WO2015045721A1 - 積層セラミック電子部品 - Google Patents
積層セラミック電子部品 Download PDFInfo
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- WO2015045721A1 WO2015045721A1 PCT/JP2014/072595 JP2014072595W WO2015045721A1 WO 2015045721 A1 WO2015045721 A1 WO 2015045721A1 JP 2014072595 W JP2014072595 W JP 2014072595W WO 2015045721 A1 WO2015045721 A1 WO 2015045721A1
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- 239000000919 ceramic Substances 0.000 title claims abstract description 151
- 238000007747 plating Methods 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 42
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 8
- 229910052681 coesite Inorganic materials 0.000 abstract 6
- 229910052906 cristobalite Inorganic materials 0.000 abstract 6
- 239000000377 silicon dioxide Substances 0.000 abstract 6
- 229910052682 stishovite Inorganic materials 0.000 abstract 6
- 229910052905 tridymite Inorganic materials 0.000 abstract 6
- 230000003628 erosive effect Effects 0.000 abstract 1
- 239000003985 ceramic capacitor Substances 0.000 description 22
- 239000011521 glass Substances 0.000 description 17
- 238000005452 bending Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000002003 electrode paste Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- -1 and B 2 O 3 Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
- H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also titanates
-
- 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
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
- H01G4/0085—Fried electrodes
-
- 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
- H01G4/005—Electrodes
- H01G4/012—Form of non-self-supporting electrodes
-
- 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
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- 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
-
- 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
-
- 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
- H01G4/248—Terminals the terminals embracing or surrounding the capacitive element, e.g. caps
-
- 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
Definitions
- the present invention relates to a multilayer ceramic electronic component, and more specifically, a ceramic body having a structure in which internal electrodes are stacked via a ceramic layer, and external electrodes arranged in a manner that wraps around from the end surface to the side surface.
- the present invention relates to a provided multilayer ceramic electronic component.
- One typical ceramic electronic component is, for example, a multilayer ceramic capacitor having a structure as shown in FIG.
- the multilayer ceramic capacitor has both end faces of a ceramic laminate (ceramic body) 60 in which a plurality of internal electrodes 52 (52a, 52b) are laminated via a ceramic layer 51 which is a dielectric layer.
- the external electrodes 54 are disposed on the 53a, 53b so as to be electrically connected to the internal electrodes 52 (52a, 52b).
- the external electrodes 54 are formed by a method in which a conductive paste is applied to both end faces of a ceramic multilayer body (ceramic body) and fired. Is common.
- a conductive paste comprising at least a metal powder, BaO—SrO—ZnO—B 2 O 3 —SiO 2 glass frit
- BaO 10 to 50% by weight
- SrO 5 to 40% by weight
- ZnO 10 to 30% by weight
- B 2 O 3 15 to 30% by weight
- SiO 2 3 to 20% by weight
- a conductive paste containing 0.5 to 10% by weight of glass frit with respect to 100% by weight of metal powder has been proposed (see Patent Document 1).
- the other conductive paste is at least one conductive powder selected from copper powder, nickel powder, copper-nickel alloy powder and mixtures thereof, lead-free, bismuth-free and cadmium-free, 530 to 650 ° C. And a glass paste having a thermal expansion coefficient of 9.0 to 11.5 ppm / ° C., and a conductive paste in which the conductive powder and the glass frit are dispersed in an organic medium have been proposed (Patent Document) 2).
- the conductive paste of Patent Document 1 has a small amount of SiO 2 in the glass frit used, the glass contained in the external electrode formed using the conductive paste of Patent Document 1 is dissolved in the plating solution. In the process of plating on the external electrode, there is a problem that the plating solution penetrates into the external electrode or the ceramic body and lowers the mechanical strength of the multilayer ceramic electronic component.
- the conductive paste of Patent Document 2 has the same problem as that described for the conductive paste of Patent Document 1.
- the present invention solves the above problems, and even when the external electrode is plated, it is possible to prevent a decrease in mechanical strength due to the plating solution entering the external electrode or the ceramic body.
- An object of the present invention is to provide a highly reliable multilayer ceramic electronic component.
- the multilayer ceramic electronic component of the present invention is: A ceramic body having a structure in which a plurality of internal electrodes are stacked with a ceramic layer interposed therebetween, and an external electrode electrically connected to the internal electrode, wherein the ceramic body has a structure that extends from an end surface to a side surface of the ceramic body.
- another multilayer ceramic electronic component of the present invention is A ceramic body having a structure in which a plurality of internal electrodes are stacked with a ceramic layer interposed therebetween, and an external electrode electrically connected to the internal electrode, wherein the ceramic body has a structure that extends from an end surface to a side surface of the ceramic body.
- the inorganic substance present at the interface has a molar ratio of B 2 O 3 to SiO 2 of the following formula (2): 0.25 ⁇ B 2 O 3 / SiO 2 ⁇ 0.5 (2) It is preferable to contain so that it may become the range represented by these.
- the interface between the external electrode tip region and the ceramic body suppresses and prevents the glass from crystallizing and acid resistance from decreasing, thereby reducing the mechanical strength more reliably. It is possible to prevent this, and the present invention can be further effectively realized.
- the tip region is a region within 10 ⁇ m from the tip of the wraparound portion of the external electrode that wraps around the side surface of the ceramic body.
- the tip region By setting the tip region to a region within 10 ⁇ m from the tip of the wraparound portion of the external electrode, the effect of the present invention can be reliably exerted, and the present invention can be more effectively realized.
- the external electrode has a plating film layer on the surface.
- the multilayer ceramic electronic component of the present invention has the above-described configuration, and the ceramic At the interface between the tip region of the wraparound portion of the external electrode that wraps around the side surface of the element body (that is, the region where stress is easily applied and is likely to start a crack) and the ceramic constituting the surface of the ceramic element, Because of the presence of such inorganic substances, the ceramic-glass reaction layer at the interface and the ceramic on the surface of the ceramic body elute into the plating solution in the plating process, and the plating solution external electrodes and ceramic elements It is possible to provide a monolithic ceramic electronic component having high mechanical strength and high reliability by suppressing intrusion into the body.
- the “interface between the external electrode tip region and the ceramic body” It is possible to improve the plating resistance by suppressing the elution of the existing ceramic-glass reaction layer and ceramic on the surface of the ceramic body more reliably, and it has excellent mechanical strength and high reliability.
- a multilayer ceramic electronic component can be provided.
- FIG. 1 It is a front sectional view showing the composition of the multilayer ceramic capacitor concerning the embodiment of the present invention. It is a figure which expands and shows the principal part of the multilayer ceramic capacitor shown in FIG. It is a figure which shows an example of the conventional multilayer ceramic electronic component.
- this multilayer ceramic capacitor has a ceramic element body (multilayer ceramic capacitor element) 10 in which a plurality of internal electrodes 2 (2a, 2b) are laminated via a ceramic layer 1 which is a dielectric layer.
- the external electrode 4 (4a, 4b) is disposed on the end face 3 (3a, 3b) of the first electrode 2 so as to be electrically connected to the internal electrode 2 (2a, 2b).
- the external electrodes 4 (4a, 4b) are arranged so as to extend from the end faces 3 (3a, 3b) on both sides of the ceramic body 10 to the four side surfaces 15 of the ceramic body over the ridge line portion. Yes.
- the external electrode 4 (4a, 4b) is formed on the external electrode body 11 formed by baking a conductive paste, the Ni plating film layer 12 formed on the surface of the external electrode body 11, and the surface of the Ni plating film layer 12.
- the Sn plating film layer 13 is a multilayer structure.
- the ceramic layer 1 constituting the ceramic body 10 of the multilayer ceramic capacitor is made of a dielectric ceramic having a perovskite structure (in this embodiment, a BaTiO 3 ceramic).
- the internal electrodes 2 (2a, 2b) are base metal electrodes having Ni as a conductive component.
- a perovskite type compound (BaTiO 3 ceramic powder) mainly composed of Ba and Ti containing an organic binder, an organic solvent, a plasticizer, and a dispersant in a predetermined ratio.
- a mixed ceramic slurry was prepared. Then, this ceramic slurry was applied on a resin film so that the thickness after drying was 4.0 ⁇ m, thereby producing a ceramic green sheet.
- a conductive paste for forming internal electrodes (internal electrode paste) was produced.
- a base metal powder such as a Ni alloy, Cu, or Cu alloy can be appropriately used as the conductive component constituting the internal electrode paste.
- noble metal powder such as Ag can be used.
- Conductive paste (internal electrode paste) containing Ni produced in the step (2) as a conductive component on the ceramic green sheet used in the step (1) is the size of the ceramic element after firing.
- the electrode pattern-formed ceramic green sheet applied by screen printing so as to have a pattern corresponding to (3.2 mm (length) ⁇ 1.6 mm (width)) and having a thickness after drying of 2 ⁇ m is the above (3).
- the predetermined number of sheets (350 sheets in this embodiment) was laminated on the lower outer layer portion formed in the process (1).
- a predetermined number of layers are laminated on the electrode pattern forming ceramic green sheet laminated in the step (4) so that an outer layer portion having a predetermined thickness is formed after firing, thereby forming an upper outer layer portion.
- An unfired laminated block was formed.
- An unfired ceramic body was obtained by cutting the unfired laminated block produced in the step (5) above at a predetermined position.
- the unfired ceramic body obtained in the step (6) is degreased in a nitrogen atmosphere at 400 ° C. for 10 hours using a batch furnace, and then a nitrogen-hydrogen-water vapor mixed atmosphere Baking was performed under conditions of a top temperature of 1200 ° C. and an oxygen partial pressure of 10 ⁇ 9 to 10 ⁇ 10 MPa to obtain a fired ceramic body before forming external electrodes.
- the ceramic body has a rectangular parallelepiped shape having dimensions of length (L): 3.2 mm, width (W): 1.6 mm, and thickness (T): 1.6 mm.
- External electrode As a conductive paste used to form an external electrode, (A) 70 parts by weight of Cu powder; (B) 10 parts by weight of a zinc borosilicate glass frit adjusted so that the content of SiO 2 , TiO 2 and ZrO 2 is the ratio shown in Table 1, (C) A conductive paste for forming an external electrode was prepared by dispersing and mixing 20 parts by weight of a resin solution obtained by dissolving 20 parts by weight of ethyl cellulose in butyl carbitol.
- the conductive paste produced as described above was applied to the ceramic body by a dip coating method.
- a conductive paste for forming an external electrode is applied to a surface plate with a predetermined thickness, and one end surface side of the ceramic body held by the holding jig is immersed from above, and from the end face and end face of the ceramic body An external electrode paste was applied to a region that wraps around the side surface.
- the coating thickness of the external electrode paste was adjusted so that the coating thickness of the conductive paste on the end face of the ceramic body after drying was 50 ⁇ m.
- the other end face side of the ceramic body is dipped in the same manner, and the conductive paste is applied to the end face on the other side of the ceramic body and the region that goes from the end face to the side face. Applied.
- the ceramic body was heat-treated in order to fire the conductive paste for forming external electrodes applied to the ceramic body.
- the heat treatment was performed under the conditions of a top temperature (880 ° C.) and an oxygen electromotive force of 280 mV, and Cu-baked electrodes (external electrode bodies) were formed on both ends of the ceramic body.
- the carrier gas is N 2
- the atmosphere is such that the electromotive force is 600-900 mV by adding H 2 into the carrier gas (N 2 ). Was adjusted and fired.
- Ni plating is performed by a wet electrolytic plating method, a Ni plating film is formed on the surface of the external electrode, and further Sn plating is performed by a wet electrolytic plating method. An Sn plating film was formed on the Ni plating film. As a result, a multilayer ceramic capacitor having a configuration as shown in FIGS. 1 and 2 was obtained.
- the multilayer ceramic capacitor (sample) shown in FIG. 1 is measured from the LW surface, which is a surface defined by the length L and the width W, until the dimension in the thickness T direction becomes 1/2.
- SiO 2 , TiO 2 , and ZrO 2 were quantified.
- Table 1 the values of B 2 O 3 , SiO 2 , TiO 2 , and ZrO 2 are average values.
- Table 1 shows B 2 O 3 , SiO 2 , TiO 2 , and B 2 O 3 , SiO 2 , and TiO 2 at the interface portion (interface portion between the tip region within 10 ⁇ m from the tip of the wraparound portion of the external electrode and the ceramic constituting the surface of the ceramic body). Quantitative results of ZrO 2 , B 2 O 3 / SiO 2 value (molar ratio), (TiO 2 + ZrO 2 ) / (SiO 2 + TiO 2 + ZrO 2 ) value (molar ratio) at the interface, bending test The bending strength examined is shown.
- samples with sample numbers marked with * are samples that do not satisfy the requirements of the present invention, and other samples (samples with sample numbers of 6 to 22) satisfy the requirements of the present invention. It is a sample to be filled.
- SiO 2 is present in a range of 26 mol% or more and less than 45 mol% at the interface between the tip region within 10 ⁇ m from the tip of the wraparound portion of the external electrode and the ceramic constituting the surface of the ceramic body.
- the ratio of TiO 2 and ZrO 2 that is supposed to improve the acid resistance is set to 0.154 or more. It is considered that the elution resistance to Ni plating in the wrap-around tip region is improved and the bending strength is improved.
- the mechanical strength (bending strength) of the multilayer ceramic capacitor changes depending on the ratio of B 2 O 3 and SiO 2 at the interface as in samples Nos. 14 to 22. This is because the glass existing at the interface between the tip region within 10 ⁇ m from the tip of the wraparound portion of the external electrode and the ceramic constituting the surface of the ceramic body is crystallized or the acid resistance is reduced. Conceivable.
- the glass existing at the interface portion crystallizes, and a composition shift occurs in the glass portion at the interface portion. It is considered that the mechanical strength is lowered as a result of being easily dissolved in the plating solution.
- the mechanical strength is lowered, but this is because the glass composition at the interface portion is resistant to the plating solution. Therefore, it is considered that the glass at the interface portion was dissolved in the plating solution and the mechanical strength was lowered. From the above results, the ratio of B 2 O 3 / SiO 2 is found to be more desirable that 0.25 ⁇ B 2 O 3 / SiO 2 ⁇ 0.5.
- the amount of SiO 2 at the interface between the tip region within 10 ⁇ m from the tip of the wraparound portion of the external electrode and the ceramic constituting the surface of the ceramic body is 25 to 45 mol%.
- the value (molar ratio) of (TiO 2 + ZrO 2 ) / (SiO 2 + TiO 2 + ZrO 2 ) is 0.000 to 0.138. It was confirmed that the bending strength was as low as 22 to 38 N.
- a multilayer ceramic capacitor has been described as an example.
- the present invention is not limited to a multilayer ceramic capacitor.
- an electrode internal
- a ceramic body such as a multilayer LC composite component or a multilayer varistor.
- the present invention can be applied to various multilayer ceramic electronic components that are provided with external electrodes in such a manner as to be provided from the end face of the ceramic body to the side face.
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Abstract
Description
複数の内部電極がセラミック層を介して積層された構造を有するセラミック素体と、前記内部電極と導通する外部電極であって、前記セラミック素体の端面から側面に回り込むように前記セラミック素体の端部に形成された外部電極とを備えた積層セラミック電子部品において、
前記セラミック素体の側面に回り込んだ前記外部電極の回り込み部の先端領域と、前記セラミック素体の表面を構成するセラミックとの界面に、
SiO2を26mol%以上45mol%未満含有し、かつ、
下記の式(1):
モル比=(TiO2+ZrO2)/(SiO2+TiO2+ZrO2) ……(1)
で表されるモル比の値が0.154以上である無機物質が存在していること
を特徴としている。
複数の内部電極がセラミック層を介して積層された構造を有するセラミック素体と、前記内部電極と導通する外部電極であって、前記セラミック素体の端面から側面に回り込むように前記セラミック素体の端部に形成された外部電極とを備えた積層セラミック電子部品において、
前記セラミック素体の側面に回り込んだ前記外部電極の回り込み部の先端領域と、前記セラミック素体の表面を構成するセラミックとの界面に、
SiO2を45mol%以上含有し、かつ、
下記の式(1):
モル比=(TiO2+ZrO2)/(SiO2+TiO2+ZrO2) ……(1)
で表されるモル比の値が0.022以上である無機物質が存在していること
を特徴としている。
0.25≦B2O3/SiO2≦0.5 ……(2)
で表される範囲となるように含有していること
が好ましい。
したがって、本発明によれば、外部電極にめっきが施される場合にも、めっき液が外部電極やセラミック素体に浸入することによる機械強度の低下を抑制、防止して、信頼性の高い積層セラミック電子部品を提供することが可能になる。
この実施形態では、図1に示すような構造を有する積層セラミックコンデンサを製造する場合を例にとって説明する。
(1)Ba、Tiを主成分とするペロブスカイト型化合物(BaTiO3系セラミック粉末)に対して、有機バインダー、有機溶剤、可塑剤、および分散剤を所定の割合で混合したセラミックスラリーを調製した。
それからこのセラミックスラリーを樹脂フィルム上に、乾燥後の厚みが4.0μmとなるように塗布して、セラミックグリーンシートを作製した。
なお、内部電極ペーストを構成する導電成分としては、Ni粉末以外にも、Ni合金、Cu、Cu合金などの卑金属粉末を適宜用いることが可能である。場合によっては、Agなどの貴金属粉末を用いることも可能である。
(1)外部電極を形成するために用いる導電性ペーストとして、
(a)Cu粉末70重量部と、
(b)SiO2、TiO2およびZrO2含有量が、表1に示す割合になるように調整したホウケイ酸亜鉛系ガラスフリット10重量部と、
(c)ブチルカルビトールにエチルセルロース20重量部を溶かした樹脂溶液20重量部と
を分散・混合することにより、外部電極形成用の導電性ペーストを作製した。
そして、塗布した導電性ペーストを乾燥させた後、同様にして、セラミック素体の他方の端面側を浸漬し、セラミック素体の他方側の端面と、端面から側面に回り込む領域に導電性ペーストを塗布した。
熱処理は、トップ温度(880℃)で、酸素起電力が280mVの条件で行い、セラミック素体の両端部に、Cu焼き付け電極(外部電極本体)を形成した。
なお、熱処理工程では、外部電極の酸化を抑制するため、キャリアガスをN2とし、TOP温度ではキャリアガス(N2)中にH2を添加して起電力=600-900mVとなるように雰囲気を調整して焼成を行った。
これにより、図1および2に示すような構成を備えた積層セラミックコンデンサを得た。
上述のようにして作製した積層セラミックコンデンサについて、回り込み部先端領域の界面に存在する無機物質の組成分析および抗折試験を行い、特性を評価した。
上述のようにして作製した積層セラミックコンデンサ(試料)について、図2に示すように、外部電極4の、セラミック素体10の側面15に回り込んだ回り込み部14の先端領域(以下、単に「回り込み部先端領域」ともいう)14aと、セラミック素体10の表面を構成するセラミックとの界面に存在する無機物質20の組成を、以下に説明する方法で調べた。
なお、この実施形態では、図2に模式的に示すように、外部電極4のセラミック素体10の側面15への回り込み部14の先端から10μm以内の領域を、「回り込み部先端領域」14aとした。
上述のようにして作製した積層セラミックコンデンサ(試料)について、3点曲げにて抗折試験を行った。試料数は20個とした(n=20)。
(a)押し冶具の降下スピード :0.1[mm/sec]
(b)押し冶具先端の半径(R) :0.2[mm]
(c)試料の押し位置 :セラミック素体の中央
(d)試料数 :n=20
上記結果から、B2O3/SiO2の比率は、0.25≦B2O3/SiO2≦0.5であることがより望ましいことが分かる。
2(2a,2b) 内部電極
3(3a,3b) セラミック素体の端面
4(4a,4b) 外部電極
10 セラミック素体
11 外部電極本体
12 Niめっき膜層
13 Snめっき膜層
14 回り込み部
14a 回り込み部の先端領域
15 セラミック素体の側面
20 境界部の無機物質
Claims (5)
- 複数の内部電極がセラミック層を介して積層された構造を有するセラミック素体と、前記内部電極と導通する外部電極であって、前記セラミック素体の端面から側面に回り込むように前記セラミック素体の端部に形成された外部電極とを備えた積層セラミック電子部品において、
前記セラミック素体の側面に回り込んだ前記外部電極の回り込み部の先端領域と、前記セラミック素体の表面を構成するセラミックとの界面に、
SiO2を26mol%以上45mol%未満含有し、かつ、
下記の式(1):
モル比=(TiO2+ZrO2)/(SiO2+TiO2+ZrO2) ……(1)
で表されるモル比の値が0.154以上である無機物質が存在していること
を特徴とする積層セラミック電子部品。 - 複数の内部電極がセラミック層を介して積層された構造を有するセラミック素体と、前記内部電極と導通する外部電極であって、前記セラミック素体の端面から側面に回り込むように前記セラミック素体の端部に形成された外部電極とを備えた積層セラミック電子部品において、
前記セラミック素体の側面に回り込んだ前記外部電極の回り込み部の先端領域と、前記セラミック素体の表面を構成するセラミックとの界面に、
SiO2を45mol%以上含有し、かつ、
下記の式(1):
モル比=(TiO2+ZrO2)/(SiO2+TiO2+ZrO2) ……(1)で表されるモル比の値が0.022以上である無機物質が存在していること
を特徴とする積層セラミック電子部品。 - 前記界面に存在する前記無機物質が、B2O3をSiO2とのモル比が下記の式(2):
0.25≦B2O3/SiO2≦0.5 ……(2)
で表されるような範囲となるように含有していること
を特徴とする請求項1または2記載の積層セラミック電子部品。 - 前記先端領域が、前記セラミック素体の側面に回り込んだ前記外部電極の回り込み部の先端から10μm以内の領域であることを特徴とする請求項1~3のいずれかに記載の積層セラミック電子部品。
- 前記外部電極が、表面にめっき膜層を備えたものであることを特徴とする請求項1~4のいずれかに記載の積層セラミック電子部品。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06309921A (ja) * | 1993-04-27 | 1994-11-04 | Mitsubishi Materials Corp | チップ型電子部品用導電性ペースト |
JP2005317432A (ja) * | 2004-04-30 | 2005-11-10 | Shoei Chem Ind Co | 導電性ペースト及びガラスフリット |
JP2005317776A (ja) * | 2004-04-28 | 2005-11-10 | Murata Mfg Co Ltd | セラミック電子部品の製造方法 |
WO2006090551A1 (ja) * | 2005-02-22 | 2006-08-31 | Murata Manufacturing Co., Ltd. | 導電性ペースト、積層セラミック電子部品およびその製造方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08180731A (ja) * | 1994-12-26 | 1996-07-12 | Murata Mfg Co Ltd | 導電性厚膜組成物、厚膜電極、セラミック電子部品、および積層セラミックコンデンサ |
JPH09190950A (ja) | 1996-01-09 | 1997-07-22 | Mitsubishi Materials Corp | 電子部品の外部電極 |
JPH09266129A (ja) | 1996-03-28 | 1997-10-07 | Mitsubishi Materials Corp | チップ型電子部品の外部電極 |
US20010016252A1 (en) * | 2000-02-09 | 2001-08-23 | Murata Manufacturing Co., Ltd. | Conductive paste and ceramic electronic device using the same |
JP2003077336A (ja) | 2001-08-30 | 2003-03-14 | Kyocera Corp | 導電性ペースト及びこれを用いた積層セラミックコンデンサ |
US7147804B2 (en) | 2003-01-24 | 2006-12-12 | E. I. Du Pont De Nemours And Company | Terminal electrode compositions for multilayer ceramic capacitors |
US7339780B2 (en) * | 2004-06-09 | 2008-03-04 | Ferro Corporation | Copper termination inks containing lead free and cadmium free glasses for capacitors |
US6982864B1 (en) * | 2004-06-09 | 2006-01-03 | Ferro Corporation | Copper termination inks containing lead free and cadmium free glasses for capacitors |
WO2006003755A1 (ja) * | 2004-07-06 | 2006-01-12 | Murata Manufacturing.Co., Ltd. | 導電性ペースト及びそれを用いたセラミック電子部品 |
JP2007011805A (ja) * | 2005-06-30 | 2007-01-18 | Toshiba Corp | 通信装置及び通信方法 |
KR101053329B1 (ko) * | 2009-07-09 | 2011-08-01 | 삼성전기주식회사 | 세라믹 전자부품 |
JP5251913B2 (ja) * | 2010-03-29 | 2013-07-31 | 株式会社村田製作所 | 誘電体セラミック組成物および積層セラミックコンデンサ |
JP2012059742A (ja) * | 2010-09-06 | 2012-03-22 | Murata Mfg Co Ltd | 積層セラミックコンデンサ |
KR20120068622A (ko) * | 2010-12-17 | 2012-06-27 | 삼성전기주식회사 | 외부전극용 도전성 페이스트 조성물, 이를 포함하는 적층 세라믹 커패시터 및 그 제조방법 |
JP5939475B2 (ja) * | 2012-02-29 | 2016-06-22 | 株式会社村田製作所 | 導電性ペースト、及び電子部品、並びに電子部品の製造方法 |
-
2014
- 2014-08-28 KR KR1020167007023A patent/KR101786486B1/ko active IP Right Grant
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- 2016-03-11 US US15/067,618 patent/US10008326B2/en active Active
-
2018
- 2018-05-21 US US15/984,835 patent/US10522287B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06309921A (ja) * | 1993-04-27 | 1994-11-04 | Mitsubishi Materials Corp | チップ型電子部品用導電性ペースト |
JP2005317776A (ja) * | 2004-04-28 | 2005-11-10 | Murata Mfg Co Ltd | セラミック電子部品の製造方法 |
JP2005317432A (ja) * | 2004-04-30 | 2005-11-10 | Shoei Chem Ind Co | 導電性ペースト及びガラスフリット |
WO2006090551A1 (ja) * | 2005-02-22 | 2006-08-31 | Murata Manufacturing Co., Ltd. | 導電性ペースト、積層セラミック電子部品およびその製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160042867A1 (en) * | 2013-04-25 | 2016-02-11 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor and manufacturing method therefor |
US9842698B2 (en) * | 2013-04-25 | 2017-12-12 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor and manufacturing method therefor |
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