrate, form ferroelectric thin film.
< embodiment 3>
To adding caprylic acid bismuth that additional percentage counts 3.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 1 in addition and on substrate, form ferroelectric thin film.
< embodiment 4>
To adding caprylic acid bismuth that additional percentage counts 5.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 1 in addition and on substrate, form ferroelectric thin film.
< embodiment 5>
To adding caprylic acid bismuth that additional percentage counts 10.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 1 in addition and on substrate, form ferroelectric thin film.
< comparative example 1>
In the sol-gel liquid of embodiment 1, do not add caprylic acid bismuth as film formation solution, carry out in the same manner with implementation column 1 in addition and on substrate, form ferroelectric thin film.
< embodiment 6>
First, add four n-butoxy zirconiums and the diethanol amine as stabilizer in reaction vessel, the temperature with 150 DEG C under blanket of nitrogen refluxes.Add wherein tetraisopropoxy titanium and the diethanol amine as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/Zr/Ti=110/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 0.5mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 7>
To adding caprylic acid bismuth that additional percentage counts 1.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 6 in addition and on substrate, form ferroelectric thin film.
< embodiment 8>
To adding caprylic acid bismuth that additional percentage counts 3.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 6 in addition and on substrate, form ferroelectric thin film.
< embodiment 9>
To adding caprylic acid bismuth that additional percentage counts 5.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 6 in addition and on substrate, form ferroelectric thin film.
< embodiment 10>
To adding caprylic acid bismuth that additional percentage counts 10.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 6 in addition and on substrate, form ferroelectric thin film.
< comparative example 2>
In the sol-gel liquid of embodiment 6, do not add caprylic acid bismuth as film formation solution, carry out in the same manner with implementation column 6 in addition and on substrate, form ferroelectric thin film.
< embodiment 11>
First, add four n-butoxy zirconiums and the acetylacetone,2,4-pentanedione as stabilizer in reaction vessel, the temperature with 150 DEG C under blanket of nitrogen refluxes.Add wherein tetraisopropoxy titanium and the acetylacetone,2,4-pentanedione as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/Zr/Ti=110/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 0.5mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in dry air atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 12>
To adding caprylic acid bismuth that additional percentage counts 1.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 11 in addition and on substrate, form ferroelectric thin film.
< embodiment 13>
To adding caprylic acid bismuth that additional percentage counts 3.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 11 in addition and on substrate, form ferroelectric thin film.
< embodiment 14>
To adding caprylic acid bismuth that additional percentage counts 5.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 11 in addition and on substrate, form ferroelectric thin film.
< embodiment 15>
To adding caprylic acid bismuth that additional percentage counts 10.0mol% in this sol-gel liquid as film formation solution, carry out in the same manner with embodiment 11 in addition and on substrate, form ferroelectric thin film.
< comparative example 3>
In the sol-gel liquid of embodiment 11, do not add caprylic acid bismuth as film formation solution, carry out in the same manner with implementation column 11 in addition and on substrate, form ferroelectric thin film.
< embodiment 16>
First, in reaction vessel, add four n-propoxyzirconium and the acetylacetone,2,4-pentanedione as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein four titanium n-butoxide and the acetylacetone,2,4-pentanedione as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and 1.5 hydration lanthanum acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 3.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in dry air atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 17>
First, in reaction vessel, add zirconium tetraisopropoxide and the diethanol amine as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein four positive propoxy titaniums and the diethanol amine as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and 1.5 hydration lanthanum acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 5.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 18>
First, in reaction vessel, add four tert-butoxy zirconiums and the lactic acid as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein purity titanium tetraethoxide and the lactic acid as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and 1.5 hydration lanthanum acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 10.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 19>
First, in reaction vessel, add zirconium tetraisopropoxide and the diethanol amine as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein tetraisopropoxy titanium and the diethanol amine as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein diisopropoxy lead and three isopropoxy lanthanums and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 3.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 20>
First, in reaction vessel, add four n-propoxyzirconium and the acetylacetone,2,4-pentanedione as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein purity titanium tetraethoxide and the acetylacetone,2,4-pentanedione as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein diisopropoxy lead and three isopropoxy lanthanums and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 5.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in dry air atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 21>
First, in reaction vessel, add four n-butoxy zirconiums and the lactic acid as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein four titanium n-butoxide and the lactic acid as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein diisopropoxy lead and three isopropoxy lanthanums and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 10.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 22>
First, in reaction vessel, add four tert-butoxy zirconiums and the lactic acid as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein four positive propoxy titaniums and the lactic acid as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and three isopropoxy lanthanums and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 3.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 23>
First, in reaction vessel, add four isobutoxy zirconiums and the diethanol amine as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein tetraisopropoxy titanium and the diethanol amine as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and three isopropoxy lanthanums and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 5.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 24>
First, in reaction vessel, add zirconium tetraisopropoxide and the acetylacetone,2,4-pentanedione as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein four titanium n-butoxide and the acetylacetone,2,4-pentanedione as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and three isopropoxy lanthanums and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 10.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in dry air atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 25>
First, in reaction vessel, add zirconium tetraisopropoxide and the acetylacetone,2,4-pentanedione as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein four positive propoxy titaniums and the acetylacetone,2,4-pentanedione as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein diisopropoxy lead and 1.5 hydration lanthanum acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 3.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in dry air atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 26>
First, in reaction vessel, add four n-propoxyzirconium and the lactic acid as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein four tert-butoxy titaniums and the lactic acid as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein diisopropoxy lead and 1.5 hydration lanthanum acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 5.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 27>
First, in reaction vessel, add four n-butoxy zirconiums and the diethanol amine as stabilizer, under blanket of nitrogen, reflux with 150 DEG C of temperature.Add wherein purity titanium tetraethoxide and the diethanol amine as stabilizer, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein diisopropoxy lead and 1.5 hydration lanthanum acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/La/Zr/Ti=110/3/52/48 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 10.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< comparative example 4>
In the sol-gel liquid of embodiment 16, do not add caprylic acid bismuth as film formation solution, carry out in the same manner with implementation column 16 in addition and on substrate, form ferroelectric thin film.
< embodiment 28>
First, add four isobutoxy titaniums and the diethanol amine as stabilizer in reaction vessel, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/Ti=110/100 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 3.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 29>
First, add tetraisopropoxy titanium and the acetylacetone,2,4-pentanedione as stabilizer in reaction vessel, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/Ti=110/100 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 5.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in dry air atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< embodiment 30>
First, add purity titanium tetraethoxide and the lactic acid as stabilizer in reaction vessel, the temperature with 150 DEG C under blanket of nitrogen refluxes.Secondly, add wherein three hydration lead acetates and the propylene glycol as solvent, the temperature with 150 DEG C under blanket of nitrogen refluxes.At 150 DEG C, accessory substance is removed in decompression distillation afterwards, then adds propylene glycol and adjust concentration, thereby obtains containing the liquid that is scaled the metallic compound of 30 quality % concentration with oxide.Adding dilution alcohol obtains containing taking oxide and converts each metal than the sol-gel liquid as the metallic compound of the 10 quality % concentration of Pb/Ti=110/100 again.
Then, in this sol-gel liquid, add the caprylic acid bismuth of counting 10.0mol% with additional percentage, obtain film formation solution.
Use this film formation solution, carry out the formation of the film based on CSD method by following method.That is, by spin-coating method 3 seconds under 500rpm, afterwards under 3000rpm under the condition in 15 seconds, by above-mentioned solution coat at 6 inches of silicon substrate (Pt/TiO that form Pt film with sputtering method on surface
2/ SiO
2/ Si (100) substrate) on.Then, use heating plate to heat at 350 DEG C and within 5 minutes, carry out interim sintering.After repeating 6 these coatings, interim sintering circuit, in 100% oxygen atmosphere with 700 DEG C, 1 minute with RTA (Fast Heating processing unit) sintering, the ferroelectric thin film that to form thickness be 270nm.
< comparative example 5>
In the sol-gel liquid of embodiment 28, do not add caprylic acid bismuth as film formation solution, carry out in the same manner with implementation column 28 in addition and on substrate, form ferroelectric thin film.
< comparative evaluation >
For the substrate that is formed with the ferroelectric thin film obtaining in embodiment 1～30 and comparative example 1～5, use metal mask to make from the teeth outwards the Pt upper electrode that is about 250 μ m with sputtering method, between Pt lower electrode under ferroelectric thin film, with 1kHz frequency in the scope inner evaluation C-V of-5～5V characteristic (the voltage interdependence of static capacity), by the maximum value calculation relative dielectric constant ε r of static capacity.In addition, about the mensuration of C-V characteristic, the 4284A precision LCRmeter that uses Hewlett-Packard Corporation to manufacture measures under the condition of Bias step 0.1V, Frequency 1kHz, Oscillation level 30mV, Delay time0.2sec, 23 DEG C of Temperature, Hygrometry 50+10%.The results are shown in lower list 1～table 2.
[table 1]
[table 2]
From table 1～table 2, compared with not containing the ferroelectric thin film of comparative example 1～5 of caprylic acid bismuth in the ferroelectric thin film of embodiment 1～30 that has added 0.5mol%～10.0mol% caprylic acid bismuth film thick lower confirmed high static capacity and the high relative dielectric constant in 270nm left and right.Can judge from this result, the ferroelectric thin film of embodiment 1～30 is as the fundamental characteristics excellence of capacitor.
And, from making the result of ferroelectric thin film of the embodiment 1～30 that the addition of caprylic acid bismuth changes, in the PZT ferroelectric thin film of embodiment 1～15, the result of embodiment 4,9,14 of having added 5.0mol% is especially high, secondly for added 3.0mol% embodiment 3,8,13 result, added the result of the embodiment 5,10,15 of 10.0mol%, the result of having added the embodiment 2,7,12 of 1.0mol%, then for the result of the embodiment 1,6,11 that added 0.5mol% is low result.In the PLZT ferroelectric thin film of embodiment 16～27, the result of embodiment 17,20,23,26 of having added 5.0mol% is especially high, secondly for having added the result of embodiment 16,19,22,25 of 3.0mol%, then for the result of the embodiment 18,21,24,27 that added 10.0mol% is low result.In the PT ferroelectric thin film of embodiment 28～30, the result of embodiment 29 of having added 5.0mol% is especially high, secondly for having added the result of embodiment 28 of 3.0mol%, then for the result of the embodiment 30 that added 10.0mol% is low result.Little according to the rising value of static capacity, relative dielectric constant that has added caprylic acid bismuth in PT ferroelectric thin film in addition, but identical tendency while showing with PZT ferroelectric thin film and PLZT ferroelectric thin film in climbing.
Can confirm from this result, existence can contribute to the scope of the suitable caprylic acid bismuth addition that improves static capacity and relative dielectric constant ε r.
[industrial applicibility]
Ferroelectric thin film of the present invention forms with the formation method of composition, ferroelectric thin film and the ferroelectric thin film forming by the method, and it can be used in the purposes of film capacitor of high capacity density as the fundamental characteristics excellence of capacitor.In addition, fundamental characteristics as IPD is also excellent, can be used in the composite electronic component of IPD, DRAM capacitor, cascade capacitor, transistorized gate insulator, nonvolatile memory, thermoelectric type infrared-ray detecting element, piezoelectric element, electrooptic cell, actuator, resonator, ultrasonic motor or LC noise filter element etc. for memory.
Claims (16)
1. a ferroelectric thin film formation composition, it is used to form the a kind of ferroelectric thin film being selected from PLZT, PZT and PT, it is characterized in that,
Said composition is to be used to form the fluid composition of taking the film that mixes composite metal oxide form, and described mixing composite metal oxide is at general formula: (Pb
xla
y) (Zr
zti
(1-z)) O
3in shown composite metal oxide A, mix the composite metal oxide B that contains Bi, in described general formula, 0.9 < x < 1.3,0≤y < 0.1,0≤z < 0.9,
And formed by organo-metallic compound solution, in described organo-metallic compound solution, for forming the raw material of described composite metal oxide A and being dissolved in organic solvent for the raw material that forms described composite metal oxide B with the ratio that the metallic atom ratio shown in above-mentioned general formula is provided
Be that caprylic acid base is by the compound of its oxygen atom and metallic element bonding for forming the raw material of described composite metal oxide B.
2. ferroelectric thin film formation composition as claimed in claim 1, is characterized in that,
Be the compound that organic group passes through its oxygen atom or nitrogen-atoms and metallic element bonding for the raw material that forms described composite metal oxide A.
3. ferroelectric thin film formation composition as claimed in claim 2, is characterized in that,
Be be selected from metal alkoxide, metal two alcohol complexs, metal trihydroxy alcohol complex compound, metal carboxylate, metal beta-diketon complex compound, metal beta-diketo-ester complex compound, metal β-imino group ketone complex compound and metal amino complex compound one kind or two or more for the raw material that forms described composite metal oxide A.
4. ferroelectric thin film formation composition as claimed any one in claims 1 to 3, is characterized in that,
Ratio with respect to 1 mole of the total metal content in described composition with 0.2～3 mole further contains stabilizer, and described stabilizer is selected from one kind or two or more in beta-diketon, 'beta '-ketoester, oxyacid, glycol, trihydroxy alcohol, alkanolamine and polyamine.
5. ferroelectric thin film formation composition as claimed in claim 4, wherein, described oxyacid is beta-keto acid.
6. ferroelectric thin film formation composition as claimed in claim 4, wherein, described oxyacid is high carboxylic acid.
7. ferroelectric thin film formation composition as claimed any one in claims 1 to 3, is characterized in that,
The mol ratio B/A of described B and described A is 0 < B/A < 0.2.
8. ferroelectric thin film formation composition as claimed in claim 7, is characterized in that,
The mol ratio B/A of described B and described A is 0.005≤B/A≤0.1.
9. a formation method for ferroelectric thin film, is characterized in that,
Ferroelectric thin film formation described in any one in claim 1 to 8 is coated on heat resistant substrate with composition, carry out the operation once heating or repeat this operation until obtain the film of desired thickness in air, at least adding in final operation hanker or heat after with this film of temperature sintering more than crystallized temperature.
10. a formation method for ferroelectric thin film, is characterized in that,
Ferroelectric thin film formation described in any one in claim 1 to 8 is coated on heat resistant substrate with composition, carry out the operation once heating or repeat this operation until obtain the film of desired thickness in oxidizing atmosphere, at least adding in final operation hanker or heat after with this film of temperature sintering more than crystallized temperature.
The formation method of 11. 1 kinds of ferroelectric thin films, is characterized in that,
Ferroelectric thin film formation described in any one in claim 1 to 8 is coated on heat resistant substrate with composition, carry out the operation once heating or repeat this operation until obtain the film of desired thickness in moisture vapor atmosphere, at least adding in final operation hanker or heat after with this film of temperature sintering more than crystallized temperature.
12. 1 kinds of ferroelectric thin films, this ferroelectric thin film forms by the method described in any one in claim 9 to 11.
13. 1 kinds have the composite electronic component of capacitor, integrated passive devices, transistorized gate insulator, nonvolatile memory, thermoelectric type infrared-ray detecting element, piezoelectric element, electrooptic cell, actuator, resonator, ultrasonic motor or the LC noise filter element of the ferroelectric thin film described in claim 12.
14. as the composite electronic component of claim 13, and wherein, described capacitor is film capacitor, DRAM memory capacitor or cascade capacitor.
The composite electronic component of the capacitor with ferroelectric thin film, integrated passive devices, transistorized gate insulator, nonvolatile memory, thermoelectric type infrared-ray detecting element, piezoelectric element, electrooptic cell, actuator, resonator, ultrasonic motor or LC noise filter element described in 15. 1 kinds of claims 13 corresponding with more than 100MHz frequency band.
16. as the composite electronic component of claim 15, and wherein, described capacitor is film capacitor, DRAM memory capacitor or cascade capacitor.
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| JP5817621B2 (en) * | 2012-03-30 | 2015-11-18 | 三菱マテリアル株式会社 | Sol-gel solution for forming ferroelectric thin films |
| JP7155730B2 (en) * | 2018-03-22 | 2022-10-19 | 三菱マテリアル株式会社 | Liquid composition for forming piezoelectric film and method for forming piezoelectric film using this liquid composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276629A (en) * | 1999-06-04 | 2000-12-13 | 国际商业机器公司 | Ferroelectric random storage unit with internal oxygen source and method for releasing oxygen |
| CN1797771A (en) * | 2004-12-27 | 2006-07-05 | 精工爱普生株式会社 | Ferroelectric film, method of manufacturing ferroelectric film, ferroelectric capacitor, and ferroelectric memory |
| CN1922743A (en) * | 2004-07-13 | 2007-02-28 | 精工爱普生株式会社 | Composition for forming ferroelectric thin film, ferroelectric thin film and method for preparing ferroelectric thin film, and liquid spraying head |
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2011
- 2011-04-12 CN CN201110093553.2A patent/CN102219507B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276629A (en) * | 1999-06-04 | 2000-12-13 | 国际商业机器公司 | Ferroelectric random storage unit with internal oxygen source and method for releasing oxygen |
| CN1922743A (en) * | 2004-07-13 | 2007-02-28 | 精工爱普生株式会社 | Composition for forming ferroelectric thin film, ferroelectric thin film and method for preparing ferroelectric thin film, and liquid spraying head |
| CN1797771A (en) * | 2004-12-27 | 2006-07-05 | 精工爱普生株式会社 | Ferroelectric film, method of manufacturing ferroelectric film, ferroelectric capacitor, and ferroelectric memory |
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