CN102105954B - Multilayer electronic component - Google Patents
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- CN102105954B CN102105954B CN201080002204.9A CN201080002204A CN102105954B CN 102105954 B CN102105954 B CN 102105954B CN 201080002204 A CN201080002204 A CN 201080002204A CN 102105954 B CN102105954 B CN 102105954B
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- 239000002184 metal Substances 0.000 claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 229910018054 Ni-Cu Inorganic materials 0.000 claims abstract description 25
- 229910018481 Ni—Cu Inorganic materials 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 abstract description 46
- 239000010410 layer Substances 0.000 description 58
- 238000012360 testing method Methods 0.000 description 58
- 238000007747 plating Methods 0.000 description 18
- 239000011148 porous material Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000011159 matrix material Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000003985 ceramic capacitor Substances 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 230000004523 agglutinating effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000007581 slurry coating method Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000039 congener Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
- H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Provided is a multilayer electronic component which has: a ceramic element body (1) wherein an internal electrode (2) having Ni as the main component is embedded; and external electrodes (3a, 3b) which are formed on the both end portions of the ceramic element body (1) and are electrically connected with the internal electrode (2). The external electrodes (3a, 3b) respectively have double layer structures composed of first metal layers (4a, 4b), which are brought into contact with the ceramic element body (1), and second metal layers (5a, 5b) formed on the surfaces of the first metal layers (4a, 4b), and the external electrodes are formed by sintering after the ceramic element body (1) is formed. The first metal layers (4a, 4b) contain at least Ni, and second metal layers (5a, 5b) are formed of Cu. The first metal layers (4a, 4b) are formed of either Ni or a Ni-Cu alloy, and contain 80 atm% or less (including 0 atm%) of Cu, preferably 10-50 atm% of Cu. Thus, in the multilayer electronic component, protrusion of the internal electrode to the sides of the external electrodes is suppressed and the external electrodes having a high density are provided.
Description
Technical field
The present invention relates to the laminated electronic component of laminated ceramic capacitor etc.
Background technology
At present, the laminated electronic component of laminated ceramic capacitor using ceramic sintered bodies as part base solid etc. is well-known.
This laminated electronic component, internal electrode is embedded in part base solid.And, on the surface of this part base solid, be formed with outer electrode.In addition, as internal electrode material, consider cost aspect, preferably use base metal material, and the Ni that applicable high temperature burns till is widely used.
On the other hand, as the formation method of outer electrode, have pair sheet bury the original multilayered ceramic body of internal electrode material and method that outer electrode Cai Liao Tong Time burns till underground and after forming ceramic sintered bodies to be part base solid at the surface of part base solid coating outer electrode material and fire, the method for sintering.
For example, in patent documentation 1, motion has external electrode layer by forming take of forming in the interior electrode layer consisting of the Ni the first metal layer that Ni is principal component and being formed at the laminated ceramic capacitor that the second metal level that Cu is principal component forms of take on described the first metal layer.
In this patent documentation 1, the first metal layer of outer electrode and multilayered ceramic body are burnt till simultaneously, firing temperature uprises, and therefore, as the first metal layer, uses and take the material that the high Ni of melting point is principal component.And then, by take with the good Cu of the adaptation of Ni be principal component, the second metal level is fired and is formed on the first metal layer.
In addition, in patent documentation 2, motion has, by the average grain diameter that contains 70 % by weight～95 % by weight, be the Ni powder of 0.1 μ m～4.0 μ m, and the average grain diameter that contains 5 % by weight～30 % by weight is the laminated ceramic electronic part that the metal dust of the Cu powder of 1.0 μ m～20.0 μ m forms outer electrode.
In this patent documentation 2, in formation, be embedded with after the ceramic sintered bodies of internal electrode, fire outer electrode and form, therefore, preferably in the mode electrical characteristic not being impacted, carry out burning till under low temperature.Therefore, as outer electrode material, use that contain can be at the Ni-Cu of low sintering Cu alloy, thus, and internal electrode between obtain good connectivity.
Patent documentation 1: Unexamined Patent 06-84693 communique
Patent documentation 2: JP 2003-123535 communique
Summary of the invention
Invent technical problem to be solved
But, in patent documentation 1, internal electrode material and raw multilayered ceramic body and the first metal layer material are burnt till simultaneously and be integrally formed, therefore, the control of the firing atmosphere of partial pressure of oxygen etc. and temperature conditions etc. is numerous and diverse.And, because needs at high temperature burn till, so can not contain the such low melting point material of glass ingredient.That is,, because the glass ingredient of realization as the effect of flux can not be contained in the first metal layer, so the bonding force of the ceramic matrix after sintering and the first metal layer weakens, for example when mounting electronic parts, a part for possibility outer electrode can be peeled off.In addition, as above-mentioned, owing to can not comprising glass ingredient, so easily externally in the film of electrode and the generation of interfaces pore of ceramic matrix, therefore, there is the poor problem points of moisture-proof.
On the other hand, in patent documentation 2, after formation sintered body is ceramic matrix, coating outer electrode material and carry out sintering and form outer electrode, still, because outer electrode is the single layer structure of the Ni that contains high melting point, so agglutinating property is poor, be difficult to form fine and close electrode film.And, exist when outer electrode shortcoming compactness, after plating operation in plating solution immersion ceramic matrix, cause the problem points of reliability reduction.That is, for example, when when electrolysis plating, plating solution immerses in outer electrode, in the situation that scolding tin is installed these laminated electronic components, the plating solution of immersion seethes with excitement suddenly, may produce the unfavorable condition that scolding tin disperses and so on.
The present invention foundes in view of such situation, and its object is, provides that a kind of can to suppress internal electrode side-prominent to outer electrode, and possesses the laminated electronic component of the good outer electrode of compactness.
The technical scheme of technical solution problem
For achieving the above object, the invention provides a kind of laminated electronic component, its have be embedded with take the internal electrode that Ni is principal component sintered body and be formed at the surface of this sintered body the outer electrode being electrically connected to described internal electrode, it is characterized in that, described outer electrode has by the first metal layer joining with described sintered body and is formed at the two-layer structure that the second surperficial metal level of this first metal layer forms, and after forming described sintered body, carrying out sintering forms, described the first metal layer at least contains Ni, and described the second metal level is formed by Cu.
In addition, laminated electronic component of the present invention, is characterized in that, described the first metal layer the either party in Ni and Ni-Cu alloy form, and the content of Cu is 80 atom % following (comprising 0 atom %).
In addition, laminated electronic component is characterised in that, described the first metal layer is formed by Ni-Cu alloy, and the content of Cu is below 10～50 atom %.
Technique effect
According to described laminated electronic component, it has to be embedded with take the sintered body of the internal electrode that Ni is principal component, with the outer electrode that is formed at the surperficial of this sintered body and is electrically connected to described internal electrode, wherein, described outer electrode has by the first metal layer joining with described sintered body and is formed at the two-layer structure that the second surperficial metal level of this first metal layer forms, and after forming described sintered body, carrying out sintering forms, described the first metal layer at least contains Ni, described the second metal level is formed by Cu, therefore, internal electrode can be suppressed side-prominent to outer electrode, and can be suppressed at the inner pore that produces of outer electrode, thus, can make the compactness of outer electrode improve.
And, like this, owing to can suppressing outstanding to outer electrode side of internal electrode, so can avoid outer electrode to float from sintered body, can guarantee the reliability of laminated electronic component.In addition, due to the compactness raising of outer electrode, so can be suppressed at the inner pore that occurs of this outer electrode, therefore, even if carry out the plating such as electrolysis plating in rear operation, process, with respect to the sealing of plating solution, also can improve, can avoid plating solution to immerse outer electrode inner.
In addition, any in Ni and Ni-Cu alloy of described the first metal layer forms, and the content of Cu is 80 atom % following (comprising 0 atom %), therefore, can easily realize above-mentioned action effect.
In addition, described the first metal layer is formed by Ni-Cu alloy, and the content of Cu is below 10～50 atom %, therefore, the Cu that melting point is lower than Ni is also contained in the first metal layer in right amount, can suppress outstanding to outer electrode of internal electrode, and can further be suppressed at and in The the first metal layer, produce pore, the outstanding and membranous compactness of the internal electrode that can effectively get both.
Accompanying drawing explanation
Fig. 1 means the profile as an execution mode of the laminated ceramic capacitor of laminated electronic component of the present invention;
Fig. 2 is the figure that explanation the first metal layer has been used the problem points in the situation of Cu;
Fig. 3 is only formed the profile of the outer electrode in the situation of the first metal layer by Ni.
Embodiment
Secondly, describe embodiments of the present invention in detail.
Fig. 1 means the profile as an execution mode of the laminated ceramic capacitor of laminated electronic component of the present invention.
This laminated ceramic capacitor has outer electrode 3a, the 3b of take ceramic matrix (sintered body) 1 that the ceramic materials such as barium titanate are principal component and being formed at the both ends of this ceramic matrix 1, is embedded with to take the internal electrode 2 (2a～2f) that Ni is principal component in this ceramic matrix 1.
And, the two-layer structure that surperficial the second metal level 5a, the 5b that outer electrode 3a, 3b serve as reasons the first metal layer 4a, the 4b that join with ceramic matrix 1 and be formed at this first metal layer 4a, 4b forms, and these outer electrodes 3a, 3b form by carry out sintering after forming ceramic matrix 1.
Like this, after forming ceramic matrix 1, carry out sintering and form, therefore, can avoid the control of firing atmosphere and temperature conditions complicated.But, comparing the situation of simultaneously burning till with original ceramic matrix, can burn till at low temperatures, can use the conductive paste that contains glass ingredient (frit).And, thus, can make at ceramic matrix 2 strongly with the bonding force at the interface of outer electrode 3a, 3b, can guarantee reliability.
The first metal layer 4a, 4b comprise with the congener metal kind of internal electrode 2 and at least comprise Ni.
Like this, in the first metal layer 4a, 4b, at least comprising Ni is because following reason.
At present, in the situation that will be as the general Cu of outer electrode 3a, 3b for the first metal layer 4a, 4b, Cu be because the diffusion velocity in sintering process is larger than Ni, thus Cu to Ni side, be that the diffusion of internal electrode 2 sides is promoted.Therefore, as shown in Figure 2, likely internal electrode 2 is given prominence to and formation protuberance 6 in the first metal layer 4a, 4b, between the first metal layer 4a, 4b and ceramic matrix 2, forms gap 7.And the first metal layer 4a, 4b ( outer electrode 3a, 3b) float from ceramic matrix 2, or crack 8 on ceramic matrix 2, may cause reliability to reduce.
Therefore, in the present embodiment, it is Ni that the first metal layer 4a, 4b at least comprise with the congener metal of internal electrode material.Particularly, any forms in Ni and Ni-Cu alloy for the first metal layer 4a, 4b, and the content of Cu is preferably 80 atom % following (comprising 0 atom %).
On the other hand, the second metal level 5a, 5b are because needs are guaranteed good compactness, so form with the Cu of agglutinating property excellence.
That is, conventionally, from the viewpoint of guaranteeing that thermal endurance and scolding tin are wetting, extensively carry out, after forming outer electrode 3a, 3b, carry out the platings such as electrolysis plating and process, externally the surface of electrode 3a, 3b forms the plating epitheliums such as Ni, Ag, Au and Sn, scolding tin.
But, when the compactness of outer electrode 3a, 3b is poor and during its inner formation pore, externally immerse plating solution in electrode 3a, 3b during plating.For example, and consequently, when scolding tin is installed laminated ceramic capacitor, the plating solution of immersion seethes with excitement suddenly, scolding tin may disperse.Therefore the mode that, at least the surface of outer electrode 3a, 3b need to can not be immersed with plating solution forms densely.
So, in the present embodiment, can burn till at low temperatures, by the good Cu of agglutinating property, form the second metal level 5a, 5b.
Like this, by the metal kind by containing Ni (gold belong to Seed), form the first metal layer 4a, 4b, can suppress outstanding to outer electrode 3a, 3b of internal electrode 2, by formed the second metal level 5a, 5b by Cu, can guarantee compactness.
In addition, the present invention preferably further contains the Cu of 10～50 atom % in the first metal layer 4a, 4b.
Because the first metal layer 4a, 4b contain Ni, thereby can suppress the outstanding of internal electrode, but because Ni is high melting point material, agglutinating property is poor, therefore, if Ni amount causes compactness to reduce at most.
; because the second metal level 5a, 5b are formed by Cu, so the compactness of this second metal level 5a, 5b is good, but in the first metal layer 4a, 4b containing the Cu in the situation that; as shown in Figure 3, the first metal layer 4a, 4b may be at the interface formation pores 9 with the second metal level 5a, 5b.As above-mentioned, because the compactness of the second metal level 5a, 5b is good, so although think that above-mentioned pore 9 is conventionally on not impact of electrical characteristic, when contingency is when in plating engineering, plating solution immerses this pore 9, can cruelly split or moisture-proof reduction by generation scolding tin, may damage reliability.Therefore,, in the first metal layer 4a, 4b, preferably suppress the generation of pore 9 with doing one's utmost.That is, in the first metal layer 4a, 4b, also contain the Cu that agglutinating property is good, thus, be preferably suppressed at the interface formation pore 9 of the first metal layer 5a, 5b.
And, for obtaining such action effect, need to make the content of Cu be at least 10 atom %.On the other hand, when the content of Cu surpasses 50 atom %, the content of Ni reduces relatively, may encourage the outstanding of internal electrode.
So, as above-mentioned, the Cu that preferably contains 10～50 atom % in the first metal layer 4a, 4b.
In addition, the invention is not restricted to above-mentioned execution mode.In the above-described embodiment, as laminated electronic component example ceramic electronic component, but also go for other laminated electronic component, such as laminated piezoelectric part, cascade type ferrite part, LC compound circuit and electronic chip components etc.
In addition, in the above-described embodiment, by the mixing of Ni powder and Cu powder, make Ni-Cu alloy, even but directly use Ni-Cu alloy powder, also can access same effect, much less this be.In addition, each thickness of the first metal layer 4a, 4b and the second metal level 5a, 5b can be selected arbitrarily conventionally in the scope of 5～50 μ m that set, the film thickness ratio of the first metal layer 4a, 4b and the second metal level 5a, 5b is also not particularly limited, and can change arbitrarily.
Embodiment
Secondly, embodiments of the invention are specifically described.
(making of ceramic sintered bodies)
First, as ceramic matrix, weigh the BaCO of ormal weight
3and TiO
2, secondly, these weighing things and PSZ (partially stabilized zirconia) ball and pure water together being dropped into ball mill, the abundant co-grinding of wet type, is dried it and obtains mixed-powder.
Secondly, by this mixed-powder in atmosphere, with the temperature pre-burnings of 950 ℃ 2 hours, dry type is pulverized afterwards, makes with BaTiO
3ceramic material powder for principal component.
Secondly, take ethanol as solvent, adding polyvinyl butyral resin is adhesive, by this ceramic material powder co-grinding, obtains ceramic size.And, use and scrape the skill in using a kitchen knife in cookery, above-mentioned ceramic size is implemented to the processing that is shaped, obtain ceramic green sheet.
Secondly, by take internal electrode that Ni is principal component with conductive paste screen printing in the surface of ceramic green sheet, form the conducting film of predetermined pattern.Secondly, the ceramic green sheet that is formed with this conducting film is stacked along prescribed direction, by the ceramic green sheet clamping the crimping that do not form conducting film, make multilayered ceramic body.
Secondly, this multilayered ceramic body is cut to after plate shape, in blanket of nitrogen, be heated to the temperature of 500 ℃, adhesive is removed in burning, afterwards, and by H
2-N
2-H
2under the reducing atmosphere that O gas forms, burn till 2 hours with the temperature of 1200 ℃, obtain the ceramic sintered bodies of test piece number (Test pc No.) 1～10.
In these ceramic sintered bodies, by ceramic layer and interior electrode layer interaction cascading, and the end face of internal electrode is at the end face of different ceramic sintered bodies exposing surface alternatively.And its profile cun method is for long: 1mm, wide: 0.5mm, thick: 0.5mm.
(making of outer electrode)
(test piece number (Test pc No.) 1)
Making is by Ni powder: 65 % by weight, B-Si-Ba-O are frit: 6 % by weight, acrylic resin: 5 % by weight and vehicle: the Ni slurry that 24 % by weight form.In addition, as vehicle, use the material that 3-methyl-3-methoxyl group-n-butyl alcohol and terpineol are mixed.
Secondly, above-mentioned Ni slurry coating, in the both ends of ceramic sintered bodies, is dried to 10 minutes at the temperature of 150 ℃, forms Ni film.
Secondly, prepare to replace Ni powder and use the Cu slurry with the Cu powder of amount.And, Cu slurry coating, on Ni film, is dried to 10 minutes with the temperature of 150 ℃, form Cu film.
Secondly, the ceramic sintered bodies that is formed with like this Ni film and Cu film is dropped into batch furnace, with firing time 30 minutes, 850 ℃ of maximum sintering temperatures, the sintering curve of 10 minutes retention times, burn till, formation, by the outer electrode of Ni electrode (the first metal layer) and this two-layer structure formation of Cu electrode (the second metal level), obtains the sample of test piece number (Test pc No.) 1.
In addition, for the thickness of outer electrode, Ni electrode is that 20 μ m, Cu electrode are 20 μ m.
In addition, the control of firing atmosphere is passed through to N
2in reduction, oxidizing gas interpolation and carry out, from room temperature to maximum sintering temperature by adding H
2/ H
2o, adds air and carries out at maximum sintering temperature.
(test piece number (Test pc No.) 2～6)
90/10,70/30,50/50,40/60,20/80 the mode of being respectively with the atom ratio Ni/Cu of Ni powder and Cu powder weighs Ni powder and Cu powder, obtains Ni-Cu mixed-powder.And, make by Ni-Cu mixed-powder: 65 % by weight, B-Si-Ba-O are frit: 6 % by weight, acrylic resin: 5 % by weight and vehicle: the Ni-Cu slurry that 24 % by weight form.
Afterwards, by the method identical with test piece number (Test pc No.) 1, order, form the outer electrode being formed by Ni-Cu electrode (the first metal layer) and this two-layer structure of Cu electrode (the second metal level), obtain the sample of test piece number (Test pc No.) 2～6.
In addition, for the thickness of outer electrode, Ni-Cu electrode is that 20 μ m, Cu electrode are 20 μ m.
(test piece number (Test pc No.) 7)
The Ni slurry coating made from test piece number (Test pc No.) 1, in the both ends of ceramic sintered bodies, is dried to 10 minutes with the temperature of 150 ℃, forms Ni film.And, then with the method identical with test piece number (Test pc No.) 1, order, form the outer electrode of the single layer structure formed by Ni electrode, obtain the sample of test piece number (Test pc No.) 7.
In addition, the thickness of outer electrode is made as 40 μ m, with the total film thickness of the outer electrode of the test piece number (Test pc No.) 1～6 with two-layer structure, equates.
(test piece number (Test pc No.) 8,9)
50/50,20/80 the mode of being respectively with the atom ratio Ni/Cu of Ni powder and Cu powder weighs Ni powder and Cu powder, obtains Ni-Cu mixed-powder.And, make by Ni-Cu mixed-powder: 65 % by weight, B-Si-Ba-O are frit: 6 % by weight, acrylic resin: 5 % by weight and vehicle: the Ni-Cu slurry that 24 % by weight form.
And, then, to form the outer electrode of the single layer structure being formed by Ni-Cu electrode with the same method of test piece number (Test pc No.) 1, order, obtain the sample of test piece number (Test pc No.) 8,9.
In addition, for the thickness of outer electrode, identical with test piece number (Test pc No.) 7, be 40 μ m.
(test piece number (Test pc No.) 10)
The Cu slurry coating made from test piece number (Test pc No.) 1, in the both ends of ceramic sintered bodies, is dried to 10 minutes with the temperature of 150 ℃, forms Cu film.And, then, to form the outer electrode of the single layer structure being formed by Cu electrode with the same method of test piece number (Test pc No.) 1, order, obtain the sample of test piece number (Test pc No.) 10.
In addition, for the thickness of outer electrode, identical with test piece number (Test pc No.) 7, be 40 μ m.
(evaluation of sample)
For each sample of test piece number (Test pc No.) 1～10, with SEM (scanning electron microscope) photographic images, carry out image analysis, measure the overhang of internal electrode.And, for overhang, will be made as good (◎) less than 0.5 μ m, 0.5～1.0 μ m is made as can (zero), the situation that surpasses 1.0 μ m is made as can not (*), carries out overhang evaluation.
In addition, for the test piece number (Test pc No.) 1～6 of two-layer structure, according to the image analysis of SEM image, obtain the aperture at the pore at Ni electrode or Ni-Cu electrode and interface Cu electrode.For aperture, will be made as good (◎) less than 0.5 μ m, 0.5～1.0 μ m is made as can (zero), the situation that surpasses 1.0 μ m is made as can not (*), carries out compactness evaluation.
In addition,, for the test piece number (Test pc No.) 7～10 of single layer structure, according to the image analysis of SEM image, obtain pore incidence.And, for pore incidence, will less than 10% be made as good (◎), by 10～15% be made as can (zero), the situation that surpasses 15% is made as can not (*), carries out compactness evaluation.
In addition, each is measured and respectively 10 samples is carried out, and by mean value, evaluates each characteristic.
Table 1 represents formation and the measurement result of the outer electrode of each sample.In table 1, compactness evaluation (1) represents the measurement result of the first metal layer of the present invention (Ni electrode or Ni-Cu electrode), and compactness evaluation (2) is illustrated in the result of the Ni-Cu electrode of the single layer structure outside the scope of the invention.
[table 1]
*outside the scope of the invention
In test piece number (Test pc No.) 7,8, outer electrode is single layer structure, contains more than 50% and Ni internal electrode same material, and therefore, the overhang of internal electrode be take less than 0.5 μ m as good, but pore incidence is that more than 15% compactness is poor, and synthetic determination is bad.This thinks, because the principal component of outer electrode is that Ni is high melting point material, so agglutinating property is poor, can not form fine and close outer electrode.
In addition, in test piece number (Test pc No.) 9, the content of the Ni in metal material is 20%, less, and therefore, the overhang of internal electrode is 0.5～1.0 μ m slightly greatly.And due to the reason identical with test piece number (Test pc No.) 7,8, pore incidence is that more than 15% compactness is poor, synthetic determination is bad.
In test piece number (Test pc No.) 10, owing to forming separately outer electrode by Cu, so during pore incidence less than 10%, compactness is good, but the overhang of internal electrode surpasses 1.0 μ m, and synthetic determination is bad.This thinks, is forming the Cu of outer electrode and is forming in the Ni of internal electrode, and the diffusion velocity of Cu is larger than the diffusion velocity of Ni, therefore, has promoted the diffusion of Cu from outer electrode side direction internal electrode side, and consequently internal electrode is the overhang increase of Ni.
In contrast, in test piece number (Test pc No.) 1～6, owing to being formed with Cu electrode on Ni electrode or Ni-Cu electrode, so internal electrode is outstanding suppressed, meanwhile, the pore incidence at the interface of Ni electrode or Ni-Cu electrode and Cu electrode also reduces, and obtains good result.Each sample of the test piece number (Test pc No.) 2～4 that particularly atom ratio of Ni and Cu is 90/10～50/50, the overhang of internal electrode and pore incidence are also extremely good, obtain preferred result.
Utilizability in industry
In laminated electronic component, the compactness of the inhibition of the overhang of the internal electrode that can simultaneously get both and outer electrode, contributes to the reliability of this laminated electronic component to improve.
Symbol description
1 ceramic matrix (sintered body)
2a～2f internal electrode
3a, 3b outer electrode
4a, 4b the first metal layer
5a, 5b the second metal level
Claims (3)
1. a laminated electronic component, its have be embedded with take the internal electrode that Ni is principal component sintered body and be formed at the surface of this sintered body the outer electrode being electrically connected to described internal electrode, it is characterized in that,
Described outer electrode has by the first metal layer joining with described sintered body and is formed at the two-layer structure that the second surperficial metal level of this first metal layer forms, and after forming described sintered body, carries out sintering and form,
Described the first metal layer at least contains Ni, and described the second metal level is formed by Cu.
2. laminated electronic component as claimed in claim 1, is characterized in that, described the first metal layer the either party in Ni and Ni-Cu alloy form, and the content of Cu is below 80 atom % and comprises 0 atom %.
3. laminated electronic component as claimed in claim 1, is characterized in that, described the first metal layer is formed by Ni-Cu alloy, and the content of Cu is 10～50 atom %.
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| JP2009-016788 | 2009-01-28 | ||
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| PCT/JP2010/050157 WO2010087221A1 (en) | 2009-01-28 | 2010-01-08 | Multilayer electronic component |
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| JP5998785B2 (en) * | 2012-09-19 | 2016-09-28 | Tdk株式会社 | Laminated electronic components |
| KR20140046301A (en) * | 2012-10-10 | 2014-04-18 | 삼성전기주식회사 | Multi-layered ceramic electronic parts and method of manufacturing the same |
| KR101444536B1 (en) * | 2012-10-18 | 2014-09-24 | 삼성전기주식회사 | Multi-Layered Ceramic Electronic Component And Manufacturing Method Thereof |
| KR101508541B1 (en) | 2013-08-09 | 2015-04-07 | 삼성전기주식회사 | Embedded multilayer ceramic electronic part and print circuit board having embedded multilayer ceramic electronic part |
| KR20160125121A (en) * | 2015-04-21 | 2016-10-31 | 삼성전기주식회사 | Multi-layered ceramic capacitor and manufacturing method the same |
| KR102293032B1 (en) * | 2015-04-21 | 2021-08-24 | 삼성전기주식회사 | Multi-layered ceramic capacitor and manufacturing method the same |
| JP6558083B2 (en) * | 2015-06-05 | 2019-08-14 | 株式会社村田製作所 | Multilayer ceramic capacitor and method for manufacturing multilayer ceramic capacitor |
| JP6558084B2 (en) * | 2015-06-05 | 2019-08-14 | 株式会社村田製作所 | Multilayer ceramic capacitor and method for manufacturing multilayer ceramic capacitor |
| JP2017162956A (en) | 2016-03-09 | 2017-09-14 | 株式会社村田製作所 | Electronic component and manufacturing method for the same |
| JP7046679B2 (en) * | 2018-03-30 | 2022-04-04 | Ｊｘ金属株式会社 | External electrodes of ceramic laminate |
| JP7081543B2 (en) * | 2019-03-22 | 2022-06-07 | 株式会社村田製作所 | Multilayer ceramic capacitors |
| US11715602B2 (en) * | 2019-08-02 | 2023-08-01 | Samsung Electro-Mechanics Co., Ltd. | Multilayer electronic component |
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| JP5099609B2 (en) | 2012-12-19 |
| CN102105954A (en) | 2011-06-22 |
| WO2010087221A1 (en) | 2010-08-05 |
| JPWO2010087221A1 (en) | 2012-08-02 |
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