CN1461023A - Ultrathin temperature stable type multilayer ceramic capacitor dielectric material and its sintering process - Google Patents
Ultrathin temperature stable type multilayer ceramic capacitor dielectric material and its sintering process Download PDFInfo
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- 238000005245 sintering Methods 0.000 title claims abstract description 51
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003989 dielectric material Substances 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000010953 base metal Substances 0.000 claims description 12
- 239000004615 ingredient Substances 0.000 claims description 12
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000000280 densification Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000003891 oxalate salts Chemical class 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002305 electric material Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract 2
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 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
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses a superfine temp.-stabilized multi-layer ceramic capacitor dielectric material and its sintering process. The material contains main component BaTiO3 and secondary additive CaO, CaTiO3, BaO, SiO2, SrO, MnO2, MgO, Co2O3, Co3O4, Fe2O3 and Y2O3 and one kind of more than one kind of rare earth oxide. Said invention adopts "two-stage" type microcrystalline control technique sintering process and utilizes the above-mentioned materials to obtain the temp.-stabilized type (including XTR and X5R) MLCC antireduction dielectric material with excellent performance. The invention is suitable for producing multi-layer ceramic capacitor with large capacity and superthin dielectric layer.
Description
Technical field
The invention belongs to field of capacitor material technology, particularly a kind of ultra-fine temperature-stable multilayer ceramic capacitor dielectric material and sintering process thereof.
Background technology
High speed development along with mobile electronic devices such as polytype electronic equipment such as digital camera, mobile phone, notebook computer, palmtop PCs, miniaturization and the lightness trend that is inevitable, the components and parts that constitute these electronic equipments also must reduce volume and weight, change the needs of surface mounting technology (SMD) into the mounting technique that adapts to electronic component, the components and parts that surface mounting technology requires are chip components and parts.Multilayer ceramic capacitor is a most widely used class in the chip component.Multilayer ceramic capacitor (Multilayer Ceramic Capacitors) is called for short MLCC.It is that electrode material 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 (Electronic IndustriesAssociation) standard: temperature stabilization 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%; Temperature stabilization X5R type MLCC is meant that the capacitance with 25 ℃ is a benchmark, within the scope of from-55 to+85 ℃ of temperature, and temperature coefficient of capacitance≤± 15%, dielectric loss (DF)≤2.5%.Temperature-stable MLCC divides two big classes by forming: a class is made up of leaded ferroelectric, and is another kind of with BaTiO
3The ferroelectric of the non-plumbous system of base is formed.And the latter is because environmentally safe, and mechanical strength and reliability be better than the former, and therefore non-lead is BaTiO
3Base temperature-stable MLCC has broad application prospects.
When the multilayer ceramic capacitor that with the barium titanate is base during sintering, needs to use noble metals (Pt, Au, Pd metal and alloy thereof etc.) as interior electrode in air.The cost of electrode is 30%～70% of a multilayer ceramic capacitor production cost in the noble metal.Therefore use noble metal to become the obstacle that reduces the MLCC cost as interior electrode.Based on the consideration that reduces cost, base metals such as use such as Ni, Fe, Co, Cu and alloy thereof are as the interior electrode of MLCC, but, therefore lose effect as interior electrode when these base-metal inner-electrodes under the sintering condition oxidation can take place in the conventional air of dielectric ceramic material.In order to prevent the oxidation of base-metal inner-electrode in sintering process, must use neutrality or reducing atmosphere.To guarantee that simultaneously the barium titanate based dielectric pottery does not become semiconductor behind sintering under neutrality or the reducing atmosphere, and enough insulation resistances and superior dielectric properties are arranged.Generally dielectric layer and interior electrode mutual superposition are formed green compact, then by N
2, H
2Under the reducing atmosphere that produces with steam, in 1200 ℃～1400 ℃ temperature range, carry out sintering, under 1000 ℃～1100 ℃ temperature, have 10 then
-8Anneal in the atmosphere of the above partial pressure of oxygen of Pa,, add upper end electrode afterwards to improve the breakdown characteristics of pottery.At present, at Japan Patent JP-A-63-103861, ceramic material basic composition is BaTiO
3-MnO-MgO-rare earth oxide.The insulation resistance of this composition and dielectric temperature coefficient are influenced by the grain size of barium titanate major ingredient, therefore are difficult to form the dielectric property that obtain temperature stabilization by control material.At U.S. Pat-005403797A, the basic composition of ceramic material is BaTiO
3-Y
2O
3-MgO-V
2O
5This composition satisfies the X7R performance requirement substantially, and room temperature dielectric constant is more than 2500, but sintering temperature is too high, greater than 1350 ℃; The dielectric temperature coefficient is bigger, at-55 ℃ approaching-15%; Loss is bigger, substantially all is higher than 2.0%.Therefore be not suitable for large-scale production.
In addition, along with electronic devices and components miniaturization, high performance growth requirement, base metal inner electrode multilayer ceramic capacitor also develops to big capacity, superthin layer direction.The medium thickness in monolayer constantly reduces, and drops to 5 μ m from 10 μ m, 2 μ m even thinner.This just proposes higher requirement to the ceramic medium material crystallite dimension, and for guaranteeing the reliability of device, the ceramic crystalline grain size also will be reduced to 500 nanometers from 1000 nanometers accordingly, 200 nanometers and even littler, and require the size of ceramic crystalline grain even.But the reduction that reduces often to cause dielectric constant of crystallite dimension, in U.S. Pat 6,270, among the 9906B1, when the ceramic crystalline grain size was reduced to the 100-200 nanometer, dielectric constant was 1600～1800, all is lower than 2000.Therefore, composition, structure and sintering process how to control ceramic medium material is problem to be solved by this invention to obtain thin crystalline substance, epigranular and high performance MLCC material with the requirement of satisfying big capacity, superthin layer base metal inner electrode multilayer ceramic capacitor.
Summary of the invention
It is easy to the purpose of this invention is to provide a kind of preparation technology, and it is simply adjustable to fill a prescription, and sintering process is easily controlled, and has the temperature-stable base metal inner electrode multilayer ceramic capacitor dielectric material and the sintering process of high dielectric constant nanometer/sub-micron crystal.
A kind of ultra-fine temperature-stable multilayer ceramic capacitor dielectric material that the present invention proposes, this material mainly is made up of barium titanate major ingredient and secondary additive, it is characterized in that: described major ingredient BaTiO
3Shared molal quantity is 94～99% in prescription; The consumption of described secondary additive accounts for 1～6mol% of total amount of material.
In above-mentioned dielectric material, the crystallite dimension of described major ingredient barium titanate is less than 500nm;
Described secondary additive comprises CaTiO
3, CaO, BaO, SiO
2, SrO, MnO
2, MgO, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3And one or more rare earth oxide Re
2O
3And the presoma of these oxides, the mole proportioning of described each material is: CaTiO
3: 0～1mol%; CaO:0～3mol%; BaO:0.01～2mol%; SiO
2: 0.1～5mol%; SrO:0～2mol%; MnO
2: 0.01～3mol%; MgO:0～2mol%; Co
2O
3: 0～2mol%; Co
3O
4: 0～1mol%; Fe
2O
3: 0～1mol%; Y
2O
3: 0～4mol%; Re
2O
3: 0～4mol%;
The presoma of described oxide comprises carbonate, hydroxide, oxalates, acetate, nitrate, citrate and alkoxide;
Described rare earth oxide Re
2O
3Middle Re representative: lanthanide series lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium;
SiO in the described secondary additive
2, BaO, CaO and CaTiO
3A part be with the form of glassy state as additive, (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2), 0≤A wherein, B≤1,0.9≤x≤1.1 account for 0～3wt% of ceramic weight;
Described frit (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2) be with SiO
2, BaO, CaO and CaTiO
3Or presoma mixes according to the proportioning of A, B, x accordingly, what calcining obtained under 800～1200 ℃ then;
To mix the back with the mode of solution and major ingredient dry for oxide precursor in the described secondary additive, and the calcination processing temperature is less than 1100 ℃, and ball milling in addition.
The sintering process of the ultra-fine temperature-stable multilayer ceramic capacitor dielectric material that the present invention proposes, it is characterized in that: the sintering densification process of green compact is divided into two stages: the phase I, in temperature T
1Down, of short duration insulation 0～30 minute cools to the second stage temperature T then rapidly
2Under be incubated 1～6 hour, 1100 ℃≤T wherein
2＜T
1≤ 1350 ℃, T
1Compare T
2High 10～250 ℃, from T
1To T
2Temperature fall time between 0～60 minute; The atmosphere of described phase I and second stage all is controlled at 10
-6～10
-12Pa under 900～1100 ℃ temperature, has 10 then
-3～10
-8Anneal annealing time 0.5～4 hour in the atmosphere of Pa partial pressure of oxygen.
According to material compositing formula of the present invention, can under 1100 ℃～1350 ℃ temperature, adopt " two-part " novel sintered technology and normal sintering to prepare the temperature-stable of excellent performance (X7R and X5R type) the anti-reducing material of MLCC.Its room temperature dielectric constant can be controlled between 2000～4000, satisfies X7R and X5R performance requirement, and temperature coefficient of capacitance is little, and dielectric loss is little, and material homogeneity is good.And has high insulation resistivity, stable performance.And the uniform crystal particles of material, the ceramic crystalline grain size is below 500 nanometers, and minimum can be controlled at about 100 nanometers.Be applicable to the base metal inner electrode multilayer ceramic capacitor of producing big capacity, ultra-thin dielectric layer (medium thickness is less than 10 μ m).
Description of drawings
Fig. 1 is the characteristic curve that the dielectric constant with temperature of embodiment 1 sample changes;
Fig. 2 is the temperature variant curve of temperature coefficient of capacitance of embodiment 1 sample;
Fig. 3 is the stereoscan photograph of the sintering rear surface pattern of embodiment 1 sample;
Fig. 4 is the characteristic curve that the dielectric constant with temperature of embodiment 2 samples changes;
Fig. 5 is the temperature variant curve of temperature coefficient of capacitance of embodiment 2 samples;
Fig. 6 is the stereoscan photograph of the sintering rear surface pattern of embodiment 2 samples;
Fig. 7 is the characteristic curve that the dielectric constant with temperature of embodiment 3 samples changes;
Fig. 8 is the temperature variant curve of temperature coefficient of capacitance of embodiment 3 samples;
Fig. 9 is the stereoscan photograph of the sintering rear surface pattern of embodiment 3 samples;
Figure 10 is the characteristic curve that the dielectric constant with temperature of embodiment 4 samples changes;
Figure 11 is the temperature variant curve of temperature coefficient of capacitance of embodiment 4 samples;
Figure 12 is the stereoscan photograph of the sintering rear surface pattern of embodiment 4 samples.
Embodiment
The present invention is that a kind of preparation technology is easy, and it is simply adjustable to fill a prescription, and sintering process is easily controlled, and has the nanometer/sub-micron crystal temperature temperature mode base metal inner electrode multilayer ceramic capacitor dielectric material of high dielectric constant, and it is by the barium titanate BaTiO of granularity less than 500nm
3The shared molal quantity of major ingredient be 94～99% and the consumption of secondary additive account for 1～6mol% of total amount of material.Its secondary additive comprises CaTiO
3, CaO, BaO, SiO
2, SrO, MnO
2, MgO, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3And one or more rare earth oxide Re
2O
3And the presoma of these oxides (comprising carbonate, hydroxide, oxalates, acetate, nitrate, citrate and corresponding alkoxide etc.).Described each material mixture ratio is (in mole): CaTiO
3: 0～1mol%; CaO:0～3mol%; BaO:0.01～2mol%; SiO
2: 0.1～5mol%; SrO:0～2mol%; MnO
2: 0.01～3mol%; MgO:0～2mol%; Co
2O
3: 0～2mol%; Co
3O
4: 0～1mol%; Fe
2O
3: 0～1mol%; Y
2O
3: 0～4mol%; Re
2O
3: 0～4mol%.
Above-mentioned rare earth oxide Re
2O
3Middle Re representative: lanthanide series lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu).
It is dry that mode that the presoma of oxide can solution in the above-mentioned secondary additive and major ingredient mix the back, and the calcination processing temperature is less than 1100 ℃, and ball milling in addition.
SiO in the above-mentioned secondary additive
2, BaO, CaO and CaTiO
3A part be with the form of glassy state as additive, (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2) (0≤A, B≤1,0.9≤x≤1.1), account for 0～3wt% of ceramic weight.This frit is with SiO
2, BaO, CaO and CaTiO
3Or presoma (comprising carbonate, hydroxide, oxalates, acetate, nitrate, citrate and corresponding alkoxide etc.) mixes according to the proportioning of A, B, x accordingly, what calcining obtained under 800～1200 ℃ then.
The concrete processing step of making MLCC is as follows:
1. the major ingredient barium titanate being mixed with additive, is medium with water, ball milling 2～48 hours;
2. oven dry: under 70～130 ℃ of temperature, dry;
3. curtain coating becomes dielectric layer: medium thickness is 10 μ m or below the 10 μ m;
4. with base-metal inner-electrode layer mutual superposition, produce green compact;
5. binder removal: about 300 ℃, in the air, be incubated about 20 hours; If be higher than 300 ℃ of dump temperatures, can use nitrogen protection;
6. green compact sintering under reducing atmosphere: feed N in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-8～10
-12In the scope of MPa, can adopt normal sintering and two-part sintering: (a) " two-part " sintering refers to that two stages are experienced in the densification of green compact, in advance at T
1Under the temperature, of short duration insulation 0～30 minute cools to T then
2Temperature continues to be incubated a few hours, reaches complete densification, wherein T
1＞T
2(1100≤T
2＜T
1≤ 1350 ℃); (b) normal sintering refers to that green sintering is T at a certain temperature
1(1100～1350 ℃) directly are incubated a few hours and finish densification process.
7. anneal under the weak oxide condition: furnace temperature is incubated 0.5～4 hour at 900 ℃～1100 ℃, and partial pressure of oxygen is controlled at 10
-3～10
-8In the scope of Pa;
8. be cooled to room temperature;
9. termination electrode technology: termination electrode is Cu or Ag, and furnace temperature is incubated about 1 hour at 600 ℃～850 ℃, and nitrogen protection behind the natural cooling, obtains promptly that electrode is the multi-layer ceramic capacitance dielectric material of base metal in nanometer/sub-micron crystal temperature-stable.The present invention will be further described below in conjunction with embodiment:
Embodiment 1
Earlier according to BaTiO
3: 96.4mol%; (grain size is 30nm) CaTiO
30.5mol%; CaO:0.4mol%; SiO
20.6mol%; SrO:0.10mol%; MnO
2: 0.25mol%; MgO:0.5mol%; Co
2O
3: 0.25mol%; Y
2O
3: the weighing of 1.0mol% proportioning.And then adding frit (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2) (A=0.4, B=0.9 x=1.0), account for the 1wt% of above-mentioned batch mixing.Above-mentioned material is mixed, ball milling, dry then.This porcelain casting film-forming sheet with the stack of Ni electrode, is made the MLCC green compact, behind the binder removal, adopts " two-part " sintering (to feed N in the sintering process under reducing atmosphere
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-10Atm is warmed up to 1200 ℃ with 200 ℃/hour speed, is incubated 5 minutes, cools to 1100 ℃ again, and temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 3 hours at 1000 ℃, and partial pressure of oxygen is controlled to be 10
-5Atm).Add Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 700 ℃) afterwards.Multilayer ceramic capacitor is carried out performance test, and the dielectric property parameter sees Table one.What the curve of Fig. 1 provided is the characteristic curve of the dielectric constant with temperature variation of present embodiment sample, and Fig. 2 provides the temperature variant curve of rate of change of capacitance of sample.Fig. 3 is the stereoscan photograph of sample at sintering rear surface pattern, and ceramic crystalline grain is spherical, and epigranular, crystallite dimension are about 110 nanometers.
Table 1
| Sample | Sintering condition | Dielectric constant | ??TCC(％) | Dielectric constant (25 ℃) | Dielectric constant | ??TCC(％) | ??tgδ(％) ???(25℃) | ???ρ 25℃??(Ω·cm) | ?E B，25℃?(kV/mm) |
| ?????-55℃ | ???????125℃ | ||||||||
| ????1 | " two-part " (1200 ℃/5 minutes, 1100 ℃/2 hours) | ?1761 | ??-13.9 | ??2046 | ??1788 | ??-12.6 | ??0.56 | ??46.2× ????10 12 | ??8.15 |
Embodiment 2
Earlier according to BaTiO
3: 95.2mol%; (grain size is 200nm) CaTiO
3: 0.7mol%; CaO:0.4mol%; SiO
2: 0.8mol%; SrO:0.3mol%; MnO
2: 0.3mol%; MgO:0.3mol%; Co
2O
3: 0.2mol%; Y
2O
3: 0.8mol%; Lu
2O
3: the weighing of 1.0mol% proportioning.And then adding frit (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2) (A=0.5, B=0.8 x=1), account for the 1.5wt% of above-mentioned batch mixing.Above-mentioned material is mixed, ball milling, dry then.This porcelain casting film-forming sheet with the stack of Ni electrode, is made the MLCC green compact, and behind the binder removal, sintering under reducing atmosphere (feeds N in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-9Atm is warmed up to 1220 ℃ with 200 ℃/hour speed, and temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 4 hours at 1100 ℃, and partial pressure of oxygen is controlled to be 10
-5Atm).Add Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 700 ℃) afterwards.Multilayer ceramic capacitor is carried out performance test, satisfy the X7R requirement, the dielectric property parameter sees Table two.What the curve of Fig. 4 provided is the characteristic curve of the dielectric constant with temperature variation of present embodiment sample, and Fig. 5 provides the temperature variant curve of rate of change of capacitance of sample.Fig. 6 is the surface topography stereoscan photograph behind this sample sintering, and crystallite dimension is about 200 nanometers.
Table 2
| Sample | Sintering condition | Dielectric constant | TCC(％) | Dielectric constant (25 ℃) | Dielectric constant | ???TCC(％) | tgδ(％) ?(25℃) | ??ρ 25℃??(Ω·cm) | ??E B25℃??(kV/mm) |
| ??????-55℃ | ???????125℃ | ||||||||
| ??2 | 1220 ℃/2 hours | 1895 | ?-9.6 | ?2097 | ??2088 | ????-0.4 | ??0.92 | ??15.5×10 12 | ???8.21 |
Embodiment 3
Earlier according to BaTiO
3: 95mol%; (grain size is 300nm) CaTiO
30.5mol%; CaO:0.5mol%; SiO
20.8mol%; SrO:0.2mol%; MnO
2: 0.5mol%; MgO:0.5mol%; Co
2O
3: 0.4mol%; Y
2O
3: 0.8mol%; Er
2O
3: the weighing of 0.8mol% proportioning.And then adding frit (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2) (A=0.6, B=0.8 x=1.1), account for the 2wt% of above-mentioned batch mixing.Above-mentioned material is mixed, ball milling, dry then.This porcelain casting film-forming sheet with the stack of Ni electrode, is made the MLCC green compact, behind the binder removal, adopts " two-part " sintering (to feed N in the sintering process under reducing atmosphere
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-10Atm is warmed up to 1250 ℃ of insulations 0 minute with 200 ℃/hour speed, and cooling to 1200 ℃ of temperature retention times again is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 4 hours at 1000 ℃, and partial pressure of oxygen is controlled to be 10
-5Atm).Add Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 700 ℃) afterwards.Multilayer ceramic capacitor is carried out performance test, satisfy the X5R requirement, the dielectric property parameter sees Table five.What the curve of Fig. 7 provided is the characteristic curve of the dielectric constant with temperature variation of present embodiment sample, and Fig. 8 provides the temperature variant curve of rate of change of capacitance of sample.Fig. 9 is the surface topography stereoscan photograph behind this sample sintering, and the ceramic crystalline grain size is about 350 nanometers.
Table 3
| Sample | Sintering condition | Dielectric constant | TCC(％) | Dielectric constant (25 ℃) | Dielectric constant | ??TCC(％) | tgδ(％) (25℃) | ρ 25℃(Ω·cm) | ??E B25℃??(kV/mm) |
| ??????-55℃ | ???????85℃ | ||||||||
| ??3 | " two-part " 1250 ℃/0 minute 1200 ℃/2 hours | ?3719 | ??-5.88 | ??3950 | ??3554 | ???-10.0 | ??0.78 | 25.0×10 12 | ???6.92 |
Embodiment 4
Earlier according to BaTiO
3: 95mol%; (grain size is 450nm) CaTiO
3: 0.7mol%; CaO:0.4mol%; SiO
2: 0.7mol%; SrO:0.3mol%; MnO
2: 0.5mol%; MgO:0.4mol%; Co
2O
3: 0.2mol%; Y
2O
3: 0.7mol%; Gd
2O
3: the weighing of 1.1mol% proportioning.And then adding frit (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2) (A=0.5, B=0.9 x=1.1), account for the 2.5wt% of above-mentioned batch mixing.Above-mentioned material is mixed, ball milling, dry then.This porcelain casting film-forming sheet with the stack of Ni electrode, is made the MLCC green compact, and behind the binder removal, sintering under reducing atmosphere (feeds N in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-9Atm is warmed up to 1280 ℃ with 200 ℃/hour speed, and temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 4 hours at 1100 ℃, and partial pressure of oxygen is controlled to be 10
-5Atm).Add Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 700 ℃) afterwards.Multilayer ceramic capacitor is carried out performance test, satisfy the X7R requirement, the dielectric property parameter sees Table four.What the curve of Figure 10 provided is the characteristic curve of the dielectric constant with temperature variation of present embodiment sample, and Figure 11 provides the temperature variant curve of rate of change of capacitance of sample.Figure 12 is the surface topography stereoscan photograph behind this sample sintering, and ceramic crystalline grain is of a size of 500 nanometers.
Table 4
| Sample | Sintering condition | Dielectric constant | TCC(％) | Dielectric constant (25 ℃) | Dielectric constant | TCC(％) | tgδ(％) (25℃) | ?ρ 25℃?(Ω·cm) | ??E B25℃??(kV/mm) |
| ??????-55℃ | ??????125℃ | ||||||||
| ??4 | 1280 ℃/2 hours | 2771 | ??-10.6 | ??3100 | ??3503 | ??13 | ??0.71 | 14.9×10 12 | ???7.78 |
The foregoing description has prepared nanometer, sub-micron crystal barium phthalate base base-metal inner-electrode MLCC porcelain that satisfied temperature stable type X7R and X5R type performance index require in 1100～1350 ℃ temperature range.The room temperature dielectric constant of MLCC can be controlled between 2000 to 4000, and temperature coefficient of capacitance is less than ± 15%, and dielectric loss is less than 2.5%.Insulation resistivity is about 10
13Ω cm, puncture voltage is greater than 5KV/mm.Utilize prescription of the present invention and sintering process, it is low to obtain sintering temperature, and structure and performance are adjustable, and sintering range is wide, stability and the good barium phthalate base temperature-stable MLCC material of reproducibility.And the uniform crystal particles of material, grain size can be controlled in the scope of 100nm～500nm.Can be applied to big capacity, superthin layer (medium thickness is less than 10 μ m) multilayer ceramic capacitor, be a kind of MLCC material with wide application prospect.
Above-mentioned Fig. 1～Figure 12 is corresponding to the temperature variant curve of temperature characteristics, rate of change of capacitance of each sample dielectric constant of embodiment 1～4 and the stereoscan photograph of sintering rear surface pattern.Probe temperature is-60 ℃～+ 130 ℃.
The meaning of each parameter representative is as follows in table 1～table 4: TCC (55 ℃): temperature coefficient of capacitance in the time of-55 ℃; TCC (125 ℃): temperature coefficient of capacitance in the time of 125 ℃; Tg δ (25 ℃): dielectric loss during room temperature; TCC (T) %=100 * (ε (T)-ε (25 ℃))/ε (25 ℃): temperature coefficient of capacitance.
Claims (9)
1, ultra-fine temperature-stable multilayer ceramic capacitor dielectric material, this material mainly is made up of barium titanate major ingredient and secondary additive, it is characterized in that: described major ingredient BaTiO
3Shared molal quantity is 94～99% in prescription; The consumption of described secondary additive accounts for 1～6mol% of total amount of material.
2, dielectric material according to claim 1 is characterized in that: the crystallite dimension of described major ingredient barium titanate is less than 500nm.
3, according to the described dielectric material of claim 1, it is characterized in that: described secondary additive comprises CaTiO
3, CaO, BaO, SiO
2, SrO, MnO
2, MgO, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3And one or more rare earth oxide Re
2O
3And the presoma of these oxides, the mole proportioning of described each material is: CaTiO
3: 0～1mol%; CaO:0～3mol%; BaO:0.01～2mol%; SiO
2: 0.1～5mol%; SrO:0～2mol%; MnO
2: 0.01～3mol%; MgO:0～2mol%; Co
2O
3: 0～2mol%; Co
3O
4: 0～1mol%; Fe
2O
3: 0～1mol%; Y
2O
3: 0～4mol%; Re
2O
3: 0～4mol%.
4, according to claim 1 or 3 described dielectric materials, it is characterized in that: the presoma of described oxide comprises carbonate, hydroxide, oxalates, acetate, nitrate, citrate and alkoxide.
5, according to claim 1 or 3 described dielectric materials, it is characterized in that: described rare earth oxide Re
2O
3Middle Re representative: lanthanide series lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
6, according to claim 1 or 3 described dielectric materials, it is characterized in that: SiO in the described secondary additive
2, BaO, CaO and CaTiO
3A part be with the form of glassy state as additive, (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2), 0≤A wherein, B≤1,0.9≤x≤1.1 account for 0～3wt% of ceramic weight.
7, according to claim 1 or 6 described electric materials, it is characterized in that: described frit (Ba
ACa
(1-A)O)
x(Si
BTi
(1-B)O
2) be with SiO
2, BaO, CaO and CaTiO
3Or presoma mixes according to the proportioning of A, B, x accordingly, what calcining obtained under 800～1200 ℃ then.
8, according to claim 1 or 3 described dielectric materials, it is characterized in that: to mix the back with the mode of solution and major ingredient dry for oxide precursor in the described secondary additive, and the calcination processing temperature is less than 1100 ℃, and ball milling in addition.
9, the sintering process of preparation base metal inner electrode multilayer ceramic capacitor dielectric material according to claim 1 is characterized in that: the sintering densification process of green compact is divided into two stages: the phase I, and in temperature T
1Down, of short duration insulation 0～30 minute cools to the second stage temperature T then rapidly
2Under be incubated 1～6 hour, 1100 ℃≤T wherein
2＜T
1≤ 1350 ℃, T
1Compare T
2High 10～250 ℃, from T
1To T
2Temperature fall time between 0～60 minute; The atmosphere of described phase I and second stage all is controlled at 10
-6～10
-12Pa under 900～1100 ℃ temperature, has 10 then
-3～10
-8Anneal annealing time 0.5～4 hour in the atmosphere of Pa partial pressure of oxygen.
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|---|---|---|---|
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|---|---|---|---|
| CN 03147880 CN1461023A (en) | 2003-06-27 | 2003-06-27 | Ultrathin temperature stable type multilayer ceramic capacitor dielectric material and its sintering process |
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ID=29591402
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|---|---|---|---|
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|---|---|---|---|---|
| CN100354996C (en) * | 2004-11-08 | 2007-12-12 | 华南理工大学 | Process for preparing low frequency fine crystal ceramic capacitor dielectric material |
| CN101182201B (en) * | 2007-11-27 | 2010-06-02 | 清华大学 | Nano doping dielectric material for preparing base-metal inner-electrode multi-layer ceramic sheet type capacitor |
| CN101844927A (en) * | 2010-05-28 | 2010-09-29 | 电子科技大学 | High-low temperature circular sintering method for electronic ceramic materials |
| CN101486571B (en) * | 2009-02-25 | 2012-07-04 | 同济大学 | High Q electricity adjustable Ba1-xSrxTi1-yMnyO3 ceramic dielectric material and preparation thereof |
| CN102791654A (en) * | 2009-12-16 | 2012-11-21 | 天工方案公司 | Dielectric ceramic materials and associated methods |
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| CN114014649A (en) * | 2021-12-13 | 2022-02-08 | 深圳先进电子材料国际创新研究院 | Co-doped barium titanate ceramic dielectric material, preparation method and application thereof |
| CN114230335A (en) * | 2021-12-22 | 2022-03-25 | 福建贝思科电子材料股份有限公司 | BaTiO with giant dielectric constant, low loss and high resistivity3Fine crystal ceramic and its prepn |
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| CN100354996C (en) * | 2004-11-08 | 2007-12-12 | 华南理工大学 | Process for preparing low frequency fine crystal ceramic capacitor dielectric material |
| CN101182201B (en) * | 2007-11-27 | 2010-06-02 | 清华大学 | Nano doping dielectric material for preparing base-metal inner-electrode multi-layer ceramic sheet type capacitor |
| CN101486571B (en) * | 2009-02-25 | 2012-07-04 | 同济大学 | High Q electricity adjustable Ba1-xSrxTi1-yMnyO3 ceramic dielectric material and preparation thereof |
| CN102791654A (en) * | 2009-12-16 | 2012-11-21 | 天工方案公司 | Dielectric ceramic materials and associated methods |
| CN101844927A (en) * | 2010-05-28 | 2010-09-29 | 电子科技大学 | High-low temperature circular sintering method for electronic ceramic materials |
| CN105693237A (en) * | 2016-01-21 | 2016-06-22 | 中国科学院上海硅酸盐研究所 | High-voltage-withstanding ceramic dielectric material and preparation method thereof |
| CN110668814A (en) * | 2019-10-14 | 2020-01-10 | 天津大学 | Microwave dielectric material with near-zero temperature coefficient of resonant frequency |
| CN112645708B (en) * | 2020-12-24 | 2022-07-15 | 福建火炬电子科技股份有限公司 | Anti-reduction BME ceramic dielectric capacitor and ceramic material for capacitor |
| CN112645708A (en) * | 2020-12-24 | 2021-04-13 | 福建火炬电子科技股份有限公司 | Anti-reduction BME ceramic dielectric capacitor and ceramic material for capacitor |
| CN114014649A (en) * | 2021-12-13 | 2022-02-08 | 深圳先进电子材料国际创新研究院 | Co-doped barium titanate ceramic dielectric material, preparation method and application thereof |
| CN114014649B (en) * | 2021-12-13 | 2023-07-25 | 深圳先进电子材料国际创新研究院 | Co-doped barium titanate ceramic dielectric material, preparation method and application thereof |
| CN114230335A (en) * | 2021-12-22 | 2022-03-25 | 福建贝思科电子材料股份有限公司 | BaTiO with giant dielectric constant, low loss and high resistivity3Fine crystal ceramic and its prepn |
| CN114230335B (en) * | 2021-12-22 | 2022-12-13 | 福建贝思科电子材料股份有限公司 | BaTiO with giant dielectric constant, low loss and high resistivity 3 Fine crystal ceramic and its prepn |
| CN115504781A (en) * | 2022-08-24 | 2022-12-23 | 深圳先进电子材料国际创新研究院 | Wide-temperature-range stable ceramic dielectric material and preparation method and application thereof |
| CN116462500A (en) * | 2023-04-19 | 2023-07-21 | 杭州兴容科技有限公司 | X7R characteristic thin-layer BME ceramic dielectric material and preparation method thereof |
| CN116573931A (en) * | 2023-05-16 | 2023-08-11 | 中国科学技术大学 | Preparation method of barium titanate ceramic materials with different grain sizes and capable of improving flexural electricity response performance |
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