CN103050280A - Sintering inhibition of multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability - Google Patents
Sintering inhibition of multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability Download PDFInfo
- Publication number
- CN103050280A CN103050280A CN2011103085277A CN201110308527A CN103050280A CN 103050280 A CN103050280 A CN 103050280A CN 2011103085277 A CN2011103085277 A CN 2011103085277A CN 201110308527 A CN201110308527 A CN 201110308527A CN 103050280 A CN103050280 A CN 103050280A
- Authority
- CN
- China
- Prior art keywords
- green compact
- sintering
- family
- layer
- specified temp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Ceramic Capacitors (AREA)
Abstract
The invention discloses sintering inhibition of a multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability. By using (Ba,Ca)(Ti,Zr)O3 as a main dielectric material, a micro-structure of the (Ba,Ca)(Ti,Zr)O3 is changed by inhibition sintering, and a high-temperature stability and high-reliability dielectric substance with a non-core-shell structure is developed. Crystal grain growth of a (Ba,Ca)(Ti,Zr)O3 base material is inhibited during sintering, and further the (Ba,Ca)(Ti,Zr)O3 dielectric substance is inhibited in sintering so that smaller average crystal grain distribution is formed and the characteristics of low capacitance value temperature coefficient, high reliability and the like of a capacitor are achieved.
Description
Technical field
The present invention relates to a kind of sintering method, particularly, relate to the inhibition that improves temperature characteristic of capacitance and reliability and shrink sintering method.
Background technology
As everyone knows, monolithic ceramic capacitor mainly by the mutual storehouse of most composite beds and after pressing sintering form, each composite bed is by being comprised of ceramic layer and the electrode layer that is formed at this ceramic layer top.By u s company's development, the Japanese firms such as Murata, TKD, TAIYO YUDAN develop rapidly and industrialization thereafter at first, and part replaces sheet type aluminum electrolytic electric capacity and chip tantalum capacitor.Present laminated ceramic electric capacity (Multilayer Ceramic Capacitors, MLCC) PC, mobile phone, auto electronic have been installed in a large number, assembly as passive component (Passive Components), with storage power, present filtering, bypass, coupling, the anti-effect such as coupling and tuning vibration.Compare with microcontroller, internal memory etc. by reduced volume with the demand of information product for capacitor at present, although electric capacity is not critical components, the quality of its quality but concerns the performance of electronic product performance.
MLCC comprises that with ceramic powder Capacitance Shift Rate is-80%～+ 30% Y5V in-30 ℃～+ 85 ℃ serviceability temperature scopes ,-55 ℃～+ 125 ℃ serviceability temperatures, and Capacitance Shift Rate is ± X7R of 15%MAX.Wherein X7R belongs to lamination electric capacity, is that existing market is required, one of the maximum kind of consumption.Japanese firm uses nanoscale metatitanic acid titanate ceramics material (BaTiO
3), add the rare-earth oxide modification, manufacture the X7R ceramic powder of high reliability.
In the patent documentation Japanese Patent Laid-Open 2004-224653 communique, propose a kind of dielectric medium pottery, it has following composition: comprise principal component and adding ingredient, wherein, above-mentioned principal component contains by ABO
3(A is Ba and Ca, perhaps is Ba, Ca and Sr; B is Ti, perhaps be Ti and Zr, among the Hf at least any) represented perovskite-type compounds, above-mentioned adding ingredient contains Si, specific rare earth element R and specific metallic element M, and this dielectric medium pottery has crystal grain and occupies intercrystalline crystal boundary, 85% above person about above-mentioned crystal grain number, in the zone more than 90% in its cross section, the not solid solution of above-mentioned adding ingredient, and there is above-mentioned principal component, 85% above analysis site for the analysis in the above-mentioned crystal boundary is counted contains above-mentioned at least Ba, above-mentioned Ca, above-mentioned Ti, above-mentioned Si, above-mentioned R and above-mentioned M.In this patent documentation, with (Ba, Ca) TiO
3As principal component, Si, specific rare earth element R and specific metallic element M be as accessory ingredient, and make above-mentioned accessory ingredient hardly solid solution in order to guarantee the high temperature load life-span, thereby realize the raising of reliability in principal component but be present in the crystal boundary.
In addition, in U.S. patent application case US 6,829,136, also be to utilize by ABO
3Dielectric ceramic for chief component.Wherein, have at least 70% media ceramic crystal grain that sectional area is arranged, the first area comprises dissolved rare earth element and occupies 5 to 70% sectional area, second area for freely dissolved rare earth element and occupy 10 to 80% edge sectional area.Utilize the monolithic dielectric ceramic film layer ceramic capacitor of this material to have excellent temperature characteristic of capacitance and high reliability.
The application of commercial ceramic capacitor is take Class II as main, can slightly be divided into Y5V, X5R, X7R equal-specification, wherein comparatively rigorous with the X7R specification, X7R basically desired specification is to refer at temperature range (take 25 ℃ as benchmark) between-55 ℃～125 ℃, and its relative appearance value variable quantity is less than 15%.At present, can meet the material of X7R specification, one is exactly barium titanate (BaTiO
3) system, it is take barium titanate as the main body prescription.
The bulletin I310761 patent of dielectric ceramic device composition and electronic building brick, propose to contain Ba, Ca, Ti, Mg and Mn as the dielectric ceramic compositions of the composite oxides of metallic element a kind of comprising, and with the change of the mutual intragranular Ca of CV value representation crystalline particle concentration, the preferably is between more than 5%, between 20%, more the preferably is between more than 10%, below 18% between.Reach not having through the diffusion of white additive component and form under the dielectric ceramic compositions of core shell mechanism material, having temperature dependence characteristics and reliability is not the material behavior of deciding on additive component.The laminated ceramic capacitor of this invention dielectric ceramic meets the B feature of JIS specification specifies, and meets X7R and the X8R feature of EIA specification specifies.
In addition, the thin layer technology of laminated ceramic electric capacity (MLCC) and high dielectric constant material are for realizing the main direction of studying of high capacitance and miniaturization.The thin layer that is accompanied by dielectric layer makes the rapid increase of electric field strength, and is more and more high for the quality requirement of barium titanate based ceramic material of dielectric layer micro-structural.So how by the understanding that promotes micro-structural and dielectric property correlation, and then the dielectric ceramic material of exploitation high capacitance and high-reliability MLCC is emphasis of the present invention.The monolithic ceramic capacitor of high-temperature stability is with BaTiO at present
3The nucleocapsid structure of material system is main, and the high-temperature stability monolithic ceramic capacitor that this material system is made is except because for cooperating the dielectric layer thin layer still must 5-6 little crystal grain, so cause that dielectric constant is low and reliability is not good.
Make a general survey of above-mentioned prior art, the core-shell structure laminated ceramic of how doing variation at the capacitor composition of dielectric ceramic is main capacitor.The kind of material is selected, and the composition allotment increases the burden of preparation, and the scope of application limits to some extent.The application's purpose is " to suppress the method for low-temp ceramics sintering shrinkage and suppress layer " by the disclosed patent of Taiwan 587067 publication numbers, except on BCTZ and BT, no longer limiting component ratio, make scope relatively extensive, reach high-k, high capacitance temperature characterisitic and high reliability, and be specially adapted to utilize the monolithic ceramic capacitor of the high appearance value of thin layer dielectric layer system preparation.
Summary of the invention
The present invention utilizes (Ba, Ca) (Ti, Zr) O
3For main material is called for short BCTZ, be that metal is made laminated ceramic electric capacity with nickel, in the layer structure of its lamination, cover BaTiO
3Barium titanate is called for short BT and suppresses layer in the up and down both sides of assembly, utilizes the inhibition sintering to suppress (Ba, Ca) (Ti, Zr) O
3System's monolithic ceramic capacitor crystal grain-growth, and then improve monolithic ceramic capacitor capacitance temperature dependent characteristics and reliability.When being located at, sintering temperature suppresses between layer and the suppressed layer beginning shrinkage temperature, thus, suppressed layer BCTZ base material is when sintering begins to shrink, BCTZ is really restrained by BT inhibition layer at X and Y-direction contraction, can only shrink at above-below direction, as stress application about suppressed layer, this stress can be used for suppressing the BCTZ crystal grain-growth, obtain and the diverse microstructure of free sintering, the little crystal grain that utilizes the BCTZ that suppresses sintering will have crystal grain to grow up hardly distributes, and this kind microstructure is fit to develop the non-core-shell structure monolithic ceramic capacitor of high-temperature stability and high-reliability.Its manufacture method roughly comprises:
The first green compact are provided, and wherein these first green compact comprise metal level and ABO
XLayer, wherein A is that to be selected from one or more element, B in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3.And on these first green compact, form BaTiO
3Ceramic layer and heat simultaneously this first green compact and BaTiO
3Ceramic layer is to specified temp, and wherein this specified temp energy is so that the first green compact are finished sintering.Wherein this metal level can be the Ni electrode layer, and ABO
XThe A element of layer is the combination of Ba, Ca, and the composition of B is the combination of Ti, Zr.
The present invention at first inquires into liquid-phase sintering control to (Ba, Ca) (Ti, Zr) O
3The impact of micro-structural and dielectric property is by changing its ABO
3BaO-SiO is when added in the A/B metering in the perovskite structure
2The particle diameter of glass is observed the variation of crystal structure, micro-structural and dielectric property and on the impact of production reliability.When A/B metering when being reduced to O.9956, discovery produces second-phase (Ba, Ca) gradually
6(Ti, Zr)
17O
40, its cause and (Ba, Ca) (Ti, Zr) O
3The eutectic liquid phase promote significantly crystal grain-growth.Simultaneously, along with the A/B metering makes Curie temperature toward high-temperature mobile than reducing, thereby cause the increase of room temperature dielectric constant.On crystal boundary (Ba, Ca)
6(Ti, Zr)
17O
40The formation of second-phase defective causes the change of electric field and stress on the crystal boundary, and these form the pipeline of leakage current with the A/B metering than reducing the grain boundary defects that produces, thereby cause MLCC reliability variation.In addition, add the finer BaO-SiO of particle diameter
2Ba (Ti, the Zr) O of glass
3Pottery presents and forms uniformly distribution and larger crystal grain-growth.When the glass addition is fixed and its particle diameter is decreased to 326nm by 1200nm, along with the glass particle diameter reduce can promote add Mn
2+Ion dissolves in and causes the lattice volumetric expansion, therefore suppresses pros and changes mutually a cube mutual-assistance Curie temperature raising into.When the glass particle diameter is decreased to 185nm again because the low tetragonality of uniform grain structure, on the contrary so that Curie temperature suddenly fall toward low temperature.The present invention finds the effect of glass not only just as sintering aid, and is more closely related with the transmission distribution of crystal grain-growth control and additive, and therefore causes the Dielectric behavior marked change.Improve the uniformity of glassy phase distribution except the density that can effectively promote pottery, more can so that the addition of glassy phase minimizes, be minimized the side effect that it causes.
Second portion is for inquiring into nucleus-brilliant shell structure control to BaTiO
3The impact of dielectric property by the particle diameter that changes calcium content and interpolation oxide, is observed its nucleus-brilliant shell microstructure change, and is inquired into it for the impact of dielectric property and reliability.Be accompanied by (Ba
1-xCa
x) TiO
3The increase of middle calcium content, meeting is so that the lattice volume-diminished proves that the Ca ion of small radii can occupy BaTiO in the present invention
3The position of Ba in the lattice, thereby suppress liquid-phase sintering and crystal grain-growth.
Because (Ba
0.98Ca
0.02) TiO
3Ceramic powders presents lower tetragonality, thereby promotes the additive diffusion in sintering process, so that the grainiess major part is occupied by the ferroelectric domain of higher tetragonality behind the sintering, so that its room temperature dielectric constant and BaTiO
3Therefore the ceramic phase ratio can promote approximately 10% up to 3009.Along with the increase of calcium content, change the STRESS VARIATION meeting that causes so that Curie point toward high-temperature mobile, helps to improve the at high temperature temperature stability of electric capacity by the A-site cation.Work as BaTiO
3The additive particle diameter be contracted to nanoscale by sub-micron grade, intercrystalline alloy is Uniform Dispersion effectively, this moment in additive element can with its BaTiO
3Reaction increase, and then the lattice volume is increased.Nanometer additive such as MnO and Y
2O
3The interpolation Elements Diffusion of promotion not only own, also comprise sintering aid (Ba
0.6Ca
0.4) SiO
3Middle element such as Ca and Si etc. can promote the uniform state of its distribution and can promote its center toward crystal grain to spread equably.Make grainiess major part behind the sintering be had a ferroelectric domain of high tetragonality occupied, thereby obtain higher dielectric constant.In addition, the interpolation of nanoscale additive is except the accumulation density that can improve pottery and additive particles in the living embryo strip, reduce the chance that causes short circuit that defective causes in the dielectric layer, more can promote the distribution of composition in crystal boundary of additive, to be reduced in the possibility of the additive cohesion drain current path that caused in the crystal boundary, therefore can promote significantly yield and the trustworthiness thereof of MLCCs.
Other oxide forms common solution and improves dielectric medium in the electrically easy and ceramic layer of barium titanate, and influenced by structure, it can sinter the MLCC of dielectric medium the best into to be doped in ceramic layer to control growing into 〉=1 μ tm of crystal grain.Only have additive to form second-phase, liquid phase or nucleus shell (core-shell) to improve its dielectricity or temperature.
Monolithic ceramic capacitor is with ferroelectric material BaTiO
3Be main, in order to obtain milder capacitance temperature coefficient, usually can make the pure BaTiO of its center of crystal grain of nucleocapsid structure
3Shell then is BaTiO
3Add and contain trace mineral supplement, in order to test by the reliability under the high-temperature and high-pressure conditions making monolithic ceramic capacitor with the crystal grain of nucleocapsid structure, between two electrodes, need at least to have the crystal grain of 5-6 nucleocapsid structure, yet in order to pursue high capacity, dielectric layer more becomes thinner between two electrodes, cause the crystal grain of nucleocapsid structure must more diminish to keep 5-6 nucleocapsid structure, the crystal grain of nucleocapsid structure diminishes and will cause material dielectric constant significantly to reduce, utilization reduces by two interelectrode dielectric thickness to promote capacitance relevant unfavorable for monolithic ceramic capacitor for this, therefore material must be changed into the crystal grain of non-nucleocapsid structure, the non-nucleocapsid structure material of this kind needs 1-2 between two electrodes and just can test by the reliability under the high-temperature and high-pressure conditions, yet in order to obtain milder capacitance temperature coefficient, the material of this type of non-nucleocapsid structure must suppress crystal grain-growth at sintering, research find to utilize suppress is shunk the restraint that sintering produces can be by this sintering the time and is suppressed non-nucleocapsid structure crystal grain-growth, obtain the non-nucleocapsid structure dielectric material of mild capacitance temperature coefficient, be fit to replace the monolithic ceramic capacitor that present nucleocapsid structure dielectric material is made Gao Rongzhi.
According to the explanation of above-mentioned sintering method, the present invention also provides a kind of method of sintering, and it comprises step: the first green compact are provided, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and the formation temperature characteristic is kept medium and is heated simultaneously these first green compact and temperature characterisitic is kept medium to specified temp on these first green compact, and wherein this specified temp energy is so that this first green compact are finished sintering.
In addition, the present invention more can be used to provide a kind of method of sintering, and it comprises step: the first green compact are provided, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and formation product performance reliability is kept medium on these first green compact, and heat simultaneously these first green compact and the product performance reliability is kept medium to a specified temp, wherein this specified temp energy is so that this first green compact are finished sintering.
Based on foregoing method, can learn a kind of electronic building brick, can comprise: the first green compact, wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and the second green compact are formed on these first green compact.And a kind of electronic building brick can comprise temperature characterisitic to be kept medium and is formed on these first green compact, and a kind of electronic building brick also can comprise the product performance reliability and keep medium and be formed on these first green compact, does not repeat them here.
Description of drawings
Fig. 1 a sintering method schematic diagram
B improves temperature characterisitic sintering method schematic diagram
C improves product performance reliability sintering method schematic diagram
Fig. 2 electronic building brick sintering green compact product schematic diagram
Fig. 3 laminated ceramic capacitance structure schematic diagram
Sintering shrinkage curve such as the icon of three kinds of materials of Fig. 4 laminated ceramic electric capacity are intended to
BCTZ crystal grain under the free sintering of Fig. 5
Fig. 6 inhibition of sintering is forged BCTZ crystal grain
The capacitance change rate of Fig. 7 capacitor varies with temperature
The insulating resistance value rate temporal evolution of Fig. 8 capacitor under 125 ℃ of 100V
Fig. 9 a electric capacity sintering method schematic diagram
B improves temperature characteristic of capacitance sintering method schematic diagram
C improves capacitance characteristic reliability method schematic diagram
Figure 10 capacitance component sintering green compact product schematic diagram
[primary clustering symbol description]
11 provide first to give birth to the embryo step
13 form second gives birth to the embryo step
15 while heating stepses
21 provide first to give birth to the embryo step
23 formation temperature characteristics are kept the medium step
25 while heating stepses
31 provide first to give birth to the embryo step
33 form the product performance reliability keeps the medium step
35 while heating stepses
40 electronic building bricks
41 first green compact
411 first green compact metal levels
413 first green ceramics layer YZO
XLayer
43 second green compact
51 provide first to give birth to the embryo step
53 form second gives birth to the embryo step
55 while heating stepses
61 provide first to give birth to the embryo step
63 formation temperature characteristics are kept the medium step
65 while heating stepses
71 provide first to give birth to the embryo step
73 form the product performance reliability keeps the medium step
75 while heating stepses
80 capacitance components
81 first green compact
811 first green compact metal levels
813 first green ceramics layer YZO
XLayer
83 second green compact
Embodiment
See also Fig. 1 a, a kind of method of sintering, it comprises step: one first green compact 11 are provided, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and on these first green compact, form the second green compact 13 and heat simultaneously these first green compact and the second green compact to specified temp 15, wherein this specified temp energy is so that this first green compact are finished sintering.In preferred embodiment of the present invention, this specified temp is more than 900 ℃, and the sintering temperature of these the second green compact is higher than this specified temp.In addition, these first green compact have amount of contraction at this specified temp, and suppressed by these second green compact.In the product by the method institute sintering, the composition that this metal level can be Ni electrode layer, this Y is the combination of Ba, Ca, and the composition of this Z is the combination of Ti, Zr.
In the preferred embodiment according to above-mentioned sintering method, that is specified temp is more than 900 ℃, sintering temperature is higher than this specified temp, amount of contraction and suppressed, composition that metal level can be Ni electrode layer, Y is the combination of Ba, Ca, and the composition of Z is the combination of Ti, Zr, because all can be corresponding with other each embodiment, therefore repeat no more.
See also Fig. 1 b, according to invention spirit of the present invention, also can be used to provide a kind of method of sintering, it comprises step: the first green compact 21 are provided, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and the formation temperature characteristic is kept medium 23 and is heated simultaneously these first green compact and temperature characterisitic is kept medium to specified temp 25 on these first green compact, and wherein this specified temp energy is so that this first green compact are finished sintering.
See also Fig. 1 c, according to invention spirit of the present invention, more can be used to provide a kind of method of sintering, it comprises that step provides the first green compact 31, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and formation product performance reliability is kept medium 33 on these first green compact, and heat simultaneously these first green compact and the product performance reliability is kept medium to specified temp 35, wherein this specified temp energy is so that this first green compact are finished sintering.
See also Fig. 2, according to invention spirit of the present invention, can learn that a kind of electronic building brick 40 comprises: the first green compact 41, wherein these first green compact comprise metal level 411 and YZO
XLayer 413, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and the second green compact 43 are formed on these first green compact.
And according to the sintered products of foregoing sintering method and electronic building brick also easily as can be known, a kind of electronic building brick can comprise temperature characterisitic to be kept medium and is formed on these first green compact, and a kind of electronic building brick also can comprise a product performance reliability and keep medium and be formed on these first green compact, do not repeat them here.
See also Fig. 9 a, a kind of method of electric capacity sintering, it comprises step: the first green compact 51 are provided, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and on these first green compact, form the second green compact 53 and heat simultaneously these first green compact and the second green compact to specified temp 55, wherein this specified temp energy is so that this first green compact are finished sintering.In preferred embodiment of the present invention, this specified temp is more than 900 ℃, and the sintering temperature of these the second green compact is higher than this specified temp.In addition, these first green compact have amount of contraction at this specified temp, and suppressed by these second green compact.In the product by the method institute sintering, the composition that this metal level can be Ni electrode layer, this Y is the combination of Ba, Ca, and the composition of this Z is the combination of Ti, Zr.
In the preferred embodiment according to above-mentioned electric capacity sintering method, be that specified temp is, sintering temperature is higher than this specified temp, amount of contraction more than 900 ℃ and suppressed, composition that metal level can be Ni electrode layer, Y is the combination of Ba, Ca, and the composition of Z is the combination of Ti, Zr, because all can be corresponding with other each embodiment, therefore repeat no more.
See also Fig. 9 b, according to invention spirit of the present invention, also can be used to provide a kind of method of electric capacity sintering, it comprises step: the first green compact 61 are provided, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and on these first green compact, form temperature characteristic of capacitance and keep medium 63 and heat simultaneously these first green compact and temperature characterisitic is kept medium to specified temp 65, wherein this specified temp energy is so that this first green compact are finished sintering.
See also Fig. 9 c, according to invention spirit of the present invention, more can be used to provide a kind of method of electric capacity sintering, it comprises step: the first green compact 71 are provided, and wherein these first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and keep medium 73 on these first green compact, forming electric capacity product performance reliability, and heat simultaneously these first green compact and the product performance reliability is kept medium to specified temp 75, wherein this specified temp energy is so that this first green compact are finished sintering.
See also Figure 10, according to invention spirit of the present invention, can learn that a kind of capacitance component 80 comprises: the first green compact 81, wherein these first green compact comprise metal level 811 and YZO
XLayer 813, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3, and the second green compact 83 are formed on these first green compact.
And according to the sintered products of foregoing sintering method and capacitance component also easily as can be known, a kind of capacitance component can comprise a temperature characterisitic to be kept medium and is formed on these first green compact, and a kind of capacitance component also can comprise a product performance reliability and keep medium and be formed on these first green compact, do not repeat them here.
The embodiment of above-described all sintering methods and product, also can be corresponding for the sintering of the laminated ceramic assembly of consumption electronic products, computer product and communication device etc., repeat no more.
For more understand after the invention process the sample attitude and with respect to the progress of present technology, cooperate graphic being illustrated with literal again at this.The present invention utilizes (Ba, Ca) (Ti, Zr) O
3For main material is called for short BCTZ 513, make laminated ceramic electric capacity with nickel base metal 511, in the layer structure of its lamination, cover BaTiO
3Barium titanate is called for short BT and suppresses layer 53 both sides about assembly, modular construction such as Fig. 3, and sintering shrinkage curve such as Fig. 4 of three kinds of materials, electrode nickel shrinks the earliest, and secondly suppressed layer BCTZ suppress the shrinking zone line that layer BT has maximum temperature.When being located at, sintering temperature suppresses between layer and the suppressed layer beginning shrinkage temperature, thus, suppressed layer BCTZ base material is when sintering begins to shrink, BCTZ is restrained by BT inhibition layer really in the contraction of X and Y-direction, can only shrink toward above-below direction, just as stress application about suppressed layer, this stress can be used for suppressing the BCTZ crystal grain-growth, obtain and the diverse microstructure of free sintering, the little crystal grain that utilizes the BCTZ that suppresses sintering will have crystal grain to grow up hardly distributes, and this kind microstructure is fit to develop the non-core-shell structure monolithic ceramic capacitor of high-temperature stability and high-reliability.
Average primary particle diameter approximately 0.45 micron BCTZ is made monolithic ceramic capacitor, be clipped in assembly with the barium titanate BT of 60 micron thickness and carried out common burning 2 hours at 1150 ℃ behind the both sides up and down, significantly, under the free sintering BCTZ crystal grain-growth to about 4 microns such as Fig. 5, yet utilize barium titanate BT when suppressing layer crystal grain-growth that really can effectively suppress the BCTZ base material, behind the sintering the large I of its average crystal grain be suppressed at 0.45 micron with original average grain diameter quite such as Fig. 6, this microstructure change will affect the characteristics such as capacitance temperature coefficient that its capacitor is correlated with and reliability.The capacitance change rate of Fig. 7 illustrated capacitor varies with temperature, significantly, with respect to free sintering, it is more smooth that its capacitance change rate of capacitor of inhibition sintering varies with temperature, the insulating resistance value rate temporal evolution of capacitor under 125 ℃ of 100V at Fig. 8 in addition, this is commonly used to assess capacitor reliability in use, thus find out significantly through the capacitor that inhibition sintering because of crystal grain little and evenly the reliability life-span longer.
Claims (11)
1. the method for an electric capacity sintering, it comprises step:
The first green compact are provided, and wherein said the first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3;
Form the second green compact at described the first green compact; And
Heat simultaneously described the first green compact and the second green compact to specified temp, wherein said specified temp energy is so that the first green compact are finished sintering.
2. method according to claim 1, wherein said specified temp is more than 900 ℃.
3. method according to claim 1, the sintering temperature of wherein said the second green compact is higher than described specified temp and described the first green compact have amount of contraction at described specified temp, and suppressed by described the second green compact.
4. method according to claim 1, wherein said metal level is the Ni electrode layer, the composition of Y is the combination of Ba, Ca, and the composition of Z is the combination of Ti, Zr.
5. the method for an electric capacity sintering, it comprises step:
The first green compact are provided, and wherein said the first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3;
The formation temperature characteristic is kept medium on described the first green compact; And
Heat simultaneously described the first green compact and temperature characterisitic and keep medium to specified temp, wherein said specified temp energy is so that described the first green compact are finished sintering.
6. the method for an electric capacity sintering, it comprises step:
The first green compact are provided, and wherein said the first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3;
Form the product performance reliability at described the first green compact and keep medium; And
Heat simultaneously described the first green compact and product performance reliability and keep medium to specified temp, wherein said specified temp energy is so that described the first green compact are finished sintering.
7. the method for an electric capacity sintering, it comprises step:
The first green compact are provided, and wherein said the first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3; And
Heat described the first green compact to specified temp, wherein said specified temp energy is so that described the first green compact are finished sintering.
8. electric capacity comprises:
The first green compact, wherein said the first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3; And
The second green compact, described the second green compact are formed on described the first green compact.
9. electric capacity comprises:
The first green compact, wherein said the first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3; And
Temperature characterisitic is kept medium, and described temperature characterisitic is kept medium and is formed on described the first green compact.
10. electric capacity comprises:
The first green compact, wherein said the first green compact comprise metal level and YZO
XLayer, wherein Y is that to be selected from one or more element, Z in the IIA family be that to be selected from one or more element, X in the IV family be approximately 3; And
The product performance reliability is kept medium, and described product performance reliability is kept medium and is formed on described the first green compact.
11. consumption electronic products, computer product or communication device, comprise laminated ceramic electric capacity, wherein said laminated ceramic electric capacity is by utilizing claim 1,5, the preparation of 6 or 7 described methods, and described consumption electronic products comprise sound appliances, TV, Disc player, hand held Game device, holder for TV playing, personal digital assistant, MP3 player, MP4 player, digital camera, digital camera, printer, scanning machine, multifunctional paper feeding machine, digital frame, GPS navigation system, Electronic Paper, computer peripheral equipment commodity; Described computer product comprises desktop PC, mobile computer, Macintosh, flat computer, barebone computer, palmtop computer or little pen electricity; Described communication device comprises wireless transmit receive unit, mobile phone, intelligent mobile phone, intercom, beeper, telephone set, video phone, facsimile machine, Raido speakerphone or the networking telephone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103085277A CN103050280A (en) | 2011-10-12 | 2011-10-12 | Sintering inhibition of multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103085277A CN103050280A (en) | 2011-10-12 | 2011-10-12 | Sintering inhibition of multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103050280A true CN103050280A (en) | 2013-04-17 |
Family
ID=48062889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103085277A Pending CN103050280A (en) | 2011-10-12 | 2011-10-12 | Sintering inhibition of multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103050280A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218406A (en) * | 2018-01-19 | 2018-06-29 | 北京元六鸿远电子科技股份有限公司 | Low-temperature co-burning ceramic material of low dielectric constant and low loss and preparation method thereof |
| CN108249918A (en) * | 2018-01-19 | 2018-07-06 | 北京元六鸿远电子科技股份有限公司 | Low-temperature sintering huge dielectric constant superfine ceramics material and preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1757272A (en) * | 2003-10-17 | 2006-04-05 | 日立金属株式会社 | Multilayer ceramic substrate, manufacturing method thereof, and electronic device using same |
| CN1917106A (en) * | 2005-11-15 | 2007-02-21 | 广东风华高新科技股份有限公司 | Nonmagnetic sheet type ceramic dielectric capacitor in multiple layers, and preparation method |
| CN1921038A (en) * | 2005-11-18 | 2007-02-28 | 广东风华高新科技股份有限公司 | Non-magnetism high-voltage sheet type multilayer ceramic capacitor and its producing method |
| CN101985395A (en) * | 2010-11-26 | 2011-03-16 | 天津师范大学 | Method for preparing high dielectric constant barium titanate ceramic |
| CN102120698A (en) * | 2010-12-24 | 2011-07-13 | 钱云春 | Barium zirconate-based medium and high voltage ceramic dielectric capacitor material |
-
2011
- 2011-10-12 CN CN2011103085277A patent/CN103050280A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1757272A (en) * | 2003-10-17 | 2006-04-05 | 日立金属株式会社 | Multilayer ceramic substrate, manufacturing method thereof, and electronic device using same |
| CN1917106A (en) * | 2005-11-15 | 2007-02-21 | 广东风华高新科技股份有限公司 | Nonmagnetic sheet type ceramic dielectric capacitor in multiple layers, and preparation method |
| CN1921038A (en) * | 2005-11-18 | 2007-02-28 | 广东风华高新科技股份有限公司 | Non-magnetism high-voltage sheet type multilayer ceramic capacitor and its producing method |
| CN101985395A (en) * | 2010-11-26 | 2011-03-16 | 天津师范大学 | Method for preparing high dielectric constant barium titanate ceramic |
| CN102120698A (en) * | 2010-12-24 | 2011-07-13 | 钱云春 | Barium zirconate-based medium and high voltage ceramic dielectric capacitor material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218406A (en) * | 2018-01-19 | 2018-06-29 | 北京元六鸿远电子科技股份有限公司 | Low-temperature co-burning ceramic material of low dielectric constant and low loss and preparation method thereof |
| CN108249918A (en) * | 2018-01-19 | 2018-07-06 | 北京元六鸿远电子科技股份有限公司 | Low-temperature sintering huge dielectric constant superfine ceramics material and preparation method and application |
| CN108249918B (en) * | 2018-01-19 | 2020-12-25 | 北京元六鸿远电子科技股份有限公司 | Low-temperature sintered giant dielectric constant fine-grain ceramic material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI402874B (en) | Laminated ceramic capacitors | |
| KR101021513B1 (en) | Multilayer Ceramic Capacitor and Manufacturing Method Thereof | |
| JP5046700B2 (en) | Dielectric porcelain and multilayer ceramic capacitor | |
| JP5829232B2 (en) | Dielectric ceramic composition and multilayer ceramic capacitor including the same | |
| JP5801274B2 (en) | Dielectric composition and ceramic electronic component including the same | |
| WO2007026614A1 (en) | Dielectric ceramic, process for producing the same, and laminated ceramic capacitor | |
| JP7283019B2 (en) | Dielectric porcelain composition, multi-layer ceramic capacitor containing the same, and method for manufacturing multi-layer ceramic capacitor | |
| CN101570434B (en) | X8R type base metal inner electrode multilayer ceramic capacitor dielectric material and preparation method thereof | |
| JP4513278B2 (en) | Non-reducing dielectric ceramic manufacturing method, non-reducing dielectric ceramic and multilayer ceramic capacitor | |
| JP2016108217A (en) | Dielectric ceramic composition, and multilayer ceramic capacitor including the same | |
| CN114956806B (en) | Co-doped barium titanate ceramic dielectric material, preparation and application thereof | |
| CN113582683A (en) | BaTiO for X8R MLCC3Preparation method of base ceramic material | |
| US9064638B2 (en) | Dielectric ceramic, stack ceramic electronic component, and method of manufacturing these | |
| US8178458B2 (en) | Dielectric ceramic composition | |
| CN102992756B (en) | X8R-type capacitor ceramic material with high dielectric constant and preparation method thereof | |
| KR20150121569A (en) | Dielectric ceramic composition and multilayer ceramic capacitor comprising the same | |
| JP2008135638A (en) | Multilayer ceramic capacitor | |
| JP2008239402A (en) | Dielectric porcelain and multilayer ceramic capacitor | |
| CN103050280A (en) | Sintering inhibition of multilayer ceramic capacitor for improving capacitance temperature characteristic and reliability | |
| JP2003077754A (en) | Multilayer ceramic capacitor and its manufacturing method | |
| CN101654360A (en) | Ceramic powder composition, ceramic material and multilayer ceramic capacitor made of ceramic material | |
| KR101659143B1 (en) | Dielectric ceramic composition and multilayer ceramic capacitor comprising the same | |
| CN100568424C (en) | Multilayer ceramic capacitor and manufacturing method thereof | |
| JP2014198660A (en) | Dielectric ceramic composition and multi-layer ceramic capacitor comprising the same | |
| CN101908415A (en) | Preparation method of X8R characteristic chip multilayer ceramic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130417 |