CN100570771C - Electrodes in base metal medium material for multilayer ceramic capacitors and preparation method thereof - Google Patents
Electrodes in base metal medium material for multilayer ceramic capacitors and preparation method thereof Download PDFInfo
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- CN100570771C CN100570771C CNB031478794A CN03147879A CN100570771C CN 100570771 C CN100570771 C CN 100570771C CN B031478794 A CNB031478794 A CN B031478794A CN 03147879 A CN03147879 A CN 03147879A CN 100570771 C CN100570771 C CN 100570771C
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Abstract
The invention discloses a kind of electrodes in base metal medium material for multilayer ceramic capacitors that belongs to capacitor material technology of preparing scope and preparation method thereof.The main component of this material is BaTiO
3, BaZrO
3And BaSnO
3Solid solution Ba
x(Zr
ySn
zTi
1-y-z) O
3, and secondary additive comprises CaO, BaO, TiO
2, SiO
2, Li
2O, MnO
2, ZnO and one or more rare earth oxide Re
2O
3The pottery of forming.This material is in 1100 ℃～1350 ℃ temperature range, in the reducing atmosphere that mixes according to a certain percentage with nitrogen, hydrogen and water vapour, adopt normal sintering and " two-part " crystallite control technology to sinter fine and close ceramic body into, in 1000 ℃～1100 ℃ lower temperature range, under weak oxide atmosphere, reoxidize again, form the anti-reducing medium material of Y5V type with superior dielectric properties and aplitic texture.Material provided by the invention and preparation method thereof is applicable to that the industrialization manufacturing is the high number of plies of electrode material, big capacity, high performance multilayer ceramic capacitor with the base metal.
Description
Technical field
The present invention relates to a kind of electrodes in base metal medium material for multilayer ceramic capacitors and preparation method thereof, particularly relate to a kind of high-k of base metal inner electrode multilayer ceramic capacitor, dielectric material of thin brilliant anti-reduction and preparation method thereof of being used for, belong to field of capacitor material technology.
Background technology
Develop rapidly along with electronics industry, miniaturization and lightness become the development trend of each electronic product such as digital camera, mobile phone, notebook computer, palmtop PC etc., these components and parts that require to constitute these electronic equipments must reduce volume and weight, and can adapt to the needs of surface mounting technology (SMD).The components and parts that surface mounting technology requires are chip components and parts, and multilayer ceramic capacitor, multi-layer ceramics inductor and plate resistor are most widely used three major types passive components in the chip component.Multilayer ceramic capacitor (Multilayer Ceramic Capacitors) is called for short MLCC, it is that multilayer inner electrode and ceramic body are superimposed, burn till an only stone body altogether, and at the only two ends coating external electrode of stone body, connect with the interior electrode electricity that alternately exposes respectively and form.According to the international EIA of Electronic Industries Association (Electronic Industries Association) standard, Y5V type MLCC is meant that the capacitance with 25 ℃ is a benchmark, within-30 ℃ to+85 ℃ the scope, temperature coefficient of capacitance is between+22%～-82% in temperature, dielectric loss (DF)≤2.5%.Y5V type MLCC divides two big classes by forming: a class is made up of leaded ferroelectric, and is another kind of with BaTiO
3Solid solution be that the non-lead of base material is that ferroelectric is formed.Wherein the latter is because environmentally safe, and mechanical strength, ageing resistace, platability and reliability be better than the former, and therefore non-lead is that Y5V type MLCC has broad application prospects.
With lead is that ferroelectric ceramic is compared, the sintering of barium titanate and solid-solution material thereof needs higher temperature (1100 ℃～1350 ℃), therefore the multilayer ceramic capacitor formed of such material is in air during sintering, needs to use noble metal (metal such as Pt, Au, Pd, Ag and alloy thereof etc.) as interior electrode.These noble metal fancy prices have improved the production cost of MLCC greatly, and utilizing cheap metal material to replace noble metal becomes the important channel that reduces the MLCC cost as inner electrode.Base-metal inner-electrode material commonly used comprises Ni, Fe, Co, Cu and their alloy, when sintering in air, interior electrode base metal among the MLCC can be by airborne dioxygen oxidation, generate the not oxide of easy conductive, lose effect, so the sintering of base-metal inner-electrode MLCC must use neutrality or reducing atmosphere as interior electrode.Simultaneously be semiconductor, and have enough insulation property and higher resistance to wear characteristic in order to guarantee that the barium titanate based dielectric pottery is not reduced into during sintering under neutrality or reducing atmosphere.The sintering of base-metal inner-electrode MLCC is general to carry out sintering earlier in 1100 ℃ ~ 1350 ℃ higher temperature ranges, obtain fine and close only stone body, and the partial pressure of oxygen of sintering atmosphere is between 10
-6～10
-12Pa under 1000 ℃ ~ 1100 ℃ temperature, has 10 then
-3～10
-8Anneal in the atmosphere of Pa partial pressure of oxygen,, guarantee the reliability of MLCC to improve the insulation resistance and the breakdown characteristics of pottery.Atmosphere in the sintering process is generally by nitrogen, hydrogen and water vapour, and perhaps nitrogen, carbon monoxide and carbon dioxide are formed, and obtains sintering atmosphere and annealing atmosphere with specific partial pressure of oxygen by the component of adjusting mist.At present, in U.S. Pat 5361187, the Y5V media ceramic adopts (Ba
1-xCa
x) (Ti
1-y-zSn
yZr
z) O
3Based solid solution is a major ingredient, has obtained higher room temperature dielectric constant (8000～19000), but can only be in air sintering, limited the application of such material in base-metal inner-electrode MLCC.U.S. Pat 6078494 adopts the (Ba of modification
xCa
y) (Ti
zZr
w) O
3The perovskite ferroelectric ceramic has obtained Y5V type Gao Jie (〉=20000) pottery of anti-reduction, but its composition is very complicated, the process conditions harshness, and the crystallite dimension of pottery big (3～5 μ m), the room temperature dielectric loss is bigger, can not be used in to make the high-performance multilayer ceramic capacitor that single-layer medium thickness is lower than 10 μ m.When the medium thickness in monolayer constantly reduces, develop to 5 μ m even thinner direction from 10 μ m, for protecting the reliability and the breakdown characteristics of MLCC device, require the crystallite dimension of dielectric material correspondingly to reduce and epigranular.But when using nanometer or sub-micron dielectric powder, in the sintering densification process, occur the inhomogeneous of crystal grain easily and grow up unusually, device performance is had a significant impact.Therefore, how controlling the sintering process method of nanometer or submicron order powder body material, is problem to be solved by this invention to obtain thin crystalline substance, epigranular, high performance MLCC material.The present invention promptly proposes novel " two-part " sintering densification technology of crystallite control, can address the above problem.
Summary of the invention
The electrodes in base metal medium material for multilayer ceramic capacitors and the preparation technology that the purpose of this invention is to provide a kind of high dielectric, anti-reduction are easy, and it is simply adjustable to fill a prescription, and sintering condition is the electrodes in base metal medium material for multilayer ceramic capacitors preparation method of control easily.
The present invention propose the electrodes in base metal medium material for multilayer ceramic capacitors, this material contains the major ingredient solid solution Ba that is made up of barium titanate and barium zirconate, barium stannate
x(Zr
ySn
zTi
1-y-z) O
3And secondary additive, it is characterized in that: described major ingredient solid solution shared molal quantity in prescription is 91～99mol%; The consumption of described secondary additive accounts for 1～9mol% of total amount of material.
In above-mentioned dielectric material, described at major ingredient solid solution Ba
x(Zr
ySn
zTi
1-y-z) O
3In, 0.995≤x≤1.01,0.10≤y≤0.20,0≤z≤0.10.
In above-mentioned dielectric material, described secondary additive comprises CaO, TiO
2, BaO, SiO
2, Li
2O, MnO
2, ZnO and one or more rare earth oxide Re
2O
3Described secondary additive mole proportioning is: CaO:0～1.0mol%; TiO
2: 0～0.5mol%; BaO:0～1.0mol%; SiO
2: 0～1.0mol%; Li
2O:0～1.5mol%; MnO
2: 0.1～1.4mol%; ZnO:0～2.5mol%; Re
2O
3: 0～1.2mol%.
In above-mentioned dielectric material, also can be the presoma of oxide in the described secondary additive, it contains carbonate, hydroxide, oxalates, acetate, nitrate, citrate and alkoxide.
In above-mentioned dielectric material, the rare earth oxide Re in the described secondary additive
2O
3Middle Re representative: lanthanide series lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and yttrium.
In above-mentioned dielectric material, the presoma of oxide mixes the dry deposition in back in the mode of solution in the described secondary additive, then deposit is carried out calcination processing at 800 ℃～900 ℃, and ball milling.
The preparation method of the electrodes in base metal medium material for multilayer ceramic capacitors that the present invention proposes is characterized in that: in the densification stage of green compact sintering under reducing atmosphere, adopt the two-part sintering technology of controlling grain growth, at first at T
1Under the temperature, be incubated 0～30 minute, cool to T then
2Be incubated 0～6 hour under the temperature, reach complete densification, wherein T
1＞T
2, i.e. 1100≤T
2＜T
1≤ 1350 ℃; Feed N in the sintering process
2/ H
2/ H
2The mist of O is controlled at 10 with partial pressure of oxygen
-6～10
-12In the scope of Pa.
Beneficial effect of the present invention can go out the high dielectric of Y5V type of excellent performance, anti-reduction MLCC material at 1100 ℃～1350 ℃ sintering temperature for by material prescription of the present invention and preparation technology.Its room temperature dielectric constant can be controlled at 8,000～15, between 000,-30 ℃～+ 85 ℃ range content temperature rates of change are between+22%～-82%, satisfy the EIA-Y5V requirement, room temperature dielectric loss≤2.5%, the alternating current breakdown field intensity is higher than 4.5kY/mm, the ceramic crystalline grain size is between 500nm～2,500nm.Be applicable to that manufacturing is the thin layer (≤10 μ m) of electrode material, the high number of plies, jumbo multilayer ceramic capacitor with the base metal.
It can accomplish the end in view evidence.
Description of drawings
Fig. 1 is the temperature variant curve of temperature coefficient of capacitance of embodiment 1 sample.
Fig. 2 is the microstructure photograph of the natural surface of embodiment 1 sample.
Fig. 3 is the temperature variant curve of temperature coefficient of capacitance of embodiment 2 samples.
Fig. 4 is the microstructure photograph of the section of embodiment 2 samples.
Fig. 5 is the temperature variant curve of temperature coefficient of capacitance of embodiment 3 samples.
Fig. 6 is the microstructure photograph of the natural surface of embodiment 3 samples.
Fig. 7 is the temperature variant curve of temperature coefficient of capacitance of embodiment 4 samples.
Fig. 8 is the microstructure photograph of the natural surface of embodiment 4 samples.
Fig. 9 is the temperature variant curve of temperature coefficient of capacitance of embodiment 5 samples.
Figure 10 is the microstructure photograph of the natural surface of embodiment 5 samples.
Embodiment
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 condition is easily controlled, a kind of high dielectric of base metal inner electrode multilayer ceramic capacitor, thin brilliant anti-reduction dielectric material of being used for that dielectric property are good.This material is mainly by barium titanate BaTiO
3With barium zirconate BaZrO
3, barium stannate BaSnO
3Solid solution Ba
x(Zr
ySn
zTi
1-y-z) O
3Form with secondary additive, described major ingredient can be by solid phase method or chemical method synthetic (hydro thermal method, oxalate precipitation method etc.), and particle size is nanometer or submicron order (less than 1000nm).Described major ingredient solid solution shared molal quantity in prescription is 91～99mol%; The consumption of described secondary additive accounts for 1～9mol% of total amount of material.0.995≤x≤1.01,0.10≤y≤0.20,0≤z≤0.10 wherein.
Described secondary additive comprises CaO, TiO
2, BaO, SiO
2, Li
2O, MnO
2, ZnO and one or more rare earth oxide Re
2O
3And the presoma of these oxides: comprise carbonate, hydroxide, oxalates, acetate, nitrate, citrate and alkoxide (, not being determined at a certain alkoxide) etc. as four butanols titaniums, calcium ethoxide, four butanols zirconiums etc.Described each material mixture ratio is (in mole): CaO:0～1.0mol%; TiO
2: 0～0.5mol%; BaO:0～1.0mol%; SiO
2: 0～1.0mol%; Li
2O:0～1.5mol%; MnO
2: 0.1～1.4mol%; ZnO:0～2.5mol%; Re
2O
3: 0～1.2mol%.Described 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), and yttrium (Y).The particle size of powdered oxide requires less than 600nm in the described secondary additive.(solvent generally is water, ethanol, acetate or their mixture to the requirement of the presoma of oxide, and for salts soluble in water such as carbonate, acetate, nitrate, solvent is selected water for use with solution in the described secondary additive; Can select for use ethanol, propyl alcohol or other alcohol to prevent hydrolysis of alkoxide for alkoxide; Acetate, oxalates etc. can be selected the aqueous solution of acetic acid or acetic acid for use as solvent) mode mix the dry deposition in back, then deposit is carried out calcination processing at 800 ℃～900 ℃, and ball milling in addition.
The concrete processing step of making MLCC is as follows:
(1) with major ingredient solid solution Ba
x(Zr
ySn
zTi
1-y-z) O
3Mixing with secondary additive, is medium with water or ethanol, dries behind the ball milling.
(2) with the compound of above-mentioned oven dry, adding suitable organic solvent n-propyl acetate, binding agent polyvinyl butyral resin, plasticizer dioctyl phthalate, dispersant ammonium polyacrylate, is mill Jie ball milling 24～48 hours with zirconia ball, obtains casting slurry;
(3) become dielectric layer with above-mentioned casting slurry curtain coating: dielectric layer curtain coating thickness is 15 μ m or below the 15 μ m;
(4) printing base-metal inner-electrode layer on above-mentioned dielectric layer, the curtain coating dielectric layer mutual superposition of electrode is cut after the hot pressing in will being printed on again, forms the MLCC green compact;
(5) binder removal: in 300 ℃～340 ℃ temperature range, insulation is about 20 hours in air, gets rid of the organic substance in the MLCC green compact, and the programming rate of binder removal process is not higher than 10 ℃/h;
(6) sintering under reducing atmosphere: green compact adopt novel " two-part " sintering technology of control grain growth at the sintering densification process stage, i.e. in sintering densification process two stages of experience, go ahead of the rest at T
1Under the temperature, of short duration insulation 0～30 minute cools to T then
2Be incubated 0～6 hour under the temperature, reach complete densification, wherein T
1＞T
2And 1100≤T
2＜T
1≤ 1350 ℃.Feed N in the sintering process
2/ H
2/ H
2The mist of O is controlled at 10 with partial pressure of oxygen
-6~ 10
-12In the scope of Pa.
(7) anneal under the weak oxide condition: furnace temperature is incubated 0.5～4 hour at 800 ℃ ~ 1100 ℃, and partial pressure of oxygen is controlled at 10
-3~ 10
-8In the scope of Pa;
(8) coating termination electrode: termination electrode is Cu or Ag, and furnace temperature is incubated 1 hour at 700 ℃～850 ℃, and nitrogen protection behind the natural cooling, promptly obtains Y5V type base metal inner electrode multilayer ceramic capacitor.
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
Earlier according to Ba
x(Zr
ySn
zTi
1-y-z) O
3(x=1.005 wherein, y=0.10, z=0.01) the synthetic perovskite solid solution of solid phase method, 1150 ℃ of synthesis temperatures, the particle size of solid solution is 570nm after the ball mill grinding.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 91.5mol%; CaO:1.0mol%; TiO
2: 0.5mol%; SiO
2: 1.0mol%; Li
2O:1.5mol%; MnO
2: 1.3mol%; ZnO:2.0mol%; Sm
2O
3: 0.7mol%; Dy
2O
3: the weighing of 0.5mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, behind the binder removal, adopts normal 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
-11Pa is warmed up to 1260 ℃ with 200 ℃/hour speed, and temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 2 hours at 1100 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 1.What the curve of Fig. 1 provided is the change curve of present embodiment sample dielectric constant with temperature, and Fig. 2 provides the microstructure of sample natural surface, and crystallite dimension is between 1000～2000nm.
The electric property parameter of table 1 sample 1
| The major ingredient composition | Sintering condition | TCC(％) (-30 ℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝15 ℃) | tgδ (％) (25℃) | ρ 25℃ (Ω·cm ) | E B25℃ (ACkV/mm ) |
| Ba 1.005(Zr 0.13Sn 0. 04Ti 0.83)O 3 | 1260 ℃ * 2 hours | -62.8 | 12200 | -70.4 | +9.4 | 1.30 | 2.0×10 11 | 4.9 |
Embodiment 2
Earlier according to Ba
x(Zr
ySn
zTi
1-y-z) O
3(x=1.002 wherein, y=0.17, z=0) synthetic perovskite solid solution, 1150 ℃ of synthesis temperatures, the particle size of solid solution is 410nm after the ball mill grinding.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 97mol%; CaO:0.3mol%; TiO
2: 0.1mol%; SiO
2: 0.2mol%; Li
2O:0.2mol%; MnO
2: 0.5mol%; ZnO:1.2mol%; Nd
2O
3: 0.2mol%; La
2O
3: the weighing of 0.3mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, behind the binder removal, adopts normal 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
-11Pa 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 3 hours at 1100 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 2.What the curve of Fig. 3 provided is the change curve of present embodiment sample dielectric constant with temperature, and Fig. 4 provides the microstructure of the fresh section of sample, and crystallite dimension is between 800～1000nm.
The electric property parameter of table 2 sample 2
| The major ingredient composition | Sintering condition | TCC(％) (-30 ℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝10 ℃) | tgδ (％) (25℃) | ρ 25℃ (Ω·cm ) | E B25℃ (ACkV/mm) |
| Ba 1.002(Zr 0.17Ti 0. 83)O 3 | 1220 ℃ * 2 hours | -49.4 | 8816 | -65.3 | +9.3 | 1.07 | 3.2×10 11 | 5.1 |
Embodiment 3
Earlier according to Ba
x(Zr
ySn
zTi
1-y-z) O
3(x=0.998 wherein, y=0.115, z=0) the synthetic perovskite solid solution of hydro thermal method, crystallite dimension is 200nm.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 94.2mol%; CaO:0.7mol%; TiO
2: 0.6mol%; SiO
2: 0.8mol%; Li
2O:0.9mol%; MnO
2: 0.9mol%; ZnO:1.0mol%; Yb
2O
3: 0.4mol%; Ho
2O
3: the weighing of 0.5mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, behind the binder removal, adopts normal 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
-11Pa is warmed up to 1300 ℃ 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 1050 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 3.What the curve of Fig. 5 provided is the change curve of present embodiment sample dielectric constant with temperature, and Fig. 6 provides the microstructure of sample natural surface, and crystallite dimension is between 1000～2500nm.
The electric property parameter of table 3 sample 3
| The major ingredient composition | Sintering condition | TCC(％) (-30 ℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝15 ℃) | Tgδ (％) (25℃) | ρ 25℃ (Ω·cm ) | E B25℃ (ACkV/mm) |
| Ba 0.998(Zr 0.14Sn 0. 08Ti 0.78)O 3 | 1300 ℃ * 2 hours | -58.9 | 13520 | -67.8 | +7.2 | 1.66 | 7.5×10 11 | 4.8 |
Embodiment 4
Get sodium rice crystalline flour body (preparation of oxalate precipitation method) Ba earlier
x(Zr
ySn
zTi
1-y-z) O
3(x=1.000 wherein, y=0.15, z=0.03) perovskite solid solution, crystallite dimension is 50nm.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 98.2mol%; CaO:0.3mol%; TiO
2: 0.1mol%; SiO
2: 0.1mol%; BaO:0.5mol%; MnO
2: 0.4mol%; Dy
2O
3: 0.1mol%; Y
2O
3: the weighing of 0.3mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, behind the binder removal, adopts " two-stage method " sintering (to feed N in the sintering process to obtain thin brilliant pottery under reducing atmosphere
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-11Pa, elder generation is warmed up to 1250 ℃ with 200 ℃/hour speed, is incubated 3 minutes, is cooled to 1150 ℃ again, temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 4 hours at 1050 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 4.What the curve of Fig. 7 provided is the change curve of present embodiment sample dielectric constant with temperature, and Fig. 8 provides the microstructure of sample natural surface, and crystallite dimension is between 500-800nm, and grain size is very even.
The electric property parameter of table 4 sample 4
| The major ingredient composition | Sintering condition | TCC(％) (-30 ℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝11 ℃) | Tgδ (％) (25℃) | ρ 25℃ (Ω·cm ) | E B25℃ (ACkV/mm) |
| Ba (Zr 0.15Sn 0.02Ti 0.83)O 3 | 1250 ℃/5 minutes 1150 ℃/2 hours | -51.3 | 8030 | -60.9 | +9.4 | 0.91 | 4.5×10 12 | 6.8 |
Embodiment 5
Get sodium rice crystalline flour body (preparation of oxalate precipitation method) Ba earlier
x(Zr
ySn
zTi
1-y-z) O
3(x=1.000 wherein, y=0.15, z=0.00) perovskite solid solution, crystallite dimension is 50nm.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 97.5mol%; CaO:0.4mol%; TiO
2: 0.1mol%; SiO
2: 0.4mol%; BaO:0.4mol%; MnO
2: 0.3mol%; Tm
2O
3: 0.1mol%; Y
2O
3: the weighing of 0.8mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, behind the binder removal, adopts " two-stage method " sintering (to feed N in the sintering process to obtain thin brilliant pottery under reducing atmosphere
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-11Pa, elder generation is warmed up to 1280 ℃ with 200 ℃/hour speed, is incubated 0 minute, is cooled to 1200 ℃ again, temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 4 hours at 1050 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 5.What the curve of Fig. 9 provided is the change curve of present embodiment sample dielectric constant with temperature, and Figure 10 provides the microstructure of sample natural surface, crystallite dimension between 800-1400nm, homogeneous grain size.
The electric property parameter of table 5 sample 5
| The major ingredient composition | Sintering condition | TCC(％) (-30℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝13 ℃) | Tgδ (％) (25℃) | ρ 25℃ (Ω·cm) | E B25℃ (ACkV/mm) |
| Ba (Zr 0.15Ti 0.85)O 3 | 1280 ℃/0 minute 1200 ℃/2 hours | -66.0 | 10220 | -65.5 | +6.6 | 1.02 | 3.8×10 12 | 5.7 |
The foregoing description has prepared the high dielectric of barium titanate solid solution base base-metal inner-electrode that satisfies the EIA-Y5V performance index and require, thin brilliant, anti-reduction capacitor dielectric porcelain in 1100 ~ 1350 ℃ temperature range.Its room temperature dielectric constant can be controlled between 8000 to 1,5000, and-30 ℃～+ 85 ℃ temperature coefficient of capacitance are between+22%～-82%, and dielectric loss is less than 2.5%.Insulation resistivity is about 10
11Ω cm, ac breakdown voltage is greater than 4.5KV/mm.Utilize prescription of the present invention and technology, it is wide to obtain sintering range, and performance is adjustable, stability and the good anti-reduction barium titanate solid solution base Y5V type MLCC material of reproducibility.And the uniform crystal particles of material, the ceramic crystalline grain size is between 500nm～2,500nm.Can be applied to big capacity, superthin layer (medium thickness is less than 10 μ m) multilayer ceramic capacitor is a kind of MLCC material with wide application prospect.
Above-mentioned Fig. 1 ~ Figure 10 is temperature characteristics and the microstructure corresponding to each sample dielectric constant of embodiment 1 ~ 5.The probe temperature of Jie's temperature characteristics is-55 ℃～+ 125 ℃.
The meaning of each parameter representative is as follows in table 1 ~ table 5:
TCC (30 ℃): temperature coefficient of capacitance in the time of-30 ℃;
TCC (85 ℃): temperature coefficient of capacitance in the time of 85 ℃;
Tg δ (25 ℃): dielectric loss during room temperature, test frequency are 1kHz, test voltage 1.0V;
TCC (T) %=100 * (ε (T)-ε (25 ℃))/ε (25 ℃): temperature coefficient of capacitance;
ρ (25 ℃): room temperature resistivity, test condition are direct voltage 100V, keep 60s;
E
b(25 ℃): room temperature alternating current breakdown field intensity, AC field frequency are 50Hz.
Claims (1)
1. the preparation method of electrodes in base metal medium material for multilayer ceramic capacitors is characterized in that: described method is the two-part sintering technology that the densification stage of green compact sintering under reducing atmosphere adopts the control grain growth, at first at T
1Under the temperature, be incubated 0～30 minute, cool to T then
2Be incubated 2～6 hours under the temperature, reach complete densification, wherein T
1＞T
2, i.e. 1100≤T
2＜T
1≤ 1350 ℃; Described electrodes in base metal medium material for multilayer ceramic capacitors contains the major ingredient solid solution Ba that is made up of barium titanate and barium zirconate, barium stannate
x(Zr
ySn
zTi
1-y-z) O
3And secondary additive, described major ingredient solid solution shared molal quantity in prescription is 91～99mol%; The consumption of described secondary additive accounts for 1～9mol% of total amount of material.
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| CN100570771C true CN100570771C (en) | 2009-12-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462329C (en) * | 2007-04-27 | 2009-02-18 | 天津大学 | Multi-phase structure designed high-conductive electrical zirconate barium proton conductor and preparation method thereof |
| KR20100073704A (en) * | 2008-12-23 | 2010-07-01 | 삼성전기주식회사 | Methods of manufacturing complex oxide nano particles and complex oxide nano particles manufactured thereby |
| CN101880167B (en) * | 2010-06-11 | 2013-02-13 | 清华大学 | Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system |
| CN105174942A (en) * | 2015-09-15 | 2015-12-23 | 奈申（上海）智能科技有限公司 | Method for improving performance of barium-titanate-based electrocaloric ceramic refrigeration device |
| CN106505144A (en) * | 2016-10-17 | 2017-03-15 | 奈申（上海）智能科技有限公司 | Multilayer electric card ceramic component and preparation method thereof |
| CN109265163A (en) * | 2018-09-29 | 2019-01-25 | 苏州旷视智能科技有限公司 | The preparation method of ceramic capacitor |
| CN110668814A (en) * | 2019-10-14 | 2020-01-10 | 天津大学 | Microwave dielectric material with near-zero temperature coefficient of resonant frequency |
| CN110734292B (en) * | 2019-11-27 | 2022-03-11 | 宝鸡文理学院 | Method for uniformly mixing CuO and ceramic powder |
| CN113443910A (en) * | 2021-07-21 | 2021-09-28 | 广东工业大学 | Barium strontium titanate ceramic material matched with base metal internal electrode and preparation method thereof |
| CN114133238B (en) * | 2021-11-02 | 2022-09-16 | 广东省先进陶瓷材料科技有限公司 | Ceramic dielectric material and preparation method and application thereof |
| CN115947598B (en) * | 2022-10-21 | 2024-03-22 | 西安交通大学 | Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof |
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