CN1623955A - Ceramic material of middle-low temp. sintered temp stable type multirayer ceramic capacitor - Google Patents
Ceramic material of middle-low temp. sintered temp stable type multirayer ceramic capacitor Download PDFInfo
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- CN1623955A CN1623955A CN 200410090868 CN200410090868A CN1623955A CN 1623955 A CN1623955 A CN 1623955A CN 200410090868 CN200410090868 CN 200410090868 CN 200410090868 A CN200410090868 A CN 200410090868A CN 1623955 A CN1623955 A CN 1623955A
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 24
- 229910010293 ceramic material Inorganic materials 0.000 title abstract 2
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 10
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 9
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000010955 niobium Substances 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 239000004615 ingredient Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 238000009766 low-temperature sintering Methods 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 41
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 7
- 238000000748 compression moulding Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
A ceramic material used for X7R-model multi-layer ceramic capacitor with medium or low sinter temp and high temp stability is prepared from barium titanate and the additive chosen from cobalt oxide and niobium oxide, or their compound, yttrium oxide, RE oxide, Ag, zinc oxdie and boron oxide, or their compound. It has dielectric constant of 1800-5600, capacitance-temp variation rate less than +/-15%, and sinter temp of 900-1150 deg.C.
Description
Technical field
The invention belongs to field of capacitor material technology, particularly the temperature-stable multilayer ceramic capacitor stupalith of low temperature sintering.
Background technology
High speed development along with mobile electronic devices such as polytype electronics such as digital camera, mobile telephone, notebook computer, palm PCs, miniaturization and the lightness trend that is inevitable, the components and parts that constitute these electronicss also must reduce volume and weight, change the needs of surface mounting technology (SMD) into the field engineering that adapts to electronic component, the components and parts that surface mounting technology requires are chip components and parts.Laminated ceramic capacitor is a most widely used class in the slice component.Laminated ceramic capacitor (Multilayer CeramicCapacitors) is called for short MLCC.It is that electrode materials is replaced in parallel being superimposed together with ceramic body with multilayer, and burns till an integral body simultaneously.According to the international EIA of Electronic Industries Association USA (Electronic IndustriesAssociation) standard, temperature-stable (X7R) type MLCC is meant that the capacitance with 25 ℃ is a benchmark, within the scope of from-55 to+125 ℃ of temperature, temperature coefficient of capacitance＜± 15%, dielectric loss (DF)≤2.5%.X7R type MLCC divides two big classes by forming: a class is made up of plumbiferous ferroelectrics, and is another kind of with BaTiO
3The ferroelectrics of the non-plumbous system of base is formed.And the latter is because environmentally safe, and physical strength and reliability be better than the former, and therefore non-lead is BaTiO
3Base X7R type MLCC has broad application prospects.
In order to reduce material and technology cost, two kinds of methods are arranged: (1) adopts base metal nickel (Ni) to substitute the inner electrode of precious metal palladium (Pd) as laminated ceramic capacitor, can reduce the material cost of forming laminated ceramic capacitor so greatly, so laminated ceramic capacitor forward large vol, undersized direction develop.Both at home and abroad the research of base metal inner electrode multilayer ceramic capacitor is compared early, relevant report is also a lot.Through effort for many years, electrode has replaced electrode in traditional Ag/Pd substantially in the Ni now; (2) sintering temperature of reduction laminated ceramic capacitor, use the poor silver palladium alloy of palladium or with fine silver as inner electrode, when reducing the material cost of laminated ceramic capacitor, can also reduce the energy consumption of sintering process, thereby reduce the cost of whole multi-layer ceramic capacitor material and manufacturing.And it is few to be seen in the early stage document of report in this respect.The early stage research work that reduces sintering temperature, some used leaded or cadmium etc. to human body or the deleterious sintering agent of environment.Disclose the X7R type stupalith that a kind of sintering temperature is about 1100 ℃ among the US 5,571,767 as the nineteen ninety-five application, its room temperature dielectric constant is about 3200, but this stupalith contains Pb, therefore can not produce use.Have only MRA Laboratories in the recent period, Inc. company has applied for several relevant patents.The US 6,723,673 of application in 2003 discloses a kind of X7R type stupalith of low sintering high-k.Its sintering temperature is about 1025 ℃, and the room temperature dielectric constant that calculates according to laminated ceramic capacitor is about 3200, and the ceramics specific inductivity estimates about 2700～2800.
Therefore, need a kind of sintering temperature low, not to human body and the deleterious element of environment, specific inductivity X7R type stupalith higher, that can significantly reduce costs, excellent property.
Summary of the invention
The objective of the invention is to adjust the prescription of properties-correcting agent and the temperature-stable multilayer ceramic capacitor stupalith of the low temperature sintering that sintering process is prepared by being major ingredient with chemical process synthetic BaTiO3; It is characterized in that:
The multi-layer ceramic capacitor material of described low sintering temperature-stable comprises two kinds of porcelains:
Porcelain 1: be made up of barium titanate major ingredient and the secondary additive that improves dielectric temperature characteristic and reduce sintering temperature, described secondary additive comprises at least a in niobium oxides, cobalt oxide or their soluble solids, zinc oxide, boron oxide or their soluble solids, yttrium oxide and the rare earth oxide; The prescription of described each material is (in molar ratio):
[100-(a+b+c+d+f+g+h)]BaTiO
3+a?Nb
2O
5+bCo
3O
4+c(Nb
2O
5)
x·(Co
3O
4)
1-x+dRe
2O
3+fZnO+g?B
2O
3+h(ZnO)
y·(B
2O
3)
1-y。Wherein Re represents yttrium and rare earth element, Re
2O
3Represent the oxide compound of yttrium oxide and rare earth element, rare earth element is lanthanon lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), dysprosium (Dy), erbium (Er) and ytterbium (Yb); Wherein cerium oxide is CeO
20.0≤a≤3.0,0.0≤b≤1.5,0.0≤c≤1.2,1.0≤a+b+c≤5.0,0.1≤x≤0.9,0.1≤d≤1.2,0.0≤e≤3.0,0.0≤f≤1.5,0.0≤g≤1.2,0.0≤h≤10.0,0≤f+g+h≤10.0,0.1≤y≤0.9 wherein.
Described low sintering temperature-stable multilayer ceramic capacitor, major ingredient BaTiO in the prescription
390～99mol% of shared total amount of material; The consumption of secondary additive accounts for 1～10mol% of total amount of material.
[100-(a+b+c+d+e+f+g+h)]BaTiO
3+a?Nb
2O
5+b?Co
3O
4+c(Nb
2O
5)
x·(Co
3O
4)
1-x+d?Re
2O
3+e?Ag+f?ZnO+g?B
2O
3+h(ZnO)
y·(B
2O
3)
1-y。Wherein Re represents yttrium and rare earth element, Re
2O
3Represent the oxide compound of yttrium oxide and rare earth element, rare earth element is lanthanon lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), dysprosium (Dy), erbium (Er) and ytterbium (Yb); Wherein cerium oxide is CeO
2
0.0≤a≤3.0,0.0≤b≤1.5,0.0≤c≤1.2,1.0≤a+b+c≤5.0,0.1≤x≤0.9,0.1≤d≤1.2,0.0≤e≤15.0,0.0≤f≤1.5,0.0≤g≤1.2,0.0≤h≤10.0,0≤f+g+h≤10.0,0.1≤y≤0.9 wherein.
Described low sintering temperature-stable multilayer ceramic capacitor, major ingredient BaTiO in the prescription
380～99mol% of shared total amount of material; The consumption of secondary additive accounts for 1～20mol% of total amount of material.
The invention has the beneficial effects as follows the ultra-fine BaTiO of chemical method preparation
3Being MLCC has three advantage: a. can reduce sintering temperature, the bullion content of electrode in reducing, thus reduce cost, b. grain-size is little, and narrow particle size distribution helps the attenuate of thickness of dielectric layers, c. chemical uniformity is good, helps improving the reliability of electrical condenser.
Description of drawings:
Fig. 1 is the performance diagram that the dielectric constant with temperature of the sample of the embodiment of the invention 1 changes.
Fig. 2 is the temperature variant graphic representation of percentage of capacitance variation with temperature of the sample of the embodiment of the invention 1.
Fig. 3 is the performance diagram that the dielectric constant with temperature of the sample of the embodiment of the invention 2 changes.
Fig. 4 is the temperature variant graphic representation of percentage of capacitance variation with temperature of the sample of the embodiment of the invention 2.
Fig. 5 is the performance diagram that the dielectric constant with temperature of the sample of the embodiment of the invention 3 changes.
Fig. 6 is the temperature variant graphic representation of percentage of capacitance variation with temperature of the sample of the embodiment of the invention 3.
Fig. 7 is the performance diagram that the dielectric constant with temperature of the sample of the embodiment of the invention 4 changes.
Fig. 8 is the temperature variant graphic representation of percentage of capacitance variation with temperature of the sample of the embodiment of the invention 4.
Fig. 9 is the performance diagram that the dielectric constant with temperature of the sample of the embodiment of the invention 5 changes.
Figure 10 is the temperature variant graphic representation of percentage of capacitance variation with temperature of the sample of the embodiment of the invention 5.
Figure 11 is the performance diagram that the dielectric constant with temperature of the sample of the embodiment of the invention 6 changes.
Figure 12 is the temperature variant graphic representation of percentage of capacitance variation with temperature of the sample of the embodiment of the invention 6.
Figure 13 is the performance diagram that the dielectric constant with temperature of the sample of the embodiment of the invention 7 changes.
Figure 14 is the temperature variant graphic representation of percentage of capacitance variation with temperature of the sample of the embodiment of the invention 7.
In conjunction with top test curve figure, exemplify following examples and respectively the present invention illustrated:
Embodiment 1
Barium titanate BaTiO
3Major ingredient adopts hydrothermal method synthetic, and initial particle is about 300nm.At first the synthetic Nb/Co atomic ratio of solid phase method is respectively the soluble solids of 3: 1 and 2: 1.Add secondary additive by prescription respectively in barium carbonate powder material 20g, the dissolved solids content of Nb/Co is 1.5wt% in the prescription, and the content of Neodymium trioxide is 0.9wt%, is designated as 1-1,1-2.Batching is mixed through ball milling, after the drying, and compression moulding under 2MPa pressure, diameter is 10mm, thickness is 1mm.At 1150 ℃ of sintering 4h, heat-up rate is 6 ℃/min.Measure its dielectric properties behind the ceramics surface silver ink firing that burns till.The dielectric properties parameter of the ceramics sample that is obtained sees Table 1.What Fig. 1 curve provided is the dielectric temperature characteristic curve of sample.Fig. 2 provides the temperature coefficient of capacitance curve of sample.
Barium titanate BaTiO
3Major ingredient adopts hydrothermal method synthetic, and initial particle is about 300nm.Add secondary additive by prescription respectively in barium carbonate powder material 20g, the Nb/Co atomic ratio is that 3: 1 dissolved solids content is 1.2wt% in the prescription, and the content of lanthanum trioxide is respectively 0.8wt%, 0.9wt%, 1.0wt%, is designated as 2-1,2-2,2-3.Batching is mixed through ball milling, after the drying, and compression moulding under 2MPa pressure, diameter is 10mm, thickness is 1mm.At 1150 ℃ of sintering 4h, heat-up rate is 6 ℃/min.Measure its dielectric properties behind the ceramics surface silver ink firing that burns till.The dielectric properties parameter of the ceramics sample that is obtained sees Table 1.What Fig. 3 curve provided is the dielectric temperature characteristic curve of sample.Fig. 4 provides the temperature coefficient of capacitance curve of sample.
Embodiment 3
Barium titanate BaTiO
3Major ingredient adopts hydrothermal method synthetic, and initial particle is about 300nm.Add secondary additive by prescription in barium carbonate powder material 20g, the Nb/Co atomic ratio is that 3: 1 dissolved solids content is 1.5wt% in the prescription, and Neodymium trioxide and Samarium trioxide mix jointly, and content is respectively 0.6wt%, 0.3wt%, is designated as 3-1.Batching is mixed through ball milling, after the drying, and compression moulding under 2MPa pressure, diameter is 10mm, thickness is 1mm.At 1150 ℃ of sintering 4h, heat-up rate is 6 ℃/min.Measure its dielectric properties behind the ceramics surface silver ink firing that burns till.The dielectric properties parameter of the ceramics sample that is obtained sees Table 1.What Fig. 5 curve provided is the dielectric temperature characteristic curve of sample.Fig. 6 provides the temperature coefficient of capacitance curve of sample.
Embodiment 4
Prescription is formed fixing, uses the barium carbonate powder of different initial particle sizes.In barium carbonate powder material 20g, add secondary additive by prescription, the Nb/Co atomic ratio is that 3: 1 dissolved solids content is 1.2wt% in the prescription, the content of cerium oxide is 0.6wt%, the barium carbonate powder size of using is respectively 100nm, 150nm, 200nm, 300nm, is designated as 4-1,4-2,4-3,4-4 respectively.Batching is mixed through ball milling, after the drying, and compression moulding under 2MPa pressure, diameter is 10mm, thickness is 1mm.At 1150 ℃ of sintering 4h, heat-up rate is 6 ℃/min.Measure its dielectric properties behind the ceramics surface silver ink firing that burns till.The dielectric properties parameter of the ceramics sample that is obtained sees Table 1.What Fig. 7 curve provided is the dielectric temperature characteristic curve of sample.Fig. 8 provides the temperature coefficient of capacitance curve of sample.
At the 20g particle diameter is to add secondary additive by prescription in the barium carbonate powder material of 300nm, the Nb/Co atomic ratio is that 3: 1 dissolved solids content is 1.2wt% in the prescription, the content of Neodymium trioxide is 0.6wt%, and the amount of adding Silver Nitrate is 0.5wt%, 10wt%, is designated as 5-1,5-2 respectively.Batching is mixed through ball milling, after the drying, is incubated half an hour at 450 ℃, makes Silver Nitrate be decomposed into argent, and with the pressure compression moulding of 2MPa, diameter is 10mm then, and thickness is 1mm.At 1150 ℃ of sintering 4h, heat-up rate is 6 ℃/min.Measure its dielectric properties behind the ceramics surface silver ink firing that burns till.The dielectric properties parameter of the ceramics sample that is obtained sees Table 1.What Fig. 9 curve provided is the dielectric temperature characteristic curve of sample.Figure 10 provides the temperature coefficient of capacitance curve of sample.
At the 20g particle diameter is to add secondary additive by prescription in the barium carbonate powder material of 300m, and the Nb/Co atomic ratio is that 3: 1 dissolved solids content is 1.2wt% in the prescription, and the content of Praseodymium trioxide is 0.6wt%, adds Zn
4B
6O
13Amount be 1.5wt%, be designated as 6-1.Batching is mixed through ball milling, and after the drying, with the pressure compression moulding of 2MPa, diameter is 10mm, and thickness is 1mm.Sample 6-1 is at 920 ℃ of sintering 6h, and heat-up rate is 6 ℃/min.Measure its dielectric properties behind the ceramics surface silver ink firing that burns till.The dielectric properties parameter of the ceramics sample that is obtained sees Table 1.What Figure 11 curve provided is the dielectric temperature characteristic curve of sample.Figure 12 provides the temperature coefficient of capacitance curve of sample.
Embodiment 7
At the 20g particle diameter is to add secondary additive by prescription in the barium carbonate powder material of 450nm, and the Nb/Co atomic ratio is that 3: 1 dissolved solids content is 1.2wt% in the prescription, and the content of dysprosium oxide is 0.6wt%, adds Zn
4B
6O
13Amount be 3.5wt%, 4.0wt%, be designated as 7-1,7-2 respectively.Batching is mixed through ball milling, and after the drying, with the pressure compression moulding of 2MPa, diameter is 10mm, and thickness is 1mm.Sample 7-1,7-2 are at 1050 ℃ of sintering 2h, and heat-up rate is 6 ℃/min.Measure its dielectric properties behind the ceramics surface silver ink firing that burns till.The dielectric properties parameter of the ceramics sample that is obtained sees Table 1.What Figure 13 curve provided is the dielectric temperature characteristic curve of sample.Figure 14 provides the temperature coefficient of capacitance curve of sample.
In addition, the insulation resistance of all embodiment samples and voltage breakdown test result see Table 1.
Above-mentioned experimental example explanation by the adjustment of prescription and technology, can obtain the high performance barium phthalate base X7R type MLCC material of low temperature sintering.The room temperature dielectric constant of wafer sample can be controlled between 1800 and 5600, temperature coefficient of capacitance≤± 15%, and sintering range is from 900 ℃ to 1150 ℃.Utilize prescription of the present invention and technology, it is low to obtain sintering temperature, and performance is adjustable, and sintering range is wide, stability and the good barium phthalate base X7R type MLCC material of reproducibility.And the uniform crystal particles of material, crystal grain is tiny, and size range is from 100nm to 600nm, and good pressure-resistant performance is a kind of MLCC material with wide application prospect.
The sintering condition and the performance perameter of all embodiment samples of table 1
| Sample number into spectrum | Particle diameter (nm) | Sintering condition | Specific inductivity | ??TCC ??(％) | Specific inductivity (25 ℃) | Specific inductivity | ????TCC ????(％) | ????tgδ ?? (25℃)(％) | Insulation resistivity (10 12× ??Ω·cm) | Breaking down field strength (KV/ mm) | The X7R temperature profile |
| ????????-55℃ | ???????????125℃ | ||||||||||
| 1-1 | ????300 | ????1150℃/4h | ??2358 | ??-1.3 | ??2388 | ????2268 | ????-5.0 | ????1.30 | ????0.42 | ????6.0 | Be |
| 1-2 | ????300 | ????1150℃/4h | ??2379 | ??-4.5 | ??2491 | ????2060 | ????-17.3 | ????2.0 | ????0.11 | ????4.9 | Not |
| 2-1 | ????300 | ????1150℃/4h | ??2477 | ??-9.8 | ??2745 | ????2381 | ????-13.2 | ????0.95 | ????0.87 | ????7.5 | Be |
| 2-2 | ????300 | ????1150℃/4h | ??2306 | ??-11.3 | ??2601 | ????2386 | ????-8.2 | ????2.10 | ????0.75 | ????8.2 | Be |
| 2-3 | ????300 | ????1150℃/4h | ??2557 | ??-5.5 | ??2707 | ????2538 | ????-6.2 | ????1.21 | ????2.13 | ????5.3 | Be |
| 3-1 | ????300 | ????1150℃/4h | ??2634 | ??-0.5 | ??2647 | ????2410 | ????-8.9 | ????1.17 | ????5.16 | ????10.0 | Be |
| 4-1 | ????100 | ????1150℃/4h | ??1518 | ??-14.5 | ??1775 | ????1694 | ????-4.5 | ????1.04 | ????4.33 | ????7.2 | Be |
| 4-2 | ????150 | ????1150℃/4h | ??1750 | ??-14.9 | ??2057 | ????1948 | ????-5.3 | ????1.70 | ????0.64 | ????5.8 | Be |
| 4-3 | ????200 | ????1150℃/4h | ??1828 | ??-12.1 | ??2080 | ????2034 | ????-2.2 | ????1.14 | ????1.20 | ????9.0 | Be |
| 4-4 | ????300 | ????1150℃/4h | ??2160 | ??-4.1 | ??2252 | ????2398 | ????6.5 | ????1.05 | ????0.96 | ????5.6 | Be |
| 5-1 | ????300 | ????1150℃/4h | ??2919 | ??-6.4 | ??3119 | ????3172 | ????1.7 | ????0.89 | ????1.77 | ????9.1 | Be |
| 5-2 | ????300 | ????1150℃/4h | ??5049 | ??-9.1 | ??5560 | ????5314 | ????-4.4 | ????1.05 | ????0.96 | ????5.6 | Be |
| 6-1 | ????300 | ????920℃/6h | ??1780 | ??-5.2 | ??1876 | ????1832 | ????-2.4 | ????0.94 | ????8.39 | ????8.4 | Be |
| 7-1 | ????450 | ????1050℃/2h | ??2080 | ??-1.5 | ??2119 | ????2092 | ????-0.9 | ????1.13 | ????3.2 | ????8.6 | Be |
| 7-2 | ????450 | ????1050℃/2h | ??2479 | ??3.4 | ??2398 | ????2184 | ????-8.9 | ????0.97 | ????4.5 | ????9.1 | Be |
The meaning of each parameter representative is as follows in the table 1:
TCC: temperature coefficient of capacitance; Tg δ: dielectric loss;
Above-mentioned Fig. 1～Figure 14 is corresponding to the specific inductivity temperature characteristics of each sample of embodiment 1～7 and the temperature curve that electric capacity varies with temperature rate.Probe temperature is-60 ℃～135 ℃.
Claims (3)
1. the temperature-stable multilayer ceramic capacitor stupalith of a low temperature sintering, be in the temperature-stable multilayer ceramic capacitor stupalith of major ingredient with chemical process synthetic BaTiO3, adjust the prescription of secondary additive, obtain the multi-layer ceramic capacitor material of the low sintering temperature-stable of two kinds of porcelains; It is characterized in that:
Porcelain 1: be made up of barium titanate major ingredient and the secondary additive that improves dielectric temperature characteristic and reduce sintering temperature, described secondary additive comprises at least a in niobium oxides, cobalt oxide or their soluble solids, zinc oxide, boron oxide or their soluble solids, yttrium oxide and the rare earth oxide; The prescription of described each material is (in molar ratio):
[100-(a+b+c+d+f+g+h)]BaTiO
3+aNb
2O
5+bCo
3O
4+c(Nb
2O
5)
x·(Co
3O
4)
1-x+dRe
2O
3+fZnO+gB
2O
3+h(ZnO)
y·(B
2O
3)
1-y；
Wherein Re represents yttrium and rare earth element, Re
2O
3Represent the oxide compound of yttrium oxide and rare earth element, rare earth element is lanthanon lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), dysprosium (Dy), erbium (Er) and ytterbium (Yb); Wherein cerium oxide is CeO
2
0≤a≤3,0≤b≤1.5,0≤c≤1.2,1≤a+b+c≤5,0.1≤x≤0.9,0.1≤d≤1.2,0≤e≤3,0≤f≤1.5,0≤g≤1.2,0≤h≤10,0≤f+g+h≤10,0.1≤y≤0.9 wherein;
Porcelain 2: form by barium titanate major ingredient and the secondary additive that improves dielectric temperature characteristic and reduction sintering temperature, described secondary additive comprises at least a, zinc oxide, boron oxide or their soluble solids in the oxide compound of niobium oxides, cobalt oxide or their soluble solids, yttrium oxide and rare earth element, and argent.The prescription of described each material is:
[100-(a+b+c+d+e+f+g+h)]BaTiO
3+aNb
2O
5+bCo
3O
4+c(Nb
2O
5)
x·(Co
3O
4)
1-x+dRe
2O
3+eAg+fZnO+gB
2O
3+h(ZnO)
y·(B
2O
3)
1-y；
Wherein Re represents yttrium and rare earth element, Re
2O
3Represent the oxide compound of yttrium oxide and rare earth element, rare earth element is lanthanon lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), dysprosium (Dy), erbium (Er) and ytterbium (Yb); Wherein cerium oxide is CeO
2
0≤a≤3,0≤b≤1.5,0≤c≤1.2,1≤a+b+c≤5,0.1≤x≤0.9,0.1≤d≤1.2,0≤e≤15.0,0≤f≤1.5,0≤g≤1.2,0≤h≤10,0≤f+g+h≤10,0.1≤y≤0.9 wherein.
2. according to the temperature-stable multilayer ceramic capacitor stupalith of the described low temperature sintering of claim 1, it is characterized in that: major ingredient BaTiO in described porcelain 1 prescription
390～99mol% of shared total amount of material; The consumption of secondary additive accounts for 1～10mol% of total amount of material.
3. according to the temperature-stable multilayer ceramic capacitor stupalith of the described low temperature sintering of claim 1, it is characterized in that: major ingredient BaTiO in described porcelain 2 prescriptions
380～99mol% of shared total amount of material; The consumption of secondary additive accounts for 1～20mol% of total amount of material.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304328C (en) * | 2005-10-13 | 2007-03-14 | 浙江大学 | Temperature-stabilized electronic ceramic material with ultra-high dielectric constant and production thereof |
| CN100415682C (en) * | 2006-12-27 | 2008-09-03 | 天津大学 | Temperature stable type barium titanate system ceramic and its preparation method |
| CN101921106A (en) * | 2010-06-29 | 2010-12-22 | 上海大学 | Preparation method of (Ba, Sr)TiO3 nanometer/micrometer/nanometer laminated structure ceramics |
| CN101492293B (en) * | 2009-03-09 | 2011-08-10 | 陕西科技大学 | Barium titanate based Y5P ceramic dielectric material and method of producing the same |
| CN102351533A (en) * | 2011-07-15 | 2012-02-15 | 桂林电子科技大学 | Calcium barium zirconate titanate based leadless piezoelectric ceramics with low temperature sintering and high piezoelectric properties and preparation method thereof |
-
2004
- 2004-11-16 CN CN 200410090868 patent/CN1623955A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304328C (en) * | 2005-10-13 | 2007-03-14 | 浙江大学 | Temperature-stabilized electronic ceramic material with ultra-high dielectric constant and production thereof |
| CN100415682C (en) * | 2006-12-27 | 2008-09-03 | 天津大学 | Temperature stable type barium titanate system ceramic and its preparation method |
| CN101492293B (en) * | 2009-03-09 | 2011-08-10 | 陕西科技大学 | Barium titanate based Y5P ceramic dielectric material and method of producing the same |
| CN101921106A (en) * | 2010-06-29 | 2010-12-22 | 上海大学 | Preparation method of (Ba, Sr)TiO3 nanometer/micrometer/nanometer laminated structure ceramics |
| CN101921106B (en) * | 2010-06-29 | 2012-11-14 | 上海大学 | Preparation method of (Ba, Sr)TiO3 nanometer/micrometer/nanometer laminated structure ceramics |
| CN102351533A (en) * | 2011-07-15 | 2012-02-15 | 桂林电子科技大学 | Calcium barium zirconate titanate based leadless piezoelectric ceramics with low temperature sintering and high piezoelectric properties and preparation method thereof |
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