CN1392570A - High k dielectric composition with fine crystal particle size - Google Patents
High k dielectric composition with fine crystal particle size Download PDFInfo
- Publication number
- CN1392570A CN1392570A CN 01137766 CN01137766A CN1392570A CN 1392570 A CN1392570 A CN 1392570A CN 01137766 CN01137766 CN 01137766 CN 01137766 A CN01137766 A CN 01137766A CN 1392570 A CN1392570 A CN 1392570A
- Authority
- CN
- China
- Prior art keywords
- dielectric
- barium titanate
- composition
- calcium
- organic media
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000002245 particle Substances 0.000 title claims abstract description 28
- 239000013078 crystal Substances 0.000 title abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 12
- 239000003990 capacitor Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 238000000280 densification Methods 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical class [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- ZZCNKSMCIZCVDR-UHFFFAOYSA-N barium(2+);dioxido(dioxo)manganese Chemical compound [Ba+2].[O-][Mn]([O-])(=O)=O ZZCNKSMCIZCVDR-UHFFFAOYSA-N 0.000 claims description 5
- OOSYCERWOGUQJY-UHFFFAOYSA-N calcium;dioxido(dioxo)manganese Chemical compound [Ca+2].[O-][Mn]([O-])(=O)=O OOSYCERWOGUQJY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 239000002491 polymer binding agent Substances 0.000 claims 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical class [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 46
- 239000000843 powder Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000004907 flux Effects 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 12
- 239000010955 niobium Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 10
- 239000003989 dielectric material Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000013522 chelant Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- 239000004793 Polystyrene Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical class [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 239000004576 sand Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- 239000000080 wetting agent Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
A composite contains modified barium titanate particles and additive of Ca, Ti and Mn mixture. The modified barium titanate particles contains Zr, Zn and Nb distributed uniformly in all of the particles. The said composite can be produced into a dielectric layer with Curie temperature lower than 25 deg.C, dielectric constant being at least 10000 and size of crystal grains being 5 micrometer or even smaller, and suitable for multilayer electronic elements, such as circuits and condensers.
Description
The application is to be that March 5, application number in 1992 are dividing an application of 92102078.3 patent application the applying date.
The present invention relates to barium titanate-based composition, said composition can be made into the ceramic body with less crystallite dimension and high dielectric constant.
People are expecting to dwindle the size of multilayer ceramic capacitor (MLC ' s) always, so that take up space less in the circuit board and reduce cost.Have the more ceramic material of high-k (K) by development, and have the MLC ' s of thin dielectric layer more (general 25 microns or littler), can reach minification and reduce cost by manufacturing.Although having it has been found that some K is 15000 or higher dielectric ceramic, they are normally by high lead material such as lead magnesio-niobate, or niobium iron acid lead and similar material are made.The potential harm that brings to human body when handling the powder of high lead content, these materials also may have some MLC is used dissatisfactory characteristic, as lower mechanical strength, and the low K value that relatively poor chemical stability and MHz frequency place show.
The high dielectric constant material of barium phthalate base also is known, (for example, Burn, Proceedings of the Capacitor and Resistor TechnologySymposium (CARTS) Amsterdam 1989 of Raad and Sasaki).Yet crystallite dimension is generally greater than 5 microns, therefore, if the thickness of dielectric layer less than 25 microns, all exists some to lack the crystal grain of high reliability between each dielectric layer.The someone reports by wet chemical process method such as hydro thermal method (Neirman, J.Mats.Sc.Vol.23, P.3980,1988) or alkoxide process (Mc Sweeney, Proc.First Int.Conf.on Ceramic Powder ProcessingScience Orlando FA, 1987) barium titanate and the barium zirconate solid solution of making has high-k and less crystallite dimension.But these solid solution compositions are unsuitable for making thin layer MLC ' s, because their Curie's peak value (or Curie temperature) is too big greater than the variation of 25 ℃ and dielectric constant with temperature.It is too high that Curie temperature is higher than 25 ℃ the dissipation factor of composition, is unsuitable for making thin layer MLC ' s.Therefore, people need a kind of high-k that has always, and fine crystal particle size and Curie temperature are lower than 25 ℃ barium titanate based ceramic dielectric material.
US4,640,905 (Burn) have described the barium titanate based dielectric material, and its chemical formula is: (1-X) ((Ba
1-XPbx) Ti
1-(u+v)Zr
uSn
v) O
3)+
X (A (Zn
1/3Nb
2/3) O
3)+Y (E) wherein A is selected from Pb, Ba and their mixture, and F is the Firebrake ZB cosolvent that a kind of manganese mixes, x, u and V=0-0.125.Disclosed dielectric constant is up to 10300.
US4,855,266 (Burn) disclose the barium titanate-based composition that is applicable to the multilayer ceramic capacitor with copper electrode.This barium titanate comprises that donor and acceptor additive and a flux are mutually.The document has comprised the utilization of the barium titanate doping that contains Zr, Zn and Nb.The dielectric constant that obtains is up to 9000-10000.
US4,820,688 (people such as Kato) described a kind of K be 12000 and the sinter particle size be the barium titanate based dielectric material of 0.8-1 micron.This dielectric powder contains Ca, Zr, Sn, Bi, Y and Pb dopant, is to precipitate to obtain in the aqueous solution of barium chloride, titanium chloride and dopant.
US4,829,033 (people such as Menashi) and US4,643,984 (people such as Abe) disclose a kind of composite perofskite material of being made by hydro thermal method, and this material comprises the barium titanate of doping.
The present invention relates to a kind of composition, said composition is used to make a kind of dielectric of densification, and the dielectric constant of this dielectric is at least 10000, and Curie temperature is lower than 25 ℃, and crystallite dimension is 5 microns or littler.A first aspect of the present invention relates to a kind of composition, and said composition comprises:
(a) modified barium carbonate fine particle;
(b) (1) calcium and titanyl compound, their precursor, or calcium titanate and (2) manganese oxide, its precursor, the mixture additive of barium manganate or calcium manganate;
The barium titanate particles of this modification contains Zr, Zn and Nb dopant, and this dopant is evenly distributed in whole particles with atomic ratio (scale) by following chemical formula:
BaTi
1-(x+3y/2)(Zr
xZn
Y/2Nb
y) O
3X=0.01-0.20 wherein,
y＝0.005-0.075
Another aspect of the present invention relates to the dispersion of above-mentioned composition in a kind of organic media, and this dispersion can be poured into dielectric sheet.
A third aspect of the present invention relates to by the above-mentioned dielectric sheet of sintering, the dielectric layer made from the organic media of volatilization in the board falling, and make the inoganic solids densification by sintering.
Of the present inventionly relate in one aspect to a kind of capacitor at last, this capacitor comprises many above-mentioned dielectric layers, has scattered two metal electrode layers at least at interlayer.
In the present invention, zinc, niobium and zirconium dopant are to be incorporated in the barium titanate in the manufacture process of barium titanate.Disclose a kind of method for preparing barium titanate in common pending application U. S. application number 07/144835 (assignee's registration number CH-1412), this method may further comprise the steps:
(a) under alkalescence, high turbulent flow energy environment, with structural formula is that a kind of organo-metallic compound of TiLn or the mixture of organo-metallic compound are that a kind of compound of BaXy or the mixture solution of compound mix with general structure, wherein L is a kind of alkoxyl, aryloxy group, aminoalkoxy, acetate and acetylacetone based hydrolyzable group of being selected from, or the combination of this class group, X is a kind of anion or anion combination that is selected from hydroxyl, chloride ion, nitrate anion and acetate;
(b) make the product crystallization and
(c) crystal of emanating out.
In this method particularly preferred embodiment, barium titanate is prepared by following steps:
(a) at 80-85 ℃, under the high turbulent flow energy environment, make as the tetrabutyl titanate salt of the first component materials flow and barium hydroxide solution reaction as the second component materials flow, this step comprises that said component materials flow is pumped into a coaxial jet mixer simultaneously forms a kind of slip, and said slip is entered one fills the flooding in the groove of alkaline residue water (solution);
(b) under continuous stirring backflow heating condition, make said slip crystallization;
(c) the said crystal of emanating.
Described in detail as above-mentioned common pending application, by using for example a kind of zirconium-n-propylate, the mixture of niobium chloride and anhydrous zinc chloride partly replaces tetrabutyl titanate salt, just can be in preparation barium titanate process dopant such as Zr, Nb and Zn be mixed barium titanate.
Dopant replaced the titanium on the titanate lattice, as clearly shown in the perovskite x-ray diffraction pattern, do not have second sign that exists mutually.These dopants that mix with appropriate amount drop to from pure barium titanate about 130 ℃ of the Curie temperature of barium titanate to be lower than 25 ℃, preferably are about 5 ℃.The modified barium carbonate particle that contains an amount of dopant has following chemical formula:
BaTi
1-(x+3y/3)(Zr
xZn
Y/2Nb
y) O
3Wherein the scope of x is 0.01 to 0.20, and y is 0.005 to 0.075.In preferred particle, x is about 0.07, and y is about 0.027.
With (1) calcium and titanyl compound, their precursor, or calcium titanate and (2) manganese oxide, its precursor, the mixture of barium manganate or calcium manganate joins in the barium titanate particles of modification.Metal oxide precursor is a kind of compound, can change into metal oxide when this compound is calcined or burnt till.These precursors comprise carbonate, hydroxide and nitrate.
Well-known in the prior art, the calcium oxide inclusion in the barium titanate that mixes can be adjusted the width at Curie peak, reduces the dependence of dielectric constant to temperature.Yet we find in above-mentioned manufacture method, can not contain an amount of calcium in the barium titanate that mixes, and this is because the solubility of barium hydroxide greater than calcium hydroxide, makes barium react prior to calcium.With calcium titanate, or the mechanical impurity of precursor such as calcium carbonate and titanium oxide adds in the barium titanate of doping, attempts to adjust the width at Curie peak.We find that unexpectedly additive has stoped the growth of crystal grain well in burning till, thereby and this additive also offset the influence of dopant by the Curie peak being shifted to high-temperature slightly.Unfortunately, the insulation resistance of this modified barium carbonate and calcium oxide composition is too low, is unsuitable for practical application.In order to improve insulation resistance, also added small amounts manganese, its precursor, barium manganate or calcium manganate.Therefore, in barium titanate, add an amount of Zr, Zn and Nb, and an amount of calcium titanate and barium manganate or calcium manganate or precursor, can make the Curie temperature of dielectric material of the present invention be lower than 25 ℃, the crystallite dimension of burning till is less than 5 microns, and 25 ℃ of dielectric constants are greater than 15000, and this dielectric constant is reduced to less than about 85% in the time of 85 ℃.
The mechanical fusion method that substitutes the barium titanate of calcium, titanium and manganese additive and doping is additive-package to be coated on the surface of doped titanic acid barium dust by the common pending application number described method of 07/506966 (assignee's registration number CH-1757), and this method may further comprise the steps:
(a) stabilizing solution of a kind of concentrated metal (being additive) chelate of preparation;
(b) speed with control adds metallo-chelate solution in the barium titanate dry powder that mixes, and is being lower than this mixture of vigorous stirring under the liquid limie condition of powder simultaneously; With
(c) dry and this powder of calcining is with the decomposing metal chelate and remove volatile residue.
By with the mixture solution of metallic compound at the chelating agent that concentrates preparation metallo-chelate solution in moisture or water/organic solution.By adjusting pH value, chelating agent and metal ion form the soluble metal chelate.Chelating agent has increased the solubility of metallic compound in water or water/organic solvent.The solubility of this increase will be lower than for imposing on dry powder and applied amount that to obtain suitable coating under the situation of liquid limie of powder be necessary.
Under the speed of control, with the barium titanate powder that metallo-chelate solution is incorporated in, vigorous stirring under the condition that is lower than the powder liquid limie was finished the even distribution of particle before solvent evaporation simultaneously.Liquid limie represents with percentage by weight that with the water content of powder this powder is included in the borderline ceramic particle of determining arbitrarily between liquid and the mecystasis.ASTM standard D4318-84 has described the ortho-test of relevant soil liquid limie in detail very much, in here being incorporated herein as the reference of powder.
Powder is carried out dry and calcining with decomposing metal chelate and the uniform coating that forms on barium titanate powder.This method can make additive more be evenly distributed on the surface of powder, and compares with the method for barium titanate doping machinery fusion with additive, and the dissipation factor of this method is lower.The preferred additives coating has following composition (percentage by weight with final composition is represented):
0.25-5.0CaO
0.25-5.0TiO
2With
0.025-0.20MnO。
Barium titanate composition of the present invention can be made into the dielectric green sheet.A kind of method of making this plate is included in flexible base, board (as steel band or thin polymer film) and goes up ceramic barium titanate composition dispersion in a kind of solution that is dispersed in polymeric binder and volatile organic solvent of cast, then volatile solvent is removed in the bed of material heating of cast.
This organic media (solid ceramic is dispersed in wherein) is by polymeric binder (this binding agent is dissolved in a kind of volatile organic solvent), and at random, other dissolved material such as plasticizer, peel off that agent, anti-fouling agent and wetting agent form at release agent, dispersant.
In order to obtain better bonding efficiency, preferably the solid ceramic of 95% (wt) uses the polymeric binder of at least 5% (wt).Yet, more preferably in 80% (wt) solid ceramic, use no more than 20% (wt) polymeric binder.In these limited fields, preferably use a small amount of as far as possible binding agent with respect to solid, so that reduce the organic substance quantity that to be fallen by pyrolysis.
In the past, the binding agent that existing many kinds of polymeric materials are used as green sheet for example, (gathering) vinyl butyral, (gathering) vinyl acetate, (gathering) vinyl alcohol, cellulosic polymer is (as methylcellulose, ethyl cellulose, hydroxyethylcellulose, methyl hydroxyethylcellulose), atactic polypropylene, polyethylene, silicone polymer is (as (gathering) methylsiloxane, (gathering) tolyl siloxanes), polystyrene, butadiene/styrene copolymers, polystyrene, (gathering) vinylpyrrolidone, polyamide, high molecular weight polyether, oxirane and epoxy propane copolymer, polyacrylamide and various acrylate copolymer are (as Sodium Polyacrylate, (gathering) lower alkyl acrylate, (gathering) methacrylic acid lower alkyl esters) and the copolymer and the multiple copolymer of various lower alkyl acrylate and methacrylic acid lower alkyl esters).The terpolymer of the copolymer of EMA and methyl acrylate and ethyl acrylate, methyl methacrylate and methacrylic acid is used as the binding agent of mud injecting paste material at present.
Recently, Usala is at US4, discloses a kind of organic binder bond in 613,648, and this binding agent is 0-100% (weight) C
1-8Alkyl methacrylate, 100-0% (weight) C
1-8The mixture of the miscibility copolymer of alkyl acrylate and 0-5% (weight) ethylenically unsaturated carboxylic acids or amine.Because this polymer allows to use the binding agent of minimum and the dielectric solid of maximum, therefore preferably they are used with dielectric resistance compound of the present invention.
The selection of the solvent composition of cast solution is in order to obtain perfect polymer solution and sufficiently high effumability, so that just solvent can be evaporated from dispersion under applying less heat and atmospheric pressure.In addition, this solvent must boiling fully under the condition of boiling point that is lower than contained any other additive of organic media and decomposition temperature.Therefore, use atmospheric boiling point to be lower than 150 ℃ solvent usually.These solvents comprise acetone, dimethylbenzene, methyl alcohol, ethanol, methylethylketone, 1,1,1-trichloroethanes, tetrachloro-ethylene, pentyl acetate, 2,2,4-triethyl group pentanediol-1,3-mono isobutyrate, toluene and carrene.
Usually, organic media also can contain a small amount of (with respect to binder polymer) plasticizer, and the effect of this plasticizer is the glass transition temperature (Tg) that reduces binder polymer.Yet the consumption of this class material should be as far as possible little, so that reduce the organic material amount that must remove when sintered film waters injection.Certainly, selecting plasticizer mainly is by the polymer decision that must be modified.The plasticizer that has been used to various adhesive systems has diethyl phthalate, dibutyl phthalate, octyl phthalate, BBP(Butyl Benzyl Phthalate, alkylphosphonate, poly-(alkylidene) glycol, glycerol, (gathering) oxirane, hydroxyethylated alkyl phenol, disulfide group phosphate dialkyl ester and (gathering) isobutene.Certainly, BBP(Butyl Benzyl Phthalate is most commonly used to the acrylate copolymer system, because it can use under relatively low concentration effectively.
Multi-layered devices such as circuit and capacitor can be made with dielectric sheet green compact and aquadag metal level.For example, can metal layer be printed on the green sheet by predetermined pattern.Plate lamination after the printing is placed, and predetermined structure is made in lamination and cutting.This base assembly of sintering then is so that remove organic media in the metallization material and the organic binder bond in the dielectric material.Removing of these materials is by the combine realization of evaporation in firing operation with thermal decomposition.In some situation, can also before burning till, carry out a preliminary drying steps.Generally, the thickness that does not burn dielectric sheet generally is about the 18-30 micron, and the thickness after burning till becomes about 15-25 micron.Yet the present invention can make the thickness of dielectric sheet little of 10 microns or littler.
Required sintering temperature is to be determined by the physics of dielectric material and chemical characteristic.The temperature that will obtain the dielectric material maximum densification usually is chosen as sintering temperature.Yet, all should be understood that not to be always to need to obtain maximum densification in the art as the those of ordinary skill of making in the field of electronic devices.Therefore, term " sintering temperature " is meant the temperature (and reasonable time) that reaches the required densification degree of dielectric material for concrete application.
Under the situation that does not contain flux, composition of the present invention is at about ceramic material that sinters densification more than 1240 ℃ or 1240 ℃ into.But for sintering temperature being reduced to about 1125 ℃, can add Firebrake ZB or the known flux of other prior art, or in the bag coating of barium titanate doping, contain them, for example by the described method preparation of common pending application U. S. application sequence number 07/506964 (assignee's registration number CH-1676), this method may further comprise the steps:
(a) Firebrake ZB flux precursor is mixed with the barium titanate powder that Ca, Ti, Mn metal bag are coated with, make Firebrake ZB flux precursor on each particle, form uniform coating; With
(b) particle after dry and calcining (randomly) bag is coated with.
Finish a kind of bag coating method that this flux bag is coated with operation and be being lower than under the powder liquid limie condition and carry out fusion, this method comprises by following steps flux is distributed on the barium titanate powder particle that the metallic addition bag is coated with equably:
(a) in the barium titanate powder that the metal bag is coated with, add the concentrated solution of forming by at least a boron and a kind of zinc flux components precursor, simultaneously pH value is remained on predetermined scope and dissolve from the barium titanate powder particle surface to avoid ion;
(b) be lower than this mixture of vigorous stirring under the barium titanate powder liquid limie condition, be coated with particle so that wrap equably with the flux components precursor; With
(c) dry and this even particle that is coated with that wraps of calcining (at random).
Finishing the flux bag, to be coated with second kind of operation bag coating method be surface hydrolysis, and this method comprises that by following steps flux being distributed to the metal bag equably is coated with on the barium titanate powder particle:
(a) hydroxylating metal bag being coated with barium titanate powder is dispersed in the solution of being made up of at least a zinc and a kind of boron flux components hydrolysable precursors and a kind of water organic solvent immiscible;
(b) by filter, centrifugal or decant separates, and washing granule;
(c) dry and this even bag of calcining (at random) is coated with particle.
Finish the flux bag be coated with operation the third the bag coating method be surperficial coring, this method comprises that by following steps flux being distributed to the metal bag equably is coated with on the barium titanate powder particle
(a) the metal bag being coated with barium titanate powder is dispersed in the water;
(b) simultaneously or have sequentially a kind of aqueous solution that is made of at least a zinc and a kind of boron flux component precursor is joined in the aqueous dispersion, and simultaneously the PH with dispersion remains on 6.5-7.5, and temperature remains on 50-70 ℃ with the speed of control;
(c) reclaim the barium titanate powder particle; With
(d) dry and this even bag of calcining (at random) is coated with particle.
Sintering time also changes along with dielectric combination, but generally preferably is about 2.5 hours under sintering temperature.In case finish sintering, just the resistivity of thermal shock resistance controlled cooldown rate carefully to room temperature according to compound.
In a concrete scheme of the present invention, modified barium carbonate and additive metal oxide composition are made into dielectric sheet, and this dielectric sheet is made into monolithic capacitor.The method for optimizing of making this monolithic capacitor may further comprise the steps: (1) makes the green compact dielectric sheet with above-mentioned composition and organic binder bond; (2) apply one deck to each layer of multilayer green sheet and be dispersed in conductive electrode material in the organic media; (3) assembly of formation green compact electroplax and electrode material alternating layer; (4) burn till this assembly at about 1000 ℃, therefrom remove organic media and organic binder bond, and sintering conductor electrode material and dielectric material.The monolithic capacitor of making according to the method comprises a dielectric ceramic body, and the dielectric constant of this dielectric ceramic body is at least 10000, and crystallite dimension is not more than 5 microns and at least two and the contacted metal electrode that separates of ceramic body.
Embodiment 1
Adopt and make the barium titanate that is doped with Zr, Zn and Nb as stated above.Nominal consists of (by weight) BaO 64.44, TiO
229.71, ZrO
23.86, Nb
2O
51.51 and ZnO 0.463 forms.Chemical analysis is: BaO 63.79, TiO
229.24, ZrO
23.84, Nb
2O
51.53, ZnO 0.444, SrO 0.31.Particles of powder size (D
50) be 0.4 micron, and 900 ℃ of calcinings 5 hours.Specific area after the calcining is 6.2M
2/ gm.Make the pottery band by the immixture slip that cast is made up of 96.52% (weight) barium titanate doping, 1.79% calcium carbonate (1.00%CaO), 1.50% titanium dioxide and 0.20% manganese carbonate (0.12MnO).Has 2%AB1015 surfactant (E.I.duPont de Nemours ﹠amp; Co., 1,1 of Inc.WilmingtonDE (" Du Pont Co. "), in the 1-trichloroethanes (every gram powder 1 gram 1,1,1-trichloroethanes) powder ground and made a kind of slip in 16 hours, add acroleic acid binding agent solution (30 grams/100 gram powder) then, further ground 4 hours.This binder solution is the MEK (5200 binding agents, Du Pont Co.) of 91.7% acrylic resin and the mixture of 8.3% BBP(Butyl Benzyl Phthalate plasticizer.The pottery band is made MLC ' S (No. 1209, EIA), and this MLC ' S has 6 interior electrodes and 5 active layers, when burning till every layer about 14 microns.(for example, Du Pont 4820D) prints electrode with a kind of palladium (Pd) electrode cream.Capacitor slowly is heated to 550 ℃ removing organic binder bond, and in zircon sand, under 1240 ℃, this MLC ' S was burnt till 2.5 hours.The crystallite dimension of MLC ' the S pottery after burning till is the 2-3 micron.Average capacitance and be respectively 0.286 microfarad and 2.8% 0.5 volt of dissipation factor that records.Insulation resistance in the time of 25 ℃ surpasses 100,000 ohm of farads, 1610 ohm of farads of average out in the time of 125 ℃.Curie temperature is about 10 ℃, and 85 ℃ of capacitance deviations are-81.5%.The dielectric constant that calculates is 20500.
Embodiment 2
In the present embodiment, according to above-mentioned bag coating method 1.0%CaO, 1.50%TiO
2Be coated with above-mentioned adulterated flour end with the 0.12%MnO bag.After bag is coated with, this powder is calcined down at 700 ℃.Except MLC ' S be EIA1206 number when burning till tape thickness be 10 microns different with embodiment 1 method, be coated with powder according to embodiment 1 described method with this bag and make green compact band and MLC ' S.Burn till MLC ' S by the method for embodiment 1.The crystallite dimension of the pottery after burning till still is the 2-3 micron.Average capacitance is 0.293 microfarad, and the dissipation factor that records under 0.5 laid shoot spare is 2.0%.Insulation resistance in the time of 25 ℃ surpasses 100000 ohm of farads, at 8300 ohm of farads of 125 ℃ of average out to.Curie temperature is about 10 ℃, and 85 ℃ of capacitance deviations are-83%.The dielectric constant that calculates is 21000.
Embodiment 3
The amount of the manganese oxide in coating substitutes 0.12% with 0.06%, and present embodiment is similar to embodiment 2.The crystallite dimension of the pottery after burning till is about 1 micron.Average capacitance is 0.326 microfarad, and dissipation factor is 2.6%.25 ℃ of insulation resistances surpass 100000 ohm of farads, 3500 ohm of farads of 125 ℃ of average out to.Curie temperature is about 10 ℃.85 ℃ of capacitance deviations are-84%.The dielectric constant that calculates is 23000.
Embodiment 4
In the present embodiment, be coated with barium titanate doping with the Firebrake ZB bag as mentioned above.Zinc oxide and boron oxide level account for 0.78% and 0.22% of barium titanate doping weight respectively.Chemical analysis to zinc and boron shows: zinc oxide is 0.79% and B
2O
3Be 0.19%.Make a kind of immixture by grinding as stated above, this mixture is made up of barium titanate doping and 2.50% (weight) calcium titanate powder and 0.10% (weight) manganese carbonate that the Firebrake ZB bag is coated with.Except substituting with 70% silver medal-30% palladium electrode cream (for example, Du Pont4765 or 4803) outside No. 1206 sieves of palladium and use, according to making green compact band and MLC ' S with embodiment 1 similar methods.After binding agent is burnt, in zircon sand, MLC ' S was burnt till 2.5 hours in 1125 ℃.Burning till the back dielectric body thickness is 12.5 microns, and crystallite dimension is about 3 microns.Average capacitance 0.324 microfarad is 6.5% at 1.0 volts of DF that record, and is 2.1% at 0.1 volt of DF that records.At 76000 ohm of farads of 25 ℃ of insulation resistance average out to, be 6100 ohm of farads at 125 ℃.Curie temperature is about 10 ℃.85 ℃ of capacitance deviations are-86%.The dielectric constant that calculates is 25000.
Embodiment 5
Make and burn till MLC ' S according to embodiment 4, but in dielectric combination, do not add calcium titanate.Medium thickness is 13.5 microns, but crystallite dimension is very irregular, some crystal grain is arranged greater than 10 microns.Average capacitance is 0.09 microfarad, is 3.4% at 1 volt of DF that records.Insulation resistance changes greatly, 320 ohm of farads of 25 ℃ of average out to, and 125 ℃ is 1019 ohm of farads, some capacitor IR value＜1 ohm of farad.This relatively poor reliability may be owing to exist big crystal grain to cause in the pottery.Curie temperature is about 0 ℃ (promptly being lower than the situation that CaO is arranged).85 ℃ of capacitance deviations are-70%.The dielectric constant that calculates (25 ℃) is 8300.
Claims (4)
1. dielectric sheet, this dielectric sheet comprises a kind of pouring layer of composition, said composition is used to make a kind of Curie temperature less than 25 ℃, dielectric constant be at least 10000 and crystallite dimension be 5 microns or littler fine and close dielectric, said composition contains:
(a) modified barium carbonate fine particle;
(b) (1) calcium and titanyl compound, their precursor, or calcium titanate and (2) manganese oxide, its precursor, the mixture additive of barium manganate or calcium manganate; With
(c) a kind of organic media, this organic media contain the solution of a kind of volatile organic solvent and organic polymer binder,
This modified barium carbonate particle contains Zr, Zn and Nb, and they are evenly distributed in whole particles with atomic ratio by following formula:
BaTi
1-(x+3y/2)(Zr
xZn
y/2Nb
y)O
3
Wherein x=0.01-0.20 and
y＝0.005-0.075，
Represent with composition weight percentage that wherein the mixture additive of oxide or its precursor comprises:
0.25-5.0 weight %CaO;
0.25-5.0 weight %TiO
2With
0.025-0.20 weight %MnO,
Wherein, this dielectric sheet has been heated and has removed volatile organic media.
2. dielectric ceramic layer that comprises the plate of claim 1, this dielectric ceramic layer is burnt till, makes organic media volatilization and make the inorganic component densification by sintering from said layer.
3. multi-layered devices that comprises a plurality of dielectric ceramic layers in the claim 2, this device is being mingled with conductive layer.
4. multilayer dielectric pottery and at least two capacitors that are mingled with metal electrode therebetween that comprise claim 2, this assembly burns till through temperature more than 1000 ℃, vapors away organic media, makes inorganic material densification and sintered metal electrode in the dielectric sheet.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 01137766 CN1392570A (en) | 2001-10-30 | 2001-10-30 | High k dielectric composition with fine crystal particle size |
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| CN 01137766 CN1392570A (en) | 2001-10-30 | 2001-10-30 | High k dielectric composition with fine crystal particle size |
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| CN92102078A Division CN1084919C (en) | 1992-03-05 | 1992-03-05 | High-k dielectric composition with fine grain size |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101154479B (en) * | 2003-04-04 | 2011-05-04 | 东丽株式会社 | Dielectric composition, capacitor and light wiring using the dielectric composition |
| CN107026015A (en) * | 2015-09-15 | 2017-08-08 | Tdk株式会社 | Laminated electronic component |
| CN109285698A (en) * | 2017-07-19 | 2019-01-29 | 太阳诱电株式会社 | Multilayer ceramic capacitor and method of manufacturing the same |
-
2001
- 2001-10-30 CN CN 01137766 patent/CN1392570A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101154479B (en) * | 2003-04-04 | 2011-05-04 | 东丽株式会社 | Dielectric composition, capacitor and light wiring using the dielectric composition |
| CN107026015A (en) * | 2015-09-15 | 2017-08-08 | Tdk株式会社 | Laminated electronic component |
| US9991054B2 (en) | 2015-09-15 | 2018-06-05 | Tdk Corporation | Multilayer electronic component |
| CN107026015B (en) * | 2015-09-15 | 2019-01-01 | Tdk株式会社 | Laminated electronic component |
| CN109285698A (en) * | 2017-07-19 | 2019-01-29 | 太阳诱电株式会社 | Multilayer ceramic capacitor and method of manufacturing the same |
| CN109285698B (en) * | 2017-07-19 | 2022-03-29 | 太阳诱电株式会社 | Multilayer ceramic capacitor and method for manufacturing the same |
| US11631540B2 (en) | 2017-07-19 | 2023-04-18 | Taiyo Yuden Co., Ltd. | Multilayer ceramic capacitor of barium titanate ceramic doped with molybdenum and manufacturing method thereof |
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