CN103077822A - Conductive metal compositions, conductive electrode and multilayer ceramic capacitor comprising conductive electrode - Google Patents
Conductive metal compositions, conductive electrode and multilayer ceramic capacitor comprising conductive electrode Download PDFInfo
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- CN103077822A CN103077822A CN2011103294713A CN201110329471A CN103077822A CN 103077822 A CN103077822 A CN 103077822A CN 2011103294713 A CN2011103294713 A CN 2011103294713A CN 201110329471 A CN201110329471 A CN 201110329471A CN 103077822 A CN103077822 A CN 103077822A
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Abstract
The invention relates to two conductive metal compositions. One of the two conductive metal compositions comprises a titaniferous compound, nickel metal and copper metal or copper alloy, wherein by taking the content of the nickel metal as 100 weight percent, the titaniferous compound accounts for 10-20 weight percent, and the copper metal or the copper alloy accounts for 0.5-20 weight percent, whereas the other conductive metal composition comprises the titaniferous compound, the copper metal and the nickel metal or nickel alloy, wherein by taking the content of the copper metal as 100 weight percent, the titaniferous compound accounts for 10-20 weight percent, and the nickel metal or the nickel alloy accounts for 0.5-30 weight percent. Moreover, the invention relates to a conductive electrode made of the two conductive metal compositions. The invention also provides a multilayer ceramic capacitor comprising the conductive electrode. As the conductive electrode of the multilayer ceramic capacitor is good in continuity, the electric property quality and stability of the capacitor can be improved.
Description
Technical field
The present invention is about a kind of conducting metal constituent, and it is used for making and possesses good successional conductive electrode.In addition, the present invention is also about a kind of monolithic ceramic capacitor that comprises this conductive electrode.
Background technology
Flourish along with electronic industry in recent years, monolithic ceramic capacitor develops with the aspect of high power capacity toward miniaturization, lightweight, thin layer, high-quality rapidly, to promote its competitive advantage, becomes electronic building brick indispensable in the design of electronic circuits.
Monolithic ceramic capacitor comprises ceramic sintered bodies and outer electrode, and its ceramic sintered bodies is comprised of dielectric layer and the mutual overlapping institute that arranges of inner electrode layer.In making the method for monolithic ceramic capacitor, will stamp dielectric layer in order to the metal paste of making inner electrode layer after, both are passed through high temperature sintering jointly, to form the mutual overlapping ceramic sintered bodies of inner electrode layer and dielectric layer.
Yet, because the phenomenon that metal paste easily shrinks in the process of high temperature sintering causes the effective electrode area of inner electrode layer to descend; When more serious, the situation through the meeting of the inner electrode layer behind high temperature sintering fracture can't successfully be connected with outer electrode, and the electrical quality of deteriorated monolithic ceramic capacitor and stability.
For solving the above-mentioned problem that faces, the Taiwan patent discloses No. 201023218 and proposes a kind of monolithic ceramic capacitor, and it has the metal level of compacting as inner electrode layer, uses the internal electrical character amount that promotes capacitor, and more stable capacitance is provided simultaneously.Its characteristics are, the content of titanium dioxide is controlled between 0.25 to 5 percentage by weight in the metal level that will compact, and are higher than 85% the metal level that compacts to form the unit are coverage rate.
The present invention is different from the practice of prior art, use contains the above metal paste of two kinds of metal ingredients makes inner electrode layer, make it in sintering process, produce metal solid solution more than the binary, to reduce the mismatch between dielectric layer and inner electrode layer, to make by this inner electrode layer with good continuity and electrical quality.
Summary of the invention
Main purpose of the present invention is that a kind of conductive electrode is being provided, it makes by comprising two kinds of conducting metal constituent institute sintering more than the metal, the hole size that produces when the sintering can dwindle prepared conductive electrode is used to form and is possessed good successional conductive electrode.
For reaching above-mentioned purpose, the invention provides a kind of by the made conductive electrode of conducting metal constituent.Its conducting metal constituent comprises: a titanium-containing compound; The nickel metal; And copper metal or copper alloy; Wherein, take the content of nickel metal as 100 percentage by weights, the content of titanium-containing compound is 10 to 20 percentage by weights, and this copper metal or copper alloy account for 0.5 to 20 percentage by weight.
In above-mentioned conducting metal constituent, this nickel metal is as a Main Ingredients and Appearance, and copper metal or copper alloy can be used as a metallic additions.In addition, in above-mentioned conducting metal constituent, can further comprise at least one rare earth metal, take the content of nickel metal as 100 percentage by weights, the content sum total of this rare earth metal is 0.01 to 0.1 percentage by weight, and this rare earth metal is selected from the following group that forms: lanthanum (La), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).In this, above-mentioned various rare earth metals can form copper alloy with the copper metal, to make an addition in the conducting metal constituent.
And described titanium-containing compound is for example: the oxide of titanate, titanium oxide and titanium and other metal, but be not limited only to this.Better, titanium-containing compound is barium titanate.In addition, this conducting metal constituent further comprises resin binder and organic solvent.
In addition, for reaching above-mentioned purpose, it is a kind of by the made conductive electrode that gets of conducting metal constituent that the present invention also provides.Its conducting metal constituent comprises: a titanium-containing compound; One bronze medal metal; And nickel metal or a nickel alloy; Wherein, take the content of copper metal as 100 percentage by weights, the content of titanium-containing compound is 10 to 20 percentage by weights, and nickel metal or nickel alloy account for 0.5 to 30 percentage by weight.
In above-mentioned conducting metal constituent, this copper metal is as a Main Ingredients and Appearance, and nickel metal or nickel alloy can be used as a metallic additions.In addition, in above-mentioned conducting metal constituent, can further comprise at least one rare earth metal, take the content of copper metal as 100 percentage by weights, the content sum total of this rare earth metal is 0.01 to 0.1 percentage by weight, and this rare earth metal is selected from the following group that forms: lanthanum (La), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).In this, above-mentioned various rare earth metals can form nickel alloy with the nickel metal, to make an addition in the conducting metal constituent.
And described titanium-containing compound is for example: the oxide of titanate, titanium oxide and titanium and other metal, but be not limited only to this.Better, titanium-containing compound is selected barium titanate.In addition, this conducting metal constituent further comprises resin binder and organic solvent.
In the above-mentioned two kinds of conductive electrodes of the present invention, owing to being formed by two or more at least metals in order to the conducting metal constituent of making, make it in sintering process, can form binary or the metal solid solution more than the binary, use to make and possess good successional conductive electrode.In this, this conductive electrode can be applicable to make the assembly of various lamination type electronic ceramics, such as: Y5V, X7R, X5R or NPO etc.
Another object of the present invention is the mismatch that reduction conductive electrode layer and dielectric layer produce when common sintering, promotes the electrode continuity of monolithic ceramic capacitor, electrical quality with stable.
Another purpose of the present invention provides a kind of monolithic ceramic capacitor, because the significantly raising of its capacitance, can reduce the overlapping number of plies of conductive electrode layer and dielectric layer in the capacitor, reduces by this cost of manufacture of monolithic ceramic capacitor.
For reaching above-mentioned purpose, the invention provides a kind of monolithic ceramic capacitor, comprising: a ceramic sintered bodies, this ceramic sintered bodies comprise up and down the first dielectric layer, the first conductive electrode layer, the second dielectric layer, and second conductive electrode layer of sequentially overlapping setting; One first outer electrode be arranged at a side of this ceramic sintered bodies, and this first outer electrode is to be electrically connected this first conductive electrode layer; And one second outer electrode, be arranged at the opposite side of this ceramic sintered bodies, and this second outer electrode is to be electrically connected this second conductive electrode layer.
In monolithic ceramic capacitor of the present invention, the first conductive electrode layer and the second conductive electrode layer are aforesaid conductive electrode, and it is obtained by above-mentioned two kinds of conducting metal constituents.When dielectric layer when comprising the common sintering of conductive electrode layer of at least two kinds of metals, because the conducting metal constituent contains two or more metals, in sintering process, can produce binary or the metal solid solution more than the binary, make both sintering shrinkage trends consistent, use the better matching of generation, make the monolithic ceramic capacitor that has good successional conductive electrode layer and have higher capacity.In this, use capacitance that conducting metal constituent of the present invention can significantly improve monolithic ceramic capacitor approximately 20 to 25%.
In sum, the present invention's use comprises the above conducting metal constituent of two kinds of metals and makes conductive electrode, uses the continuity and electrical quality that promote conductive electrode.In addition, monolithic ceramic capacitor of the present invention has good successional conductive electrode layer owing to comprising, thereby the capacitance that can further promote monolithic ceramic capacitor and stability, reduce the overlapping number of conductive electrode layer and dielectric layer, and then reach the effect of minimizing cost of manufacture.
Description of drawings
Fig. 1 is the side-looking generalized section of one of monolithic ceramic capacitor of the present invention preferred embodiment.
Fig. 2 is the SEM figure of single conductive electrode layer in the embodiment of the invention 1.
Fig. 3 is the SEM figure of the section of monolithic ceramic capacitor in the embodiment of the invention 1.
Fig. 4 is the SEM figure of single conductive electrode layer in the embodiment of the invention 2.
Fig. 5 is the SEM figure of the section of monolithic ceramic capacitor in the embodiment of the invention 2.
Fig. 6 is the SEM figure of single conductive electrode layer in the embodiment of the invention 3.
Fig. 7 is the SEM figure of the section of monolithic ceramic capacitor in the embodiment of the invention 3.
Fig. 8 is the SEM figure of single conductive electrode layer in the embodiment of the invention 4.
Fig. 9 is the SEM figure of the section of monolithic ceramic capacitor in the embodiment of the invention 4.
Figure 10 is the SEM figure of single conductive electrode layer in the comparative example 1.
Figure 11 is the SEM figure of the section of monolithic ceramic capacitor in the comparative example 1.
The primary clustering symbol description
100 monolithic ceramic capacitors, 110 ceramic sintered bodies
111 first dielectric layers, 112 first conductive electrode layers
113 second dielectric layers, 114 second conductive electrode layers
120 first outer electrodes, 130 second outer electrodes
140 surface electrical coating
Embodiment
The present invention mixes two or more metal ingredients as the conducting metal constituent of making conductive electrode, makes it produce binary or the metal solid solution more than the binary in sintering process, has good successional conductive electrode with preparation.Below, with detailed description conducting metal constituent of the present invention, conductive electrode and comprise its monolithic ceramic capacitor production method and reach effect.
" preparation conducting metal constituent "
At first, nickel metal powder, copper metal powder end, barium titanate powder, rare earth metal powder are mixed with resin binder and organic solvent, make the conducting metal constituent of paste in addition behind the mix and blend.Wherein, the employed rare earth metal of each embodiment can be selected from: lanthanum (La), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu).Composition and the content of the conducting metal constituent that each embodiment and comparative example use are as shown in table 1.
The present invention is used for making the conducting metal constituent of conductive electrode, wherein take the content of nickel metal powder as 100 percentage by weights, the content of barium titanate powder is 20 percentage by weights, and the content at copper metal powder end is 0.5 to 20 percentage by weight, and the total content of rare earth metal is 0.01 percentage by weight.
Table 1: composition and the content of the employed conducting metal constituent of each embodiment and comparative example
" preparation monolithic ceramic capacitor "
At first, the conducting metal constituent of above-mentioned each embodiment and comparative example is printed in respectively on the dielectric ceramic layer, in the sintering environment, carry out sintering after, make conductive electrode layer.Then, repeatedly overlapping several layers of dielectric layer and conductive electrode layer, and after carrying out sintering under the high temperature, form ceramic sintered bodies.
In this, because conducting metal constituent of the present invention comprises nickel metal and two kinds of compositions of copper metal, can in high-temperature sintering process, produce the metal solid solution more than the binary, thereby the mismatch that produces can reduce conductive electrode layer and the common sintering of dielectric layer the time, use to form and have good successional conductive electrode.
Then, the outside coating metal layer in the both sides of ceramic sintered bodies, and carry out sintering in the sintering environment forming two external electrode layers, and further forms a surface electrical coating in these two external electrode layer electroplating surfaces.
Accordingly, see through above-mentioned production method and can form monolithic ceramic capacitor of the present invention.As shown in Figure 1, monolithic ceramic capacitor 100 comprises: ceramic sintered bodies 110, the first outer electrode 120, the second outer electrode 130 and surface electrical coating 140.
Wherein, the first dielectric layer 111, the first conductive electrode layer 112, the second dielectric layer 113 and the second conductive electrode layer 114 that comprise sequentially overlapping setting in the ceramic sintered bodies 110.The first outer electrode 120 is arranged at a side of ceramic sintered bodies 110, and be electrically connected with the first conductive electrode layer 112 in the ceramic sintered bodies 110, the second outer electrode 130 is arranged at the opposite side of ceramic sintered bodies 110, and is electrically connected with the second conductive electrode layer 114 in the ceramic sintered bodies 110.In addition, the first outer electrode 120 and the second outer electrode 130 outside more be provided with a surface electrical coating 140 on the surface.
" the electrical quality of assessment lamination conduction capacitor "
Below, will be by sweep electron microscope (scanning electron microscope, SEM) structure of conductive electrode layer in the prepared monolithic ceramic capacitor of embodiment of each conducting metal constituent of analysis comparison of aforementioned is used the addition of understanding copper metal to the impact of the electrical quality of monolithic ceramic capacitor.
See also Fig. 2,4,6,8,10, it is respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4, reaches the SEM figure of the single conductive electrode layer of comparative example 1; And seeing also Fig. 3,5,7,9,11, it is respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4, and the SEM figure of the section of the monolithic ceramic capacitor of comparative example 1.
In embodiment 1, when the content of copper metal is 0.5 percentage by weight, existing the improving (as shown in Figures 2 and 3) slightly of the electrode coverage rate of its single conductive electrode layer and electrode continuity, and its average electrical capacity also is increased to 132 μ F.In addition, along with the raising of copper content, the average electrical capacity of the monolithic ceramic capacitor of embodiment 2, embodiment 3 and embodiment 4 is increased to respectively 136 μ F, 143 μ F and 147 μ F.
In embodiment 4, when the content of copper metal is 20 percentage by weight, can in sintering process, form more binary metal solid solution, make conductive electrode layer in sintering process, only produce small pore space structure, have good successional conductive electrode layer (extremely shown in Figure 9 such as Fig. 8) and make.Accordingly, the monolithic ceramic capacitor of the embodiment of the invention 4 significantly promotes electrical quality and the stability of capacitor, makes capacitance improve approximately 22.5%.
Otherwise, because the conducting metal constituent only contains a kind of metal ingredient in the comparative example 1, make it in the process of high temperature sintering, produce obvious shrinkage phenomenon, cause the conductive electrode layer behind the sintering to form the structure of multiple hole, and reduce the electrode coverage rate (as shown in figure 10) of conductive electrode layer.In addition, when conductive electrode layer has the defect sturcture of multiple hole, conductive electrode layer will produce the many places fracture and significantly reduce its electrode continuity (as shown in figure 11), make its average electrical capacity drop to about 120 μ F.
Confirmed by experimental result, when the conducting metal constituent comprises dielectric material, nickel metal and copper metal simultaneously, content raising along with the copper metal, in sintering process, can form more binary metal solid solution, use and suppress the contraction situation of conducting metal constituent in high temperature sintering, the mismatch that produces when reducing conductive electrode layer and the common sintering of dielectric layer, make conductive electrode layer behind oversintering, can not form excessive hole, and can form comparatively complete parallel electrically conductive electrode layer, and then promote its electrode coverage rate and electrode continuity.
Therefore, the present invention uses and comprises the above conducting metal constituent making conductive electrode of two kinds of metals, can significantly promote the electrode continuity and electrical quality of conductive electrode layer.When the capacitance of monolithic ceramic capacitor improves with stability, can further reduce the required overlapping number of conductive electrode layer and dielectric layer, and then reach the effect that reduces the capacitor fabrication cost.
The above only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, although the present invention discloses as above with preferred embodiment, yet be not to limit the present invention, any those skilled in the art, in the scope that does not break away from technical solution of the present invention, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, any simple modification that foundation technical spirit of the present invention is done above embodiment, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (12)
1. a conducting metal constituent is characterized in that, comprises:
One titanium-containing compound;
One nickel metal; And
One bronze medal metal or a copper alloy;
Wherein, take the content of nickel metal as 100 percentage by weights, the content of titanium-containing compound is 10 to 20 percentage by weights, and the content of this copper metal or copper alloy is 0.5 to 20 percentage by weight.
2. conducting metal constituent as claimed in claim 1, it is characterized in that, this copper alloy comprises at least one rare earth metal, and this rare earth metal is selected from the following group that forms: lanthanum (La), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
3. conducting metal constituent as claimed in claim 1, it is characterized in that, this conducting metal constituent more comprises at least one rare earth metal, take the content of nickel metal as 100 percentage by weights, the content sum total of this rare earth metal is 0.01 to 0.1 percentage by weight, and this rare earth metal is selected from the following group that forms: lanthanum (La), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
4. conducting metal constituent as claimed in claim 1 is characterized in that, this titanium-containing compound is barium titanate.
5. such as arbitrary described conducting metal constituent in the claim 1 to 4, it is characterized in that, further comprise resin binder and organic solvent.
6. a conducting metal constituent is characterized in that, comprises:
One titanium-containing compound;
One bronze medal metal; And
One nickel metal or a nickel alloy;
Wherein, take the content of copper metal as 100 percentage by weights, the content of titanium-containing compound is 10 to 20 percentage by weights, and the content of nickel metal or nickel alloy is 0.5 to 30 percentage by weight.
7. conducting metal constituent as claimed in claim 6, it is characterized in that, this nickel alloy comprises at least one rare earth metal, and this rare earth metal is selected from the following group that forms: lanthanum (La), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
8. conducting metal constituent as claimed in claim 6, it is characterized in that, this conducting metal constituent more comprises at least one rare earth metal, take the content of copper metal as 100 percentage by weights, the content sum total of this rare earth metal is 0.01 to 0.1 percentage by weight, and this rare earth metal is selected from the following group that forms: lanthanum (La), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
9. conducting metal constituent as claimed in claim 6 is characterized in that, this titanium-containing compound is barium titanate.
10. such as arbitrary described conducting metal constituent in the claim 6 to 9, it is characterized in that, further comprise resin binder and organic solvent.
11. a conductive electrode is characterized in that, is made such as arbitrary described conducting metal constituent institute sintering in the claim 1 to 10 by a kind of.
12. a monolithic ceramic capacitor is characterized in that, comprising:
One ceramic sintered bodies, this ceramic sintered bodies comprises up and down sequentially one of overlapping setting the first dielectric layer, one first conductive electrode layer, one second dielectric layer and one second conductive electrode layer, wherein, this first conductive electrode layer and a kind of conductive electrode as claimed in claim 11 of these the second conductive electrode series of strata;
One first outer electrode be arranged at a side of this ceramic sintered bodies, and this first outer electrode is to be electrically connected this first conductive electrode layer; And
One second outer electrode be arranged at the opposite side of this ceramic sintered bodies, and this second outer electrode is to be electrically connected this second conductive electrode layer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104869767A (en) * | 2014-02-26 | 2015-08-26 | 深圳富泰宏精密工业有限公司 | Machine shell and portable electronic device with application of shell |
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| CN1411003A (en) * | 2001-10-05 | 2003-04-16 | 株式会社村田制作所 | Conducting paste, laminated ceramic electronic device mfg. method and laminated ceramic electronic device |
| CN1571855A (en) * | 2001-10-18 | 2005-01-26 | 加拿大电子粉末公司 | Powder for laminated ceramic capacitor internal electrode |
| CN101034600A (en) * | 2006-03-10 | 2007-09-12 | Tdk株式会社 | Ceramic powder, electroconductive paste, multilayer ceramic electronic component, and method for production thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1411003A (en) * | 2001-10-05 | 2003-04-16 | 株式会社村田制作所 | Conducting paste, laminated ceramic electronic device mfg. method and laminated ceramic electronic device |
| CN1571855A (en) * | 2001-10-18 | 2005-01-26 | 加拿大电子粉末公司 | Powder for laminated ceramic capacitor internal electrode |
| CN101034600A (en) * | 2006-03-10 | 2007-09-12 | Tdk株式会社 | Ceramic powder, electroconductive paste, multilayer ceramic electronic component, and method for production thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104869767A (en) * | 2014-02-26 | 2015-08-26 | 深圳富泰宏精密工业有限公司 | Machine shell and portable electronic device with application of shell |
| CN104869767B (en) * | 2014-02-26 | 2019-01-25 | 深圳富泰宏精密工业有限公司 | The portable electronic device of casing and the application casing |
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Application publication date: 20130501 |