CN103050281A - Shrinkage sintering inhibition for improving electrode continuity of multilayer ceramic assembly - Google Patents
Shrinkage sintering inhibition for improving electrode continuity of multilayer ceramic assembly Download PDFInfo
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- CN103050281A CN103050281A CN2011103089210A CN201110308921A CN103050281A CN 103050281 A CN103050281 A CN 103050281A CN 2011103089210 A CN2011103089210 A CN 2011103089210A CN 201110308921 A CN201110308921 A CN 201110308921A CN 103050281 A CN103050281 A CN 103050281A
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Abstract
The invention solves the problem of incapability of achieving better electrode continuity after sintering due to mismatching of internal electrode shrinkage rate and ceramic material shrinkage rate of a multilayer ceramic assembly in a sintering process. A former document indicates that the problem of electrode discontinuity of the multilayer ceramic assembly can be improved by using rapid sintering. According to the method provided by the invention, the better electrode continuity can be achieved by the multilayer ceramic assembly without using the rapid sintering.
Description
Technical field
The present invention is a kind of sintering method, particularly, the present invention relates to improve the successional inhibition of laminated ceramic assembly electrode and shrinks sintering method.
Background technology
Passive component (Passive Components) for electron product circuit design in indispensable spare part.Compare with microcontroller, internal memory etc., although electric capacity is not critical components, the quality of its quality but is related to the performance of electronic product performance.Traditional mica capacitor, papery electric capacity, ceramic condenser, plastic film electric capacity, electrochemical capacitor and present advanced laminated ceramic electric capacity (Multilayer Ceramic Capacitors, MLCC) etc. all be capacitor, its purposes is storage, filtering, bypass, coupling, anti-coupling and the tuning vibration etc. of energy; Capacitor is the assembly of PC, mobile phone, auto electronic at present, with the demand of information product " compact ".Volume is little, capacitance is large, the low laminated ceramic electric capacity of attempt loss late when using high frequency, owing to can take a large amount of productions, reach cheap and stable high characteristic, thereby under the development trend of existing industry application surface mount technology (Surface Mount Technology, SMT) a large amount of production, and more can popularly develop with respect to single-layer ceramic electric capacity.
In order to realize the thin layer of ceramic layer, therefore increase the laminated chip number of ceramic layer.General laminated ceramic electronic component is to be made of ceramic layer and the mutual lamination of internal electrode, but its internal electrode is not to cover whole ceramic layers, and only at the inner side of the little retrude in the peripheral part of ceramic layer internal electrode being exposed from chip sides, this is because exist section poor between internal electrode and ceramic layer.Therefore, if when the laminated chip number of ceramic layer increases, construct defective with regard to the easy delamination etc. of producing because this section is poor.Although, can by after internal electrode pattern being printed on ceramic undressed, in the part printing ceramic paste of not printing internal electrode pattern, come absorber portion poor (with reference to Japanese kokai publication sho 56-94719 communique) by this ceramic paste.
Yet the method, but when burning till because of the existing difference of sintering shrinkage behavior of internal electrode and ceramic layer, cause presenting between internal electrode end and ceramic layer fine gap, although the section that can absorb between ceramic layer and internal electrode is poor, yet when the infiltration of the moisture such as moisture, the bad flaw of moisture-proof is caused in this gap on the contrary.In addition with SiO
2The section of making an addition to is poor in order to absorb ceramic paste, although can shorten pottery and the measures of dispersion (with reference to patent documentation 2004-96010 communique) of internal electrode because of the sintering shrinkage behavior, yet, in fact be not easy to make pottery in full accord with the sintering shrinkage behavior of internal electrode, industry not yet can solve the moisture-proof problem of poor that this gap produces fully at present.
Capacitor system stores electric charge and utilizes the electronics passive component that moment disengages stored electric charge, and can the performance of its function be the insulative dielectric material of institute's double team between two parallel conducting electrodes, present the ability of stored electric charge.The size of relevant capacitance, formula is as follows: C=8.84x10
-12K (n-1) S/e, wherein, C represents capacitance, and unit is farad (F); K represents dielectric constant; N represents the inner electrode layer number; The area of electrode crossover in the S representative, unit is a square metre (m
2); E represents the thickness of dielectric material, and unit is rice (m).
The electrical of laminated ceramic electric capacity is one of quality-critical pointer, learn from creation data demonstration and the senior engineer's of industry experience, the electrical quality fraction defective of MLCC processing procedure can reach 5%～40%, and its main cause, and approximately 70%～80%, because Pd/Ag cream printing process.The sintering shrinkage behavior of above-mentioned pottery and internal electrode is in full accord, also may cause the defective of its implosion, and affects reliability and the yields of assembly, impels discontinuous contact, resistance value change, capacitance fall-off, and the defective such as electric leakage is excessive.When stock's temperature and humidity change, this implosion, the electrical bad MLCC of quality, impaired because of function, present the phenomenons such as electric current that short circuit, stream pass through is uncontrolled, out-of-sequence, thereby the product heating, may cause Sony lithium battery this class event of exploding.
Although 201023218 publication numbers disclosed a kind of metal level that is compacted by the titanium dioxide of dielectric layer and nickel and trace in Taiwan has promoted the internal electrical character amount of monolithic ceramic capacitor and stable capacitance is provided.
Be devoted to the research of laminated ceramic electric capacity processing procedure for many years inventor etc., after Taiwan 587067 publication numbers disclosed " suppress the method for low-temp ceramics sintering shrinkage and suppress layer ", more design " utilization suppresses to shrink sintering and improves laminated ceramic assembly electrode continuity " was to promote the quality of laminated ceramic electric capacity.
Summary of the invention
The present invention mainly is the method that suppresses the low-temp ceramics sintering shrinkage about a kind of, it comprises storehouse and suppresses layer on dielectric layer and form ceramic green, in order to suppress the contraction of this dielectric layer, wherein be printed with dissimilar materials on this dielectric layer and/or be placed with conductor, resistance, electric capacity and analog thereof, it is characterized in that these inhibition series of strata have with this dielectric layer on dissimilar materials and/or place conductor, resistance, corresponding the punchinging of electric capacity and analog position thereof makes these dissimilar materialss and/or conductor, resistance, electric capacity and analog thereof can not cover by suppressed layer when dielectric layer and inhibition layer stack.
The present invention utilizes the Shrinkage behavior when suppressing sintering to improve the discontinuous problem of electrode layer, and can still can keep good electrode continuity reducing under the print thickness, reduces the use cost that printed layers thickness can significantly reduce metal paste.Can be known by document, must use the Fast Sintering mode if want to improve the electrode continuity, but general laminated ceramic assembly company is when considering the cost of output, and can't consider simultaneously the Fast Sintering mode, because Fast Sintering need to expend very large power, extremely can not realize for cost calculation.Utilize technology of the present invention, all applicable under the sintering condition of general passive component company, do not need significantly to change process conditions and step, can not affect the making flow process of whole company, just can in a large amount of production, use.
For monolithic ceramic capacitor, it is to be formed by ceramic layer and interior metal electrode layer interleaving stack, namely ceramic layer is wrapped by two parallel pole layers up and down and holds under the arm, if the capacity plate antenna that forms, rely on again internal electrode and outer electrode to be connected, make each Capacitance parallel connection, to improve total storage electric weight of capacitor.And first ceramic powders is prepared into strip, strip being piled up moulding (tape casting) mode is to increase the laminated ceramic number of layers again, in order to improve the processing procedure of monolithic ceramic capacitor.Yet residual porosity can cause electrical quality bad phenomenon behind the sintering because of the segregation of powder particle.
The invention provides a kind of sintering method, it comprises step: the first green compact are provided, on these first green compact, form the second green compact and heat simultaneously these first green compact and this second green compact to specified temp, wherein this specified temp energy is so that this first green compact are finished sintering.
According to above-mentioned conception, wherein the first green compact are dielectric layer and the metal levels with the ceramic powders preparation, and are printing dissimilar materials on its dielectric layer and/or be placed with conductor, resistance, electric capacity and analog thereof.Metal level then be add different proportion Cu content in the Ni metal paste, form nickel (Ni)-copper (Cu) alloy.Or silver-palladium alloy also or simple metal.Need to expend a large amount of type metal cream in the laminated ceramic making, therefore need reduce the cost cost of metal paste (Metalization Paste) on assembly as far as possible, utilize technical characterstic of the present invention, just can significantly reduce the metal paste use amount, the lamination component characteristic can be do not affected yet, cost can also be reduced to a great extent.
Dielectric layer comprises with other metal oxide of various combined dopants (such as BaO, Y
2O
3, ZrO
2, SiO
2, MgO, MnO, MoO
3, CaO, Lu
2O
3, Yb
2O
3, or WO
3) the basic material of barium titanate.The present invention is in heating these first green compact and this second green compact to specified temp simultaneously, and wherein this specified temp only can be so that these first green compact be finished sintering, and the heating rate of its heating there is no the restriction of speed.During these first green compact of sintering, keep this metal level and both shrinkages of this ceramic layer are close.
The present invention also provides a kind of sintering method, it comprises step: the first green compact are provided, wherein these first green compact comprise metal level and ceramic layer, and provide contraction to keep medium, when these first green compact of specified temp sintering, must keep this metal level and both shrinkages of this ceramic layer, it is complementary.
According to above-mentioned conception, the ceramic layer of ceramic powders preparation wherein, print dissimilar materials on it and/or placing conductor, resistance, electric capacity and analog thereof, to keep medium be that sintering process is kept this metal level and the close inhibition layer of both shrinkages of this ceramic layer and wherein shrink, and need not add ceramic powders.
In addition, the present invention also provides a kind of sintering method, and it comprises step: the first green compact are provided, wherein these first green compact comprise metal level and ceramic layer, and provide the electrode continuity to keep medium, when being used to these first green compact of specified temp sintering, keep the electrode continuity of this metal level.
Particularly, that X, Y, Z three directions are shunk approximately 15-20% simultaneously during the free sintering of ceramic component, yet when add need higher sintering temperature the inhibition layer in ceramic component up and down during both sides, suppress the layer material contraction because under the temperature of sintered ceramic assembly, can't allow, so ceramic component does not shrink in X, Y-direction under sintering temperature, all shrinkage directions concentrate on the Z direction, and its shrinkage can be up to 30-40%.Illustrate significantly with respect to free sintering, when utilizing inhibition sintering ceramic component, be applied to ceramic component in Z direction generation imaginary force and facilitate ceramic component significantly to shrink in the Z direction.
With respect to general sintering laminated ceramic assembly, only under the speed sintering that is rapidly heated, just can make the electrode continuity good, suppress to shrink sintering laminated ceramic assembly yet utilize, then no matter the heating rate speed, the electrode continuity of laminated ceramic assembly is all good, thus, utilize and suppress to shrink sintering laminated ceramic assembly, can adjust its needed heating rate according to the needed characteristic of laminated ceramic assembly.
In addition; can effectively improve ceramic green in the laminated ceramic assembly and metal electrode green compact bi-material at X, Y-direction sintering shrinkage mismatch problem owing to utilize suppressing sintering; this receives at X, Y-direction sintering and produces mismatch problem in order to reduce ceramic green in the laminated ceramic assembly and metal electrode green compact bi-material during for original sintering laminated ceramic assembly; usually can add the ceramic powder of 5-20wt% in interior electrode cream, the coupling of shrinking when improving sintering between the two.But thus, then in order to improve the electrode continuity, but significantly increased thickness of electrode, the inner electrode layer number of the laminated capacitor of ultrahigh capacitance values is up to more than hundreds of layers now, this effect is just obvious especially, adds pottery and improves the electrode continuity in interior electrode and but increase interior thickness of electrode because utilize, and interior electrode number is many, very large to component thickness, so can only limit interior electrode number.
Therefore for the laminated capacitor of ultrahigh capacitance values, how reducing interior electrode metal layer thickness and keeping good electrode continuity then is the emphasis of studying at present.When utilizing the inhibition sintering, it has not been problem that electrode and ceramic post sintering shrink coupling, namely can make interior electrode with the simple metal electrode cream that does not add ceramic powder thus, reach under thinner interior thickness of electrode, still have the good electrode continuity, so can increase the capacitance that the interior electrode storehouse number of plies of unit volume promotes monolithic ceramic capacitor.
Medium thickness in the monolithic ceramic capacitor of high appearance value can be down to 1.5 μ m and electrode layers thickness can be down to 1.2 μ m now, however its electrode continuity only reach about 75%, 25% the space of improving is nearly arranged.Suppress sintering processing when using, the electrode continuity is obviously improved a lot than free sintering processed, and from electrode layers thickness and electrode continuity relation, and observable goes out utilizing simple metal to work as electrode and during at the inhibition sintering, even thickness of electrode is below 1 μ m, the electrode continuity also can reach more than 90%.So not only can improve the electrode continuity, again can be because of the thin increase electrode of thickness of electrode storehouse number, this has very big help to the monolithic ceramic capacitor that develops high appearance value.
Improvement mode of the present invention be with laminated ceramic assembly upper and lower add need to higher sintering temperature the inhibition layer, utilize needing higher sintering temperature to suppress layer comes the interior ceramic material of establishment laminated ceramic assembly and electrode material in the shrinkage of X-Y direction, make in Z direction generation imaginary force to put on the laminated ceramic assembly that contains interior electrode, facilitate the interior electrode of inhibition in time to add the imperial palace electrode in the contraction of Z-direction in the shrinkage of X, Y-direction.Thus, because interior electrode is just like large-area sheet metal green compact, the electrode continuity mainly is that the interior ceramic green of ceramic component and metal electrode green compact bi-material cause in the institute of not mating of X, Y-direction sintering shrinkage in the impact, when bi-material is sintering X, can reduce the mismatch problem of sintering shrinkage when Y-direction is suppressed, improve the successional problem of electrode to reach.During free sintering and during suppressed layer ceramic material, inhibition sintering when electrode material Shrinkage behavior difference is to suppress layer can produce larger longitudinal contraction, reach inhibition electrode material and ceramic material in cross-direction shrinkage, can reach thus electrode material and cause better continuity because of less cross-direction shrinkage.
Interior electrode shrinks and ceramic material shrinkage mismatch problem, can't reach the good electrode continuity after causing being created in sintering, point out to utilize Fast Sintering just can improve laminated ceramic assembly electrode discontinuity problem by previous document, the present invention utilizes the method need not utilize Fast Sintering, the laminated ceramic assembly can be reached the good electrode continuity.
Improve the interior ceramic green of laminated ceramic assembly and metal electrode green compact bi-material at X, Y-direction sintering shrinkage mismatch problem, way is to have two kinds at present:
(1) utilize the interpolation ceramic powder to reduce bi-material sintering matching problem in interior electrode cream, this way major defect is the electrode continuity that need to thicker interior electrode obtains, thus except can't increasing electrode storehouse number, easily produce from splitting problem when thick electrode green compact and ceramic green storehouse very much.
(2) utilization is rapidly heated to reduce bi-material sintering matching problem; yet be rapidly heated except easily causing the laminated ceramic assembly that causes because of the material thermal expansion coefficient difference easily to occur from splitting problem; usually the laminated ceramic assembly is before sintering; temperature-rise period can help and remove remaining organic adhesive agent; a large amount of production; heat up and too fastly easily cause the inadequate time to remove remaining organic adhesive agent, this carbon residue enters the sintering zone and easily causes the ceramic component abnormal grain to grow up to cause electrically bad and assembly reliability issues.
The present invention utilizes the Shrinkage behavior when suppressing sintering to improve the discontinuous problem of electrode layer, and can still can keep good electrode continuity reducing under the print thickness, reduces the use cost that printed layers thickness can significantly reduce metal paste.Can be known by document, must use the Fast Sintering mode if want to improve the electrode continuity, but general laminated ceramic assembly company is when considering the cost of output, and can't considers simultaneously the Fast Sintering mode, because Fast Sintering need expend sizable power, extremely can not realize for cost calculation.Utilize the technology of the present invention, all applicable under the sintering condition of general passive component company, do not need significantly to change process conditions and step, can not affect the making flow process of whole company, just can in a large amount of production, use easily.
The present invention can access more deep understanding by following detailed description.
Description of drawings
Fig. 1 a suppresses the sintering method schematic diagram
The b passive component suppresses to shrink the sintering method schematic diagram
The c passive component improves electrode continuity method schematic diagram
Fig. 2 a suppresses to shrink passive component sintering green compact schematic diagram
B improves electrode continuity passive component sintering green compact schematic diagram
The free agglomerated material x-y-z-of Fig. 3 direction Shrinkage behavior schematic diagram
Fig. 4 suppresses agglomerated material x-y-z-direction Shrinkage behavior schematic diagram
The free sintering of Fig. 5 laminated ceramic assembly and inhibition sintering Material shrinkage behavior schematic diagram
The sintering shrinkage behavior difference of the electrode of Fig. 6 laminated ceramic assembly, suppressed layer, three kinds of material of inhibition layer
Under the free sintering of Fig. 7 a, 200 ℃/hr of heating rate affects the electrode continuity
Under the free sintering of b, 3000 ℃/hr of heating rate affects the electrode continuity
Fig. 8 a inhibition of sintering is forged, and 200 ℃/hr of heating rate affects the electrode continuity
The b inhibition of sintering is forged, and 3000 ℃/hr of heating rate affects the electrode continuity
9 figure monolithic ceramic capacitors are forged electrode layers thickness to electrode continuity and capacitance impact at free sintering or inhibition of sintering
[primary clustering symbol description]
1 provides the first green compact step
2 form the second green compact step
3 while heating stepses
11 provide the first green compact step
12 form contraction keeps the medium step
13 heating stepses
21 provide the first green compact step
22 form the electrode continuity keeps the medium step
23 heating stepses
The sintering green compact of 31 passive components
32 first green compact
33 metal levels
34 ceramic layers
Medium is kept in 35 contractions
The sintering green compact of 41 passive components
42 first green compact
43 metal levels
44 ceramic layers
45 electrode continuitys are kept medium
52 sinter layers
62 sintered ceramic assemblies
65 bond courses
72 laminated ceramic assemblies
73 interior electrodes
75 suppress layer
Embodiment
See also Fig. 1 a, the invention provides a kind of sintering method, it comprises step: the first green compact 1 are provided, on these first green compact, form the second green compact 2 and heat simultaneously these first green compact and this second green compact to specified temp 3, wherein this specified temp energy is so that this first green compact are finished sintering 4.In preferred embodiment of the present invention, this specified temp be can be more than 600～2000 ℃, the sintering temperature of these the second green compact then need be higher than this specified temp.In addition, these first green compact have amount of contraction, and the contraction of this amount of contraction is suppressed by these second green compact.These first green compact can replace storehouse by a plurality of ceramic greens and a plurality of electrode green compact and form.
See also Fig. 1 b, according to invention spirit of the present invention, also can be used to provide another kind of sintering method, the method comprising the steps of: the first green compact 11 are provided, wherein these first green compact comprise metal level and ceramic layer, and provide contraction to keep medium 12, when these first green compact 13 of specified temp sintering, must keep this metal level and both shrinkages of this ceramic layer, it is complementary.In preferred embodiment of the present invention, this specified temp is more than 600～2000 ℃, this metal level and ceramic layer have respectively the first amount of contraction and the second amount of contraction at this specified temp, and the contraction of this first amount of contraction is subjected to this contraction to keep medium to suppress.In addition, this metal level and ceramic layer can replace storehouse by a plurality of ceramic greens and a plurality of electrode green compact and form.
See also Fig. 1 c, according to invention spirit of the present invention, more can be used to provide another kind of sintering method, the method comprising the steps of: the first green compact 21 are provided, wherein these first green compact comprise metal level and ceramic layer, and provide the electrode continuity to keep medium 22, when being used to these first green compact 23 of specified temp sintering, keep the electrode continuity of this metal level.In preferred embodiment of the present invention, this specified temp is more than 600～2000 ℃, this metal level and ceramic layer have respectively the first amount of contraction and the second amount of contraction at this specified temp, and the contraction of this first amount of contraction is subjected to this electrode continuity to keep medium to suppress.In addition, this metal level and ceramic layer are to replace storehouse by a plurality of ceramic greens and multiple a plurality of electrode green compact to be formed.
See also Fig. 2 a, according to invention spirit of the present invention, a kind of sintering green compact 31 of passive component comprise the first green compact 32, wherein these first green compact 32 comprise metal level 33 and ceramic layer 34, shrink and keep medium 35, when being used to these first green compact 31 of specified temp sintering, keep both shrinkages of this metal level 33 and this ceramic layer 34, it is complementary.In preferred embodiment of the present invention, this specified temp is more than 600～2000 ℃, this metal level 33 and ceramic layer 34 have respectively the first amount of contraction and the second amount of contraction at this specified temp, and the contraction of this first amount of contraction is subjected to this contraction to keep medium to suppress.In addition, this metal level and ceramic layer are to replace storehouse by a plurality of ceramic greens and a plurality of electrode green compact to be formed.
See also Fig. 2 b, according to invention spirit of the present invention, also have a kind of sintering green compact 41 of passive component to comprise the first green compact 42, wherein these first green compact 42 comprise metal level 43 and ceramic layer 44, the electrode continuity is kept medium 45, when being used to these first green compact 41 of specified temp sintering, keep the electrode continuity of this metal level 43, it is complementary.In preferred embodiment of the present invention, this specified temp is more than 600～2000 ℃, this metal level 43 and ceramic layer 44 have respectively the first amount of contraction and the second amount of contraction at this specified temp, and the contraction of this first amount of contraction is subjected to this electrode continuity to keep medium to suppress.In addition, this metal level and ceramic series of strata replace storehouse by a plurality of ceramic greens and a plurality of electrode green compact and are formed.
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., for clearly representing its corresponding relation and shown by reference numeral is succinctly reached to reduce repeatability, only row are as follows in detail with key step:
The laminated ceramic assembly sintering method of a kind of consumption electronic products, computer product or communication device, it comprises that step provides the first green compact, forms the second green compact on these first green compact, and heat simultaneously these first green compact and this second green compact to specified temp, wherein this specified temp energy is so that this first green compact are finished sintering.
The laminated ceramic assembly sintering method of a kind of consumption electronic products, computer product or communication device, it comprises that step provides the first green compact, wherein these first green compact comprise metal level and ceramic layer, and provide contraction to keep medium, when being used to these first green compact of specified temp sintering, keep this metal level and both shrinkages of this ceramic layer, it is complementary.
The laminated ceramic assembly sintering method of a kind of consumption electronic products, computer product or communication device, it comprises that step provides the first green compact, wherein these first green compact comprise metal level and ceramic layer, and provide the electrode continuity to keep medium, when being used to these first green compact of specified temp sintering, keep the electrode continuity of this metal level.
A kind of consumption electronic products, computer product or communication device comprise by green sintering and are formed the laminated ceramic assembly, and shrink and keep medium, are connected with this ceramic component.And the laminated ceramic assembly can be the passive components such as resistance, electric capacity.This laminated ceramic assembly more can be further defined to a plurality of ceramic layers, and a plurality of electrode layer and these ceramic layers replace storehouse, to form assembly.And these 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.This computer product comprises desktop PC, mobile computer, Macintosh, flat computer, barebone computer, palmtop computer or little pen electricity.This communication device comprises wireless transmit receive unit (wireless transmit/receive unit, WTRU), mobile phone, intelligent mobile phone, intercom, beeper, telephone set, video phone, facsimile machine, Raido speakerphone or the networking telephone.
In order more to understand sample attitude and the difference with the prior art after the invention process, cooperate graphic being illustrated with literal again at this.Please refer to Fig. 3 and Fig. 4.Among Fig. 3, during free sintered ceramic assembly sinter layer 52, shrink simultaneously approximately 15-20% in X, Y, Z three directions.Yet, in Fig. 4, when add need higher sintering temperature bond course 65 on ceramic component 62 time, because can't allow bond course 65 Material shrinkages in the temperature of sintered ceramic assembly 62, so ceramic component 62 does not shrink in X, Y-direction under sintering temperature, all shrinkage directions concentrate on the Z direction, and its shrinkage can be up to 30-40%.Illustrate significantly with respect to free sintering, when utilizing inhibition sintering ceramic component, be applied to ceramic component in Z direction generation imaginary force and facilitate ceramic component significantly to shrink in the Z direction.
Refer again to Fig. 5, improvement mode of the present invention be with laminated ceramic assembly 72 upper and lowers add need to higher sintering temperature inhibition layer 75, utilize needing higher sintering temperature to suppress layer 75 comes the interior ceramic material of establishment laminated ceramic assembly 72 and electrode material in the shrinkage of X-Y direction, make in Z direction generation imaginary force to be applied on the laminated ceramic assembly that contains interior electrode 73, facilitate the interior electrode 73 of inhibition in time to add imperial palace electrode 73 in the contraction of Z-direction in the shrinkage of X, Y-direction.Thus, because interior electrode has for example large-area sheet metal green compact, electrode 73 continuitys mainly are that ceramic component 72 interior ceramic green and metal electrode green compact bi-materials cause in the institute of not mating of X, Y-direction sintering shrinkage in the impact, when bi-material is sintering X, can reduce the mismatch problem of sintering shrinkage when Y-direction is suppressed, improve the successional problem of electrode to reach.
In addition, the present invention will and cooperate diagram by following preferred embodiment, do further to describe in detail.Quote the described principle of summary of the invention and carry out the present invention's experiment, utilize (Ba, Ca) (Ti, Zr) O
3+ SiO
2Working as sintering aid, is the dielectric ceramic layer so lower sintering temperature (＜1150 ℃) is arranged, BaTiO
3For suppressing layer higher sintering temperature (＞1250 ℃) is arranged, Ni is interior electrode cream, and three kinds of storeroom shrinkages vary with temperature, and has otherness in order to shrink each other between testimonial material, as shown in Figure 6.
The free sintering of this monolithic ceramic capacitor is under 200 ℃/hr and 3000 ℃/hr heating rate, sintering temperature is 1150 ℃, hold warm 2hr, present the Different electrodes continuity, from Fig. 7 a micro-structural can find out under heating rate at a slow speed (200 ℃/hr), because electrode and storeroom begin differing greatly of sintering shrinkage temperature, cause the interior ceramic green of monolithic ceramic capacitor and metal electrode green compact bi-material at X, not seriously not mating of Y-direction sintering shrinkage, so electrode is discontinuous, only have 70% good continuity is arranged, but when improving the sintering heating rate, 3000 ℃/hr for example, so significantly shorten because be rapidly heated electrode and storeroom begin the sintering shrinkage temperature, cause the interior ceramic green of monolithic ceramic capacitor and metal electrode green compact bi-material at X, the Y-direction sintering shrinkage reaches coupling, shown in Fig. 7 b, the electrode continuity can significantly rise to 92%.Yet suppress layer and do when suppressing sintering when monolithic ceramic capacitor adds, under 200 ℃/hr of two kinds of heating rates and 3000 ℃/hr, sintering temperature is 1150 ℃, when holding warm 2hr, all presents extraordinary electrode continuity such as Fig. 8 a and Fig. 8 b.Significantly, because the existence relation that suppresses layer is arranged, the electrode continuity can further be improved, and irrelevant with the sintering heating rate.This main cause is exactly that the existence that suppresses layer has significantly reduced ceramic green in the monolithic ceramic capacitor and metal electrode green compact bi-material at X, Y-direction sintering shrinkage mismatch problem.
Medium thickness in the monolithic ceramic capacitor of present high appearance value can be down to 1.5 μ m and electrode layers thickness can be down to 1.2 μ m, however its electrode continuity only reach about 75%, 25% the space of improving is nearly arranged.Suppress sintering processing when using, the electrode continuity is obviously than freely sintering improvement processed is a lot, and from electrode layers thickness and the successional relation of electrode, observable goes out utilizing simple metal to work as electrode and when suppressing sintering, even thickness of electrode is below 1 μ m, the electrode continuity also can reach more than 90%, as shown in Figure 9.
Claims (10)
1. sintering method, it comprises step:
The first green compact are provided;
On described the first green compact, form the second green compact; And
Heat simultaneously described the first green compact and described the second green compact to specified temp, wherein said specified temp energy is so that described the first green compact are finished sintering.
2. method according to claim 1, wherein said specified temp is more than 600～2000 ℃.
3. method according to claim 1, the sintering temperature of wherein said the second green compact is higher than described specified temp.
4. method according to claim 1, wherein said the first green compact have amount of contraction in described sintering temperature, and suppressed by described the second green compact.
5. method according to claim 1, wherein said the first green compact are to replace storehouse by a plurality of ceramic greens and a plurality of electrode green compact to be formed.
6. sintering method, it comprises step:
The first green compact are provided, and wherein said the first green compact comprise metal level and ceramic layer; And
Provide to shrink and keep medium, when wherein said contraction is kept medium and is used to described the first green compact of specified temp sintering, keep described metal level and both shrinkages of described ceramic layer, it is complementary.
7. method according to claim 6, wherein:
Described metal level and ceramic layer have respectively the first amount of contraction and the second amount of contraction at described specified temp, and the contraction of described the first amount of contraction is subjected to described contraction to keep medium to suppress; Or described metal level and ceramic series of strata replace storehouse by a plurality of ceramic greens and a plurality of electrode green compact and are formed.
8. sintering method, it comprises step:
The first green compact are provided, and wherein said the first green compact comprise metal level and ceramic layer; And
Provide the electrode continuity to keep medium, when wherein said electrode continuity is kept medium and is used to described the first green compact of specified temp sintering, keep the electrode continuity of this metal level.
9. the sintering green compact of a passive component comprise:
The first green compact, wherein said the first green compact comprise metal level and ceramic layer; And
Medium is kept in contraction, when wherein said contraction is kept medium and is used to described the first green compact of specified temp sintering, keeps this metal level and both shrinkages of this ceramic layer, and it is complementary.
10. the sintering green compact of a passive component comprise:
The first green compact, wherein said the first green compact comprise metal level and ceramic layer; And
The electrode continuity is kept medium, when wherein said electrode continuity is kept medium and is used to described the first green compact of specified temp sintering, keeps the electrode continuity of this metal level.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103440982A (en) * | 2013-07-29 | 2013-12-11 | 无锡商业职业技术学院 | Preparation method for multilayer ceramic capacitor |
| CN108987286A (en) * | 2018-06-29 | 2018-12-11 | 广东风华高新科技股份有限公司 | A kind of ameliorative way of LTCC cofiring mismatch |
| CN112979285A (en) * | 2019-12-17 | 2021-06-18 | 深圳市大富科技股份有限公司 | Ceramic device and method for manufacturing the same |
| CN112979284A (en) * | 2019-12-17 | 2021-06-18 | 深圳市大富科技股份有限公司 | Ceramic device and method for manufacturing the same |
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| CN1294395A (en) * | 1999-10-28 | 2001-05-09 | 株式会社村田制作所 | One-chip ceramic electronic parts and mfg. method thereof |
| CN1757272A (en) * | 2003-10-17 | 2006-04-05 | 日立金属株式会社 | Multi-layer ceramic substrate, method for manufacturng the same and electronic device using the same |
| CN101347058A (en) * | 2006-08-07 | 2009-01-14 | 株式会社村田制作所 | Method of producing multilayer ceramic substrate |
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| CN1294395A (en) * | 1999-10-28 | 2001-05-09 | 株式会社村田制作所 | One-chip ceramic electronic parts and mfg. method thereof |
| CN1757272A (en) * | 2003-10-17 | 2006-04-05 | 日立金属株式会社 | Multi-layer ceramic substrate, method for manufacturng the same and electronic device using the same |
| CN101347058A (en) * | 2006-08-07 | 2009-01-14 | 株式会社村田制作所 | Method of producing multilayer ceramic substrate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103440982A (en) * | 2013-07-29 | 2013-12-11 | 无锡商业职业技术学院 | Preparation method for multilayer ceramic capacitor |
| CN108987286A (en) * | 2018-06-29 | 2018-12-11 | 广东风华高新科技股份有限公司 | A kind of ameliorative way of LTCC cofiring mismatch |
| CN108987286B (en) * | 2018-06-29 | 2020-11-24 | 广东风华高新科技股份有限公司 | Method for improving co-firing mismatch of LTCC (Low temperature Co-fired ceramic) |
| CN112979285A (en) * | 2019-12-17 | 2021-06-18 | 深圳市大富科技股份有限公司 | Ceramic device and method for manufacturing the same |
| CN112979284A (en) * | 2019-12-17 | 2021-06-18 | 深圳市大富科技股份有限公司 | Ceramic device and method for manufacturing the same |
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Application publication date: 20130417 |