WO2010087221A1 - Composant électronique multicouche - Google Patents

Composant électronique multicouche Download PDF

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Publication number
WO2010087221A1
WO2010087221A1 PCT/JP2010/050157 JP2010050157W WO2010087221A1 WO 2010087221 A1 WO2010087221 A1 WO 2010087221A1 JP 2010050157 W JP2010050157 W JP 2010050157W WO 2010087221 A1 WO2010087221 A1 WO 2010087221A1
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electrode
metal layers
metal layer
electronic component
ceramic
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PCT/JP2010/050157
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English (en)
Japanese (ja)
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才規 永元
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株式会社 村田製作所
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Priority to CN201080002204.9A priority Critical patent/CN102105954B/zh
Priority to JP2010548455A priority patent/JP5099609B2/ja
Publication of WO2010087221A1 publication Critical patent/WO2010087221A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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

Definitions

  • the present invention relates to a multilayer electronic component such as a multilayer ceramic capacitor.
  • the internal electrode is embedded in the component element body, and the external electrode is formed on the surface of the component element body. Further, as the internal electrode material, it is desirable to use a base metal material in consideration of cost, and Ni suitable for high-temperature firing is actively used.
  • the external electrode after the raw ceramic laminate having the internal electrode material embedded in a sheet shape and the external electrode material are simultaneously fired, and after the component body that is a ceramic sintered body is formed There is a method in which an external electrode material is applied to the surface of a component body, and is baked and sintered.
  • the external electrode layer includes a first metal layer mainly composed of Ni formed simultaneously with an internal electrode layer made of Ni, and Cu formed on the first metal layer.
  • a multilayer ceramic capacitor composed of a second metal layer as a main component has been proposed.
  • the first metal layer of the external electrode is simultaneously fired with the ceramic laminate, and the firing temperature is also high, the first metal layer is a material mainly composed of Ni having a high melting point. Is used. Thereafter, a second metal layer mainly composed of Cu having good adhesion to Ni is baked and formed on the first metal layer.
  • Patent Document 2 includes 70 wt% to 95 wt% of Ni powder having an average particle diameter of 0.1 ⁇ m to 4.0 ⁇ m and 5 wt% of Cu powder having an average particle diameter of 1.0 ⁇ m to 20.0 ⁇ m. There has been proposed a multilayer ceramic electronic component in which external electrodes are formed of metal powder containing from 30% to 30% by weight.
  • Patent Document 1 since the internal electrode material and the raw ceramic laminate and the first metal layer material are integrally fired and integrally formed, control of the firing atmosphere such as oxygen partial pressure and temperature conditions is controlled. Is complicated. Moreover, since firing at a high temperature is required, a low melting point material such as a glass component cannot be included. That is, since the glass component that acts as a fusing agent cannot be included in the first metal layer, the adhesion between the sintered ceramic body and the first metal layer is weak, for example, an electronic component There is a possibility that a part of the external electrode may be peeled off during mounting. Furthermore, as described above, since a glass component cannot be included, pores are likely to be generated in the film of the external electrode or at the interface of the ceramic body, so that there is a problem of poor moisture resistance.
  • Patent Document 2 after forming a ceramic body that is a sintered body, an external electrode material is applied and sintered to form an external electrode.
  • the external electrode contains Ni having a high melting point. Therefore, the sinterability is inferior, and it is difficult to form a dense electrode film. If the external electrode lacks denseness, there is a problem in that the plating solution enters the ceramic body in the subsequent plating step, leading to a decrease in reliability. That is, for example, when the plating solution enters the external electrode during electrolytic plating, there is a risk that when these multilayer electronic components are solder-mounted, the invaded plating solution bumps and the solder scatters.
  • the present invention has been made in view of such circumstances, and can provide a multilayer electronic component including an external electrode with good internal density that can suppress the internal electrode from protruding toward the external electrode. Objective.
  • a multilayer electronic component includes a sintered body in which an internal electrode mainly composed of Ni is embedded, and is formed on the surface of the sintered body to electrically connect to the internal electrode.
  • the external electrode includes a first metal layer in contact with the sintered body, and a second metal layer formed on the surface of the first metal layer.
  • the first metal layer contains at least Ni
  • the second metal layer is made of Cu, and is sintered after the sintered body is formed. It is characterized by being.
  • the first metal layer is formed of one of Ni and a Ni—Cu alloy, and the content of Cu is 80 atomic% or less (less than 0 atomic%). Is included).).
  • the multilayer electronic component is characterized in that the first metal layer is formed of a Ni—Cu alloy and the Cu content is 10 to 50 atomic% or less.
  • the sintered body in which the internal electrode mainly composed of Ni is embedded, and the external electrode formed on the surface of the sintered body and electrically connected to the internal electrode are provided.
  • the external electrode has a two-layer structure including a first metal layer in contact with the sintered body and a second metal layer formed on the surface of the first metal layer. Since the sintered body is formed and sintered, the first metal layer contains at least Ni and the second metal layer is formed of Cu, so that the internal electrode is an external electrode. Protruding to the side can be suppressed, and generation of pores inside the external electrode can be suppressed, thereby improving the denseness of the external electrode.
  • the external electrode can be prevented from floating from the sintered body, and the reliability of the multilayer electronic component can be ensured. Further, since the density of the external electrode is improved, the generation of pores inside the external electrode can be suppressed. Therefore, even if a plating process such as electrolytic plating is performed in a subsequent process, the seal against the plating solution is prevented. Thus, the plating solution can be prevented from entering the external electrode.
  • the first metal layer is formed of one of Ni and a Ni—Cu alloy and has a Cu content of 80 atomic% or less (including 0 atomic%). An effect can be produced easily.
  • the first metal layer is formed of a Ni—Cu alloy and the Cu content is 10 to 50 atomic% or less, Cu having a melting point lower than that of Ni is also present in the first metal layer.
  • An appropriate amount is included, and it is possible to further suppress the generation of pores in the first metal layer while suppressing the protrusion of the internal electrode to the external electrode, effectively reducing the protrusion of the internal electrode and the denseness of the film quality. It is possible to achieve both.
  • 1 is a cross-sectional view showing an embodiment of a multilayer ceramic capacitor as a multilayer electronic component according to the present invention. It is a figure explaining the problem at the time of using Cu for the 1st metal layer. It is sectional drawing of an external electrode at the time of forming a 1st metal layer only with Ni.
  • FIG. 1 is a cross-sectional view showing an embodiment of a multilayer ceramic capacitor as a multilayer electronic component according to the present invention.
  • This multilayer ceramic capacitor has a ceramic body (sintered body) 1 mainly composed of a ceramic material such as barium titanate, and external electrodes 3 a and 3 b formed at both ends of the ceramic body 1.
  • An internal electrode 2 (2a to 2f) containing Ni as a main component is embedded in the ceramic body 1.
  • the external electrodes 3a and 3b are composed of first metal layers 4a and 4b in contact with the ceramic body 1, and second metal layers 5a and 5b formed on the surfaces of the first metal layers 4a and 4b.
  • the external electrodes 3a and 3b are sintered after the ceramic body 1 is formed.
  • the ceramic body 1 Since the ceramic body 1 is thus sintered after being formed, it is possible to avoid complicated control of the firing atmosphere and temperature conditions. Moreover, it can be fired at a lower temperature than the case of simultaneous firing with the raw ceramic body, and a conductive paste containing a glass component (glass frit) can be used. As a result, the fixing force at the interface between the ceramic body 2 and the external electrodes 3a and 3b can be strengthened, and the reliability can be ensured.
  • the first metal layers 4a and 4b contain the same kind of metal as that of the internal electrode 2, that is, at least Ni.
  • the reason why at least Ni is contained in the first metal layers 4a and 4b is as follows.
  • the diffusion rate of Cu in the firing process is higher than that of Ni. Diffusion to the electrode 2 side is promoted. For this reason, as shown in FIG. 2, the internal electrode 2 protrudes into the first metal layers 4 a and 4 b to form a protruding portion 6, and the first metal layers 4 a and 4 b and the ceramic body 2 are interposed. There is a possibility that the gap 7 is formed. Then, the first metal layers 4a, 4b (external electrodes 3a, 3b) may be lifted from the ceramic body 2, or cracks 8 may be generated in the ceramic body 2, leading to a decrease in reliability.
  • the first metal layers 4a and 4b contain at least Ni which is the same kind of metal as the internal electrode material.
  • each of the first metal layers 4a and 4b is formed of one of Ni and a Ni—Cu alloy and has a Cu content of 80 atomic% or less (including 0 atomic%). preferable.
  • the second metal layers 5a and 5b are made of Cu having excellent sinterability because it is necessary to ensure good denseness.
  • plating treatment such as electrolytic plating is performed, and Ni, Ag, Au, Sn, and the like are formed on the surfaces of the external electrodes 3a and 3b.
  • Forming a plating film such as solder is widely performed.
  • the plating solution may enter the external electrodes 3a and 3b during plating.
  • the infiltrated plating solution may bump and the solder may be scattered.
  • the second metal layers 5a and 5b are formed of Cu that can be fired at a low temperature and has good sinterability.
  • the first metal layers 4a and 4b with a metal species containing Ni, the protrusion of the external electrodes 3a and 3b of the internal electrode 2 can be suppressed, and the second metal layers 5a and 5b are formed of Cu. By doing so, denseness can be ensured.
  • the first metal layers 4a and 4b further contain 10 to 50 atomic% of Cu.
  • the protrusion of the internal electrode can be suppressed.
  • Ni is a high melting point material and has poor sinterability, a large amount of Ni causes a decrease in denseness. There is a fear.
  • the second metal layers 5a and 5b are made of Cu, the denseness of the second metal layers 5a and 5b is good, but the first metal layers 4a and 4b contain Cu. Otherwise, as shown in FIG. 3, the first metal layers 4a and 4b may have pores 9 formed at the interfaces with the second metal layers 5a and 5b. As described above, since the denseness of the second metal layers 5a and 5b is good, the pores 9 are considered not to affect the electrical characteristics normally. If the plating solution enters, solder explosion may occur or the moisture resistance may be reduced, and reliability may be impaired. Therefore, it is preferable to suppress the generation of pores 9 in the first metal layers 4a and 4b as much as possible. That is, it is preferable to contain Cu having good sinterability in the first metal layers 4a and 4b, thereby suppressing the formation of pores 9 at the interfaces of the first metal layers 5a and 5b.
  • the Cu content needs to be at least 10 atomic%.
  • the content of Cu exceeds 50 atomic%, the content of Ni is relatively lowered, so that the protrusion of the internal electrode may be promoted.
  • the first metal layers 4a and 4b preferably contain 10 to 50 atomic% of Cu.
  • the present invention is not limited to the above embodiment.
  • the ceramic electronic component is exemplified as the multilayer electronic component.
  • the present invention can also be applied to other multilayer electronic components such as multilayer piezoelectric components, multilayer ferrite components, LC composite circuits, and chip electronic components. It is.
  • the Ni—Cu alloy is produced by mixing Ni powder and Cu powder, but it goes without saying that the same effect can be obtained by using Ni—Cu alloy powder directly.
  • the thickness of each of the first metal layers 4a and 4b and the second metal layers 5a and 5b can usually be arbitrarily selected within a set range of 5 to 50 ⁇ m, and the first metal layer 4a
  • the film thickness ratio between 4b and the second metal layers 5a and 5b is not particularly limited, and can be arbitrarily changed.
  • the mixed powder was calcined in the atmosphere at a temperature of 950 ° C. for 2 hours, and then pulverized in a dry manner to produce a ceramic raw material powder containing BaTiO 3 as a main component.
  • this ceramic raw material powder was mixed and pulverized by using ethanol as a solvent and adding a polyvinyl butyral binder to obtain a ceramic slurry. Then, the ceramic slurry was molded using a doctor blade method to obtain a ceramic green sheet.
  • a conductive paste for internal electrodes mainly composed of Ni was screen-printed on the surface of the ceramic green sheet to form a conductive film having a predetermined pattern.
  • the ceramic green sheets on which the conductive film was formed were laminated in a predetermined direction, sandwiched between the ceramic green sheets on which the conductive film was not formed, and pressed to produce a ceramic laminate.
  • this ceramic laminate is cut into chips, and then heated to a temperature of 500 ° C. in a nitrogen atmosphere to burn and remove the binder, and then a reducing atmosphere composed of H 2 —N 2 —H 2 O gas. Thereafter, firing was performed at a temperature of 1200 ° C. for 2 hours, and ceramic sintered bodies of sample numbers 1 to 10 were obtained.
  • ceramic layers and internal electrode layers are alternately laminated, and the end faces of the internal electrodes are alternately exposed on the end faces of different ceramic sintered bodies.
  • the external dimensions were 1 mm in length, 0.5 mm in width, and 0.5 mm in thickness.
  • Example No. 1 A Ni paste consisting of Ni powder: 65% by weight, B—Si—Ba—O glass frit: 6% by weight, acrylic resin: 5% by weight, and organic vehicle: 24% by weight was prepared.
  • organic vehicle a mixture of 3-methyl-3-methoxy-1-butanol and terpineol was used.
  • the Ni paste was applied to both ends of the ceramic sintered body and dried at a temperature of 150 ° C. for 10 minutes to form a Ni film.
  • the ceramic sintered body in which the Ni film and the Cu film are formed in this manner is put into a batch furnace and fired with a firing profile of 30 minutes, a maximum firing temperature of 850 ° C., and a holding time of 10 minutes, An external electrode having a two-layer structure of a Ni electrode (first metal layer) and a Cu electrode (second metal layer) was formed, and a sample No. 1 was obtained.
  • the film thickness of the external electrode was 20 ⁇ m for the Ni electrode and 20 ⁇ m for the Cu electrode.
  • the firing atmosphere was controlled by reduction into N 2 and the addition of an oxidizing gas. From room temperature to the highest firing temperature, H 2 / H 2 O was added, and at the highest firing temperature, air was added.
  • Ni powder and Cu powder are weighed so that the atomic ratio Ni / Cu of Ni powder and Cu powder is 90/10, 70/30, 50/50, 40/60, and 20/80, respectively, and Ni-Cu mixed A powder was obtained.
  • a Ni—Cu paste comprising Ni—Cu mixed powder: 65 wt%, B—Si—Ba—O glass frit: 6 wt%, acrylic resin: 5 wt%, and organic vehicle: 24 wt% was prepared. .
  • an external electrode having a two-layer structure of a Ni—Cu electrode (first metal layer) and a Cu electrode (second metal layer) is formed by the same method and procedure as in sample number 1, and sample numbers 2 to Six samples were obtained.
  • the thickness of the external electrode was 20 ⁇ m for the Ni—Cu electrode and 20 ⁇ m for the Cu electrode.
  • Example No. 7 The Ni paste produced in Sample No. 1 was applied to both ends of the ceramic sintered body and dried at a temperature of 150 ° C. for 10 minutes to form a Ni film. Thereafter, an external electrode having a single layer structure made of a Ni electrode was formed by the same method and procedure as in Sample No. 1, and a sample No. 7 was obtained.
  • the thickness of the external electrode was set to 40 ⁇ m so as to be equal to the total thickness of the external electrodes of the sample numbers 1 to 6 having a two-layer structure.
  • Ni powder and Cu powder were weighed so that the atomic ratio Ni / Cu between Ni powder and Cu powder would be 50/50 and 20/80, respectively, to obtain a Ni—Cu mixed powder.
  • a Ni—Cu paste comprising Ni—Cu mixed powder: 65 wt%, B—Si—Ba—O glass frit: 6 wt%, acrylic resin: 5 wt%, and organic vehicle: 24 wt% was prepared. .
  • the film thickness of the external electrode was 40 ⁇ m as in sample number 7.
  • Sample No. 10 The Cu paste prepared in Sample No. 1 was applied to both ends of the ceramic sintered body and dried at a temperature of 150 ° C. for 10 minutes to form a Cu film. Thereafter, a single layer external electrode composed of a Cu electrode was formed by the same method and procedure as in Sample No. 1, and a sample No. 10 was obtained.
  • the film thickness of the external electrode was 40 ⁇ m as in sample number 7.
  • Example evaluation For each of the samples Nos. 1 to 10, images were taken with an SEM (scanning electron microscope), and image analysis was performed to measure the amount of protrusion of the internal electrodes. The protrusion amount was evaluated as good ( ⁇ ) when the protrusion amount was less than 0.5 ⁇ m, acceptable ( ⁇ ) when 0.5 to 1.0 ⁇ m was exceeded, and impossible ( ⁇ ) when the protrusion amount exceeded 1.0 ⁇ m.
  • the pore diameter of the interface between the Ni electrode or Ni—Cu electrode and the Cu electrode was obtained from image analysis of the SEM image. Density evaluation was performed with a pore size of less than 0.5 ⁇ m being good ( ⁇ ), 0.5 to 1.0 ⁇ m being acceptable ( ⁇ ), and exceeding 1.0 ⁇ m being unacceptable ( ⁇ ).
  • the porosity generation rate was determined from image analysis of SEM images. Then, the porosity generation rate was evaluated as dense (less than 10%) (good), 10-15% as acceptable ( ⁇ ), and more than 15% as unacceptable (x).
  • Table 1 shows the configuration of external electrodes and measurement results of each sample.
  • the denseness evaluation (1) shows the measurement results in the first metal layer (Ni electrode or Ni—Cu electrode) of the present invention
  • the denseness evaluation (2) is a single layer outside the scope of the present invention. The measurement result of the structure Ni-Cu electrode is shown.
  • the external electrode has a single layer structure and contains 50% or more of Ni, which is the same material as the internal electrode, so the protruding amount of the internal electrode was good, less than 0.5 ⁇ m.
  • the porosity generation rate was 15% or more and the density was inferior, and the overall judgment was poor. This is probably because Ni, which is the main component of the external electrode, is a high melting point material, so that it has poor sinterability and a dense external electrode could not be formed.
  • Sample Nos. 1 to 6 have the Cu electrode formed on the Ni electrode or Ni—Cu electrode, so that the protrusion of the internal electrode is suppressed, and the Ni electrode or Ni—Cu electrode is the same as the Cu electrode.
  • the porosity generation rate at the interface was low, and good results were obtained.
  • the samples Nos. 2 to 4 having an atomic ratio of Ni and Cu of 90/10 to 50/50 were very good in the protruding amount of the internal electrode and the porosity generation rate, and more preferable results were obtained.

Abstract

L'invention porte sur un composant électronique multicouche qui comprend : un corps d'élément en céramique (1) dans lequel est incorporée une électrode interne (2) contenant du nickel (Ni) en tant que composant principal ; et des électrodes externes (3a, 3b), qui sont formées sur les deux parties d'extrémité du corps d'élément en céramique (1) et électriquement connectées à l'électrode interne (2). Les électrodes externes (3a, 3b) comprennent respectivement des structures à double couche composées de premières couches métalliques (4a, 4b), qui sont amenées en contact avec le corps d'élément en céramique (1), et de deuxièmes couches métalliques (5a, 5b), formées sur les surfaces des premières couches métalliques (4a, 4b), et les électrodes externes sont formées par frittage après formation du corps d'élément en céramique (1). Les premières couches métalliques (4a, 4b) contiennent au moins Ni, et les deuxièmes couches métalliques (5a, 5b) sont faites de cuivre (Cu). Les premières couches métalliques (4a, 4b) sont faites soit de Ni soit d'un alliage Ni-Cu, et contiennent 80 % atomiques ou moins (y compris 0 % atomique) de Cu, de préférence 10 à 50 % atomiques de Cu. Ainsi, dans le composant électronique multicouche, une saillie de l'électrode interne vers les côtés des électrodes externes est supprimée et les électrodes externes obtenues présentent une densité élevée.
PCT/JP2010/050157 2009-01-28 2010-01-08 Composant électronique multicouche WO2010087221A1 (fr)

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CN201080002204.9A CN102105954B (zh) 2009-01-28 2010-01-08 层叠型电子零件
JP2010548455A JP5099609B2 (ja) 2009-01-28 2010-01-08 積層型電子部品

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JP2014060331A (ja) * 2012-09-19 2014-04-03 Tdk Corp 積層電子部品
JP2014078674A (ja) * 2012-10-10 2014-05-01 Samsung Electro-Mechanics Co Ltd 積層セラミック電子部品及びその製造方法
KR101444536B1 (ko) * 2012-10-18 2014-09-24 삼성전기주식회사 적층 세라믹 전자 부품 및 그 제조방법
US20160314902A1 (en) * 2015-04-21 2016-10-27 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic capacitor and method of manufacturing the same
US10418180B2 (en) 2016-03-09 2019-09-17 Murata Manufacturing Co., Ltd. Electronic component and manufacturing method for the same
JP2019179874A (ja) * 2018-03-30 2019-10-17 Ｊｘ金属株式会社 セラミック積層体の外部電極
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JP2014060331A (ja) * 2012-09-19 2014-04-03 Tdk Corp 積層電子部品
JP2014078674A (ja) * 2012-10-10 2014-05-01 Samsung Electro-Mechanics Co Ltd 積層セラミック電子部品及びその製造方法
KR101444536B1 (ko) * 2012-10-18 2014-09-24 삼성전기주식회사 적층 세라믹 전자 부품 및 그 제조방법
US20160314902A1 (en) * 2015-04-21 2016-10-27 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic capacitor and method of manufacturing the same
US10418180B2 (en) 2016-03-09 2019-09-17 Murata Manufacturing Co., Ltd. Electronic component and manufacturing method for the same
JP2019179874A (ja) * 2018-03-30 2019-10-17 Ｊｘ金属株式会社 セラミック積層体の外部電極
JP7046679B2 (ja) 2018-03-30 2022-04-04 Ｊｘ金属株式会社 セラミック積層体の外部電極
JP2020155719A (ja) * 2019-03-22 2020-09-24 株式会社村田製作所 積層セラミックコンデンサ
CN111724991A (zh) * 2019-03-22 2020-09-29 株式会社村田制作所 层叠陶瓷电容器
JP7081543B2 (ja) 2019-03-22 2022-06-07 株式会社村田製作所 積層セラミックコンデンサ
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