CN116313511A - Preparation method of multilayer ceramic capacitor - Google Patents
Preparation method of multilayer ceramic capacitor Download PDFInfo
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- CN116313511A CN116313511A CN202310378474.9A CN202310378474A CN116313511A CN 116313511 A CN116313511 A CN 116313511A CN 202310378474 A CN202310378474 A CN 202310378474A CN 116313511 A CN116313511 A CN 116313511A
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 49
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 238000004321 preservation Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 9
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- 238000010438 heat treatment Methods 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
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- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims 1
- 229910000278 bentonite Inorganic materials 0.000 claims 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000002003 electrode paste Substances 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 24
- 238000010304 firing Methods 0.000 description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 17
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- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 229940116411 terpineol Drugs 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
- H01G4/0085—Fried electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/006—Apparatus or processes for applying 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
- H01G4/30—Stacked capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention discloses a preparation method of a multilayer ceramic capacitor, which comprises the following steps: step S1, casting dielectric paste into a green film sheet, and printing inner electrode paste on the green film sheet to form an inner electrode layer; s2, laminating, pressing, cutting, adhesive discharging and sintering the inner electrode layer to obtain a sintered laminated body; s3, covering end electrode copper slurry on the sintered laminated body, and sintering the end to the multilayer ceramic capacitor; the end electrode copper slurry comprises copper powder and glass powder; the glass powder comprises metal oxides with divalent or higher valence states; the oxygen potential value of the burning end is 600-800 mv, the temperature of the burning end is 800-830 ℃, and the heat preservation time is 10-15 min. According to the invention, on one hand, the conductive component is introduced into the glass component of the copper slurry, so that the glass has certain conductivity, and on the other hand, the conductive component is partially reduced by controlling and adjusting the terminal burning process, so that the conductivity of the conductive component is further enhanced, and the terminal electrode binding force is enhanced.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a preparation method of a multilayer ceramic capacitor.
Background
Multilayer ceramic capacitors (MLCCs) are the largest chip components used in electrical devices, and are widely used in the fields of notebook computers, mobile phones, automobiles, home appliances, unmanned aerial vehicles, and the like. The conventional multilayer ceramic capacitor includes a plurality of stacked dielectric layers, internal electrodes disposed opposite to each other with the dielectric layers therebetween, and terminal electrodes electrically connected to the internal electrodes, respectively. In general, in order to form a terminal electrode, a conductive paste containing a conductive powder is applied to a laminate, and then sintered to form the terminal electrode.
The end electrode slurry is usually composed of a copper metal phase, an organic phase and a glass phase, the components and the proportion of the end electrode slurry and the end burning process determine the performance of the sintered end electrode, and the performance of the end electrode copper slurry and the end burning process have important influences on the appearance, the basic electrical performance, the reliability, the welding resistance and the like of the capacitor.
The end electrode prepared by adopting the existing copper paste and end burning process has the problems of easy outward overflow of glass compatibility, uneven electroplating and low electroplating efficiency, and finally, poor tensile property and poor welding of the product and low production efficiency of the product.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention aims to provide a preparation method of a multilayer ceramic capacitor, which comprises the steps of leading a conductive component into a glass component of copper slurry to enable the glass to have certain conductivity, and controlling and adjusting a firing process to enable the conductive component to be partially reduced to further enhance the conductivity of the conductive component and enhance the bonding force of a terminal electrode.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for manufacturing a multilayer ceramic capacitor, comprising the steps of:
covering the copper paste of the terminal electrode on the laminated body, and burning the terminal to obtain the multilayer ceramic capacitor;
the end electrode copper slurry comprises copper powder and glass powder;
the glass powder comprises metal oxides with divalent or higher valence states;
the oxygen potential value of the burning end is 600-800 mv, the temperature of the burning end is 800-830 ℃, and the heat preservation time is 10-15 min.
Through researches, in the later stage of copper firing, the copper end is gradually densified, a large amount of glass is flushed to the surface of a copper electrode, and if the glass does not have conductivity, the phenomenon that the glass cannot be electroplated can be caused during the subsequent electroplating treatment, so that the performance of an MLCC product is affected.
In order to avoid the occurrence of the situation, divalent or more metal oxides are added into the glass phase, the metal oxides are partially reduced in a high-temperature reducing atmosphere which is introduced during end firing, and elements in the metal oxides have valence changes and have certain conductivity, so that the glass phase has certain conductivity, and the plating is facilitated and the bonding force of the end electrode is enhanced.
The invention is to add divalent or higher valence metal oxide and then reduce at high temperature, not directly add metal, in order to make specific metal element be combined into glass system in oxide form, then to convert valence state under specific condition, wherein lower valence oxide shows better conductivity. The simple addition of the metal simple substance cannot be a glass composition component, the glass cannot be made to exhibit a uniform conductive state, and the metal oxide in a high valence state is poor in conductivity, and the glass cannot be made to have good conductivity.
By controlling the process conditions during end firing, the degree of reduction of metal elements in the end electrode after firing and the degree of densification of the end electrode can be controlled. If the metal element is reduced to a smaller extent, the conductivity of the glass phase is weaker, which is insufficient to realize the beneficial effect of the scheme; if the degree of reduction of the metal element is too large, which means that the atmosphere in the furnace body is strong in reducibility, the fluidity of the glass is reduced, and the densification degree of the terminal electrode is poor.
In some embodiments of the present invention, the terminal electrode copper paste comprises the following components in percentage by mass: 65-75% of copper powder and 7-15% of glass powder.
In some embodiments of the invention, the glass frit includes 9 to 15% by mass of divalent and higher valence metal oxides.
The glass powder comprises 9-15% by mass of divalent or higher-valence metal oxide. If the content of the metal oxide in the glass powder is too small, the conductivity is not ideal enough, and the technical effect to be achieved by the scheme cannot be well achieved; if the metal oxide content in the glass frit is too high, the number of crystal nuclei increases and the crystal nuclei easily grow when the melt cools, and the system easily devitrifies and does not easily form glass.
In some embodiments of the invention, the divalent and higher valence state metal oxides include CuO, fe 3 O 4 、SnO 2 、MnO 2 、TiO 2 、V 2 O 5 、ZnO、RuO 2 、Ni 3 O 4 At least one of them.
In some embodiments of the invention, the divalent and higher valence metal oxides are selected from CuO.
CuO is preferred in the present invention because CuO is partially reduced to have good conductivity and compatibility with glass.
In some embodiments of the present invention, the glass frit further comprises the following components in percentage by mass: 45-60% ZnO, 20-35% B 2 O 3 、8～15％ SiO 2 、0～5％ Na 2 O、0～5％ CaO、0～5％ Al 2 O 3 。
In some embodiments of the invention, the preparation of the laminate comprises the steps of:
step S1, casting dielectric paste into a green film sheet, and printing inner electrode paste on the green film sheet to form an inner electrode layer;
and S2, laminating, pressing, cutting, discharging glue and sintering the inner electrode layer to obtain a laminated body.
In some embodiments of the present invention, the terminal electrode copper paste further comprises the following components in percentage by mass: 5-10% of resin, 10-18% of solvent and 1-5% of thixotropic agent.
In some preferred embodiments of the present invention, the resin includes at least one of ethyl cellulose, acrylic resin, epoxy resin, nitrocellulose resin, styrene resin, phenolic resin.
In some preferred embodiments of the present invention, the thixotropic agent comprises at least one of polyamide wax, fumed silica, hydrogenated castor oil, organobentonite.
In some preferred embodiments of the present invention, the organic solvent comprises at least one of terpineol, hydrogenated terpineol, butyl carbitol acetate, tributyl citrate, dipropylene glycol propyl ether.
In some preferred embodiments of the present invention, the copper powder comprises at least one of flake copper powder, spherical copper powder.
In some preferred embodiments of the invention, the copper powder has a D50 of 2 to 6 μm.
The invention further aims at providing a preparation method of the end electrode copper paste, which comprises the following steps:
s1, mixing and sieving the components of the glass powder, and obtaining the glass powder through melting, cooling, crushing, sieving and grinding;
s2, adding the resin into a solvent, heating and stirring until the resin is completely dissolved, and obtaining glue;
s3, uniformly mixing the copper powder and the glass powder to obtain mixed powder;
s4, adding the glue into the mixed powder, stirring, adding a thixotropic agent, and uniformly mixing to obtain the end electrode copper paste.
It is still another object of the present invention to provide a multilayer ceramic capacitor manufactured by the manufacturing method of the multilayer ceramic capacitor.
The multilayer ceramic capacitor has a plurality of stacked dielectric layers, internal electrodes disposed opposite to each other with the dielectric layers therebetween, and terminal electrodes electrically connected to the internal electrodes, respectively, the terminal electrodes being made of the copper paste described above.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were either commercially available from conventional sources or may be obtained by prior art methods unless specifically indicated. Unless otherwise indicated, assays or testing methods are routine in the art.
Example 1
The embodiment provides a multilayer ceramic capacitor, which comprises the following specific processes:
glass powder is prepared according to 45 percent of ZnO and 25 percent of B 2 O 3 、8％ SiO 2 、2％ Na 2 O、15％ CuO、0％ CaO、5％ Al 2 O 3 Weighing the raw materials of each oxide according to the proportion, uniformly mixing in a V-type mixer, and sieving to obtain a mixed material B;
adding the mixed material B into a crucible, carrying out rapid cooling treatment on molten glass after heat preservation for 1h at 1100 ℃, wherein the rapid cooling operation is that the temperature is reduced from 1100 ℃ to 25 ℃ within 2 seconds, the crucible used for heat preservation is a quartz crucible, and the cooling treatment mode is rolling mill cooling, so that glass is obtained;
crushing the glass, sieving the glass, enabling a screen to be 80 meshes, and reducing the granularity of the glass powder to 0.5-1.0 mu m through an air flow mill to obtain the glass powder;
the copper paste was prepared by mixing 65% copper powder, 15% glass frit, 5% resin, 10% solvent, and 5% additive. Firstly, adding resin into an organic solvent, heating and stirring at 80 ℃ until the resin is completely dissolved, wherein the stirring frequency is 10-20 Hz, and obtaining glue; the resin is ethyl cellulose, and the organic solvent is terpineol;
weighing copper powder and glass powder, and uniformly mixing to obtain mixed powder;
adding the glue into the mixed powder, stirring to enable the glue to carry out preliminary wetting on the mixed powder until no dry powder exists, and adding a thixotropic agent in the stirring process to obtain a mixed material A; the thixotropic agent is fumed silica;
and rolling the mixed material A by using a three-roller mill, and uniformly mixing to obtain the end electrode copper slurry.
Preparing dielectric paste and tape-casting to form a green film, printing inner electrode paste on the green film, laminating, cutting, discharging glue, sintering and the like to obtain a sintered laminated body. And (3) covering the end electrode copper slurry on the firing laminated body, wherein in the process of firing the end electrode, the oxygen potential value in the furnace is controlled to be 600mv, the temperature during firing the end is controlled to be 800 ℃, and the heat preservation time is controlled to be 10min. Electroplating after firing the ends to obtain the multilayer ceramic capacitor.
Example 2
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of each component in the copper paste:
the copper paste was prepared by mixing 70% copper powder, 11% glass frit, 5% resin, 12% solvent, and 2% additive.
Example 3
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of each component in the copper paste:
the copper paste was prepared by mixing 75% copper powder, 9% glass frit, 5% resin, 10% solvent, and 1% additive.
Example 4
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of each component in the copper paste:
the copper paste was prepared by mixing 65% copper powder, 7% glass frit, 9% resin, 18% solvent, and 1% additive.
Example 5
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of various oxides in the glass frit:
glass powder is prepared according to 45 percent of ZnO and 20 percent of B 2 O 3 、15％ SiO 2 、5％ Na 2 O、9％ CuO、5％ CaO、1％ Al 2 O 3 Is weighed according to the proportion.
Example 6
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of various oxides in the glass frit:
glass powder is prepared by mixing 60% ZnO and 20% B 2 O 3 、8％ SiO 2 、0％ Na 2 O、9％ CuO、0％ CaO、3％ Al 2 O 3 Is weighed according to the proportion.
Example 7
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of various oxides in the glass frit:
glass powder is prepared according to 45 percent of ZnO and 35 percent of B 2 O 3 、8％ SiO 2 、1％ Na 2 O、10％ CuO、1％ CaO、0％ Al 2 O 3 Is weighed according to the proportion.
Example 8
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of various oxides in the glass frit:
glass powder is prepared according to 45 percent of ZnO and 35 percent of B 2 O 3 、8％ SiO 2 、1％ Na 2 O、10％ SnO 2 、1％ CaO、0％ Al 2 O 3 Is weighed according to the proportion.
Example 9
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of various oxides in the glass frit:
glass powder is prepared according to 45 percent of ZnO and 35 percent of B 2 O 3 、8％ SiO 2 、1％ Na 2 O、10％ RuO 2 、1％ CaO、0％ Al 2 O 3 Is weighed according to the proportion.
Example 10
This example provides a multilayer ceramic capacitor differing from example 1 only in the content of various oxides in the glass frit:
glass powder is prepared according to 45 percent of ZnO and 35 percent of B 2 O 3 、8％ SiO 2 、1％ Na 2 O、10％ Ni 3 O 4 、1％ CaO、0％ Al 2 O 3 Is weighed according to the proportion.
Example 11
This example provides a multilayer ceramic capacitor differing from example 1 only in the process conditions of firing the ends:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 700mv, the temperature during burning the end is controlled at 820 ℃, and the heat preservation time is controlled at 11min.
Example 12
This example provides a multilayer ceramic capacitor differing from example 1 only in the process conditions of firing the ends:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 800mv, the temperature during burning the end is controlled at 830 ℃, and the heat preservation time is controlled at 15min.
Example 13
This example provides a multilayer ceramic capacitor differing from example 1 only in the process conditions of firing the ends:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 600mv, the temperature during burning the end is controlled at 810 ℃, and the heat preservation time is controlled at 14min.
Comparative example 1
This comparative example produced a multilayer ceramic capacitor differing from example 1 in the content of various oxides in the glass frit by the following procedure:
glass powder is prepared according to 53 percent of ZnO and 30 percent of B 2 O 3 、9％ SiO 2 、3％ Na 2 O、5％ Al 2 O 3 Is weighed according to the proportion.
Comparative example 2
This comparative example produced a multilayer ceramic capacitor differing from example 1 in the content of various oxides in the glass frit by the following procedure:
glass powder is prepared according to 50 percent of ZnO and 28 percent of B 2 O 3 、9％ SiO 2 、3％ Na 2 O、5％ CuO、5％ Al 2 O 3 Is weighed according to the proportion.
Comparative example 3
This comparative example produced a multilayer ceramic capacitor differing from example 1 in the content of various oxides in the glass frit by the following procedure:
glass powder is prepared according to 45 percent of ZnO and 20 percent of B 2 O 3 、8％ SiO 2 、2％ Na 2 O、20％ CuO、5％ Al 2 O 3 Is weighed according to the proportion.
Comparative example 4
This comparative example produced a multilayer ceramic capacitor differing from example 1 in the content of various oxides in the glass frit by the following procedure:
glass powder is prepared according to 45 percent of ZnO and 20 percent of B 2 O 3 、8％ SiO 2 、2％ Na 2 O、20％ Cu、5％ Al 2 O 3 Is weighed according to the proportion.
Comparative example 5
This comparative example produced a multilayer ceramic capacitor differing from example 1 only in firing end process conditions, and the specific process was:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 400mv, the temperature during burning the end is controlled at 800 ℃, and the heat preservation time is controlled at 10min.
Comparative example 6
This comparative example produced a multilayer ceramic capacitor differing from example 1 only in firing end process conditions, and the specific process was:
in the process of burning the end, the oxygen potential value in the furnace is controlled to be 1000mv, the temperature during burning the end is controlled to be 800 ℃, and the heat preservation time is controlled to be 10min.
Comparative example 7
This comparative example produced a multilayer ceramic capacitor differing from example 1 only in firing end process conditions, and the specific process was:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 600mv, the temperature during burning the end is controlled at 750 ℃, and the heat preservation time is controlled at 10min.
Comparative example 8
This comparative example produced a multilayer ceramic capacitor differing from example 1 only in firing end process conditions, and the specific process was:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 600mv, the temperature during burning the end is controlled at 850 ℃, and the heat preservation time is controlled at 10min.
Comparative example 9
This comparative example produced a multilayer ceramic capacitor differing from example 1 only in firing end process conditions, and the specific process was:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 600mv, the temperature during burning the end is controlled at 800 ℃, and the heat preservation time is controlled at 5min.
Comparative example 10
This comparative example produced a multilayer ceramic capacitor differing from example 1 only in firing end process conditions, and the specific process was:
in the process of burning the end, the oxygen potential value in the furnace is controlled at 600mv, the temperature during burning the end is controlled at 800 ℃, and the heat preservation time is controlled at 20min.
Performance test:
copper oxide is reduced: the test method is characterized in that XPS is used for representing the valence state of copper element in the terminal electrode, and the index is as follows: the valence distribution of the copper oxide in the glass after reduction is as follows: cu (0): cu (I): cu (II) =0 (1-5): 1.
Glass element distribution: grinding the LT surface of the sample to 1/2 position, and characterizing the overflow degree of the end glass by EPMA; the index is as follows: 40-60% of glass overflows.
Copper end compactness: placing the LT surface of a copper-fired sample in a plastic mould, solidifying a resin solvent, grinding the sample to a position of 1/2 of the sample on a metallographic grinder, and observing the proportion of non-compact holes at the copper end to the section of the copper end by using SEM; the index is as follows: the non-dense cavity cannot be less than 90%.
Coating continuity: the test method is characterized in that the connection condition of electroplated layers is represented by a metallographic microscope; the index is as follows: the continuity of the coating layer cannot be less than 95%, and the discontinuous length cannot be more than 20 μm.
And (3) welding resistance test: and evaluating whether the product is bad after welding. The index is as follows: after the welding resistance test, the surface of the plating layer is smooth, no cavity exists, 500 samples are tested, and the yield is up to 100%.
Table 1. Results of performance test of multilayer ceramic capacitor.
Table 1 shows the test results of each of examples and comparative examples, and it is understood from comparative examples 1 to 4 that when CuO is not added or CuO is added too little, the glass is not conductive or is not conductive enough after overflowing, resulting in poor solder resistance test and plating continuity; when too much CuO is added, the glass cannot be molded, and the proportion of the non-compact holes is large; according to comparative examples 5 to 10, the oxygen potential value in the firing process is too low, the temperature is too low or the heat preservation time is too short, the reduction of copper oxide is less, the conductivity of glass is insufficient, and the welding resistance test and the plating continuity are poor; when the oxygen potential value is too high, the temperature is too high or the heat preservation time is too long, copper oxide is excessively reduced into metallic copper, so that the glass cannot be molded, and the proportion of non-compact cavities is large.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a multilayer ceramic capacitor is characterized in that: the method comprises the following steps:
covering the copper paste of the terminal electrode on the laminated body, and burning the terminal to obtain the multilayer ceramic capacitor;
the end electrode copper slurry comprises copper powder and glass powder;
the glass powder comprises metal oxides with divalent or higher valence states;
the oxygen potential value of the burning end is 600-800 mv, the temperature of the burning end is 800-830 ℃, and the heat preservation time is 10-15 min.
2. The method for manufacturing a multilayer ceramic capacitor according to claim 1, wherein: the end electrode copper slurry comprises the following components in percentage by mass: 65-75% of copper powder and 7-15% of glass powder.
3. The method for manufacturing a multilayer ceramic capacitor according to claim 1, wherein: the glass powder comprises 9-15% by mass of divalent or higher-valence metal oxides.
4. The method for manufacturing a multilayer ceramic capacitor according to claim 1, wherein: the divalent or higher metal oxide comprises CuO and Fe 3 O 4 、SnO 2 、MnO 2 、TiO 2 、V 2 O 5 、ZnO、RuO 2 、Ni 3 O 4 At least one of them.
5. The method for manufacturing a multilayer ceramic capacitor according to claim 4, wherein: the metal oxide of divalent and higher valence is selected from CuO.
6. The method for manufacturing a multilayer ceramic capacitor according to claim 2, wherein: the glass powder also comprises the following components in percentage by mass: 45 to 60 percent of ZnO and 20 to 35 percent of B 2 O 3 、8～15％SiO 2 、0～5％Na 2 O、0～5％CaO、0～5％Al 2 O 3 。
7. The method for manufacturing a multilayer ceramic capacitor according to claim 2, wherein: the end electrode copper slurry also comprises the following components in percentage by mass: 5-10% of resin, 10-18% of solvent and 1-5% of thixotropic agent; the resin comprises at least one of ethyl cellulose, acrylic resin, epoxy resin, nitrocellulose resin, styrene resin and phenolic resin; the thixotropic agent comprises at least one of polyamide wax, fumed silica, hydrogenated castor oil and organic bentonite.
8. The method for manufacturing a multilayer ceramic capacitor according to claim 1, wherein: the copper powder comprises at least one of flake copper powder and spherical copper powder; the D50 of the copper powder is 2-6 mu m.
9. The method for manufacturing a multilayer ceramic capacitor according to claim 1, wherein: the preparation method of the end electrode copper slurry comprises the following steps:
s1, mixing and sieving the components of the glass powder, and obtaining the glass powder through melting, cooling, crushing, sieving and grinding;
s2, adding the resin into a solvent, heating and stirring until the resin is completely dissolved, and obtaining glue;
s3, uniformly mixing the copper powder and the glass powder to obtain mixed powder;
s4, adding the glue into the mixed powder, stirring, adding a thixotropic agent, and uniformly mixing to obtain the end electrode copper paste.
10. A multilayer ceramic capacitor characterized in that: the multilayer ceramic capacitor produced by the production method according to any one of claims 1 to 9.
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