CN115223792B - Multilayer ceramic capacitor and method for manufacturing the same - Google Patents

Multilayer ceramic capacitor and method for manufacturing the same Download PDF

Info

Publication number
CN115223792B
CN115223792B CN202210950501.0A CN202210950501A CN115223792B CN 115223792 B CN115223792 B CN 115223792B CN 202210950501 A CN202210950501 A CN 202210950501A CN 115223792 B CN115223792 B CN 115223792B
Authority
CN
China
Prior art keywords
copper
layer
copper layer
silver
multilayer ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210950501.0A
Other languages
Chinese (zh)
Other versions
CN115223792A (en
Inventor
请求不公布姓名
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chizhou Yunzhong Electronic Technology Co ltd
Original Assignee
Chizhou Yunzhong Electronic Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chizhou Yunzhong Electronic Technology Co ltd filed Critical Chizhou Yunzhong Electronic Technology Co ltd
Priority to CN202210950501.0A priority Critical patent/CN115223792B/en
Publication of CN115223792A publication Critical patent/CN115223792A/en
Application granted granted Critical
Publication of CN115223792B publication Critical patent/CN115223792B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • 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
    • H01G4/30—Stacked capacitors

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

The application discloses a multilayer ceramic capacitor and a preparation method thereof, wherein the multilayer ceramic capacitor comprises: the ceramic body comprises a first inner electrode, a second inner electrode and a dielectric layer, wherein the first inner electrode and the second inner electrode are arranged in a stacked mode; the first external electrode is electrically connected with the first internal electrode, and the second external electrode is electrically connected with the second internal electrode; the first external electrode and/or the second external electrode comprises a first copper layer, a second copper layer or a second silver layer, a nickel layer and a tin layer which are sequentially laminated from inside to outside of the ceramic body. The external electrode of the multilayer ceramic capacitor adopts a double-layer copper structure, solves the problem that nickel liquid of a subsequent electroplating process permeates into the first copper layer, reduces the internal stress of the first copper layer and the ceramic body, reduces the thermal shrinkage stress of materials in the soldering process, and avoids cracks caused by overlarge residual stress of the ceramic body.

Description

Multilayer ceramic capacitor and method for manufacturing the same
Technical Field
The application relates to the technical field of ceramic capacitors, in particular to a multilayer ceramic capacitor and a preparation method thereof.
Background
Multilayer ceramic capacitors (Multi-layer Ceramic Capacitor, MLCC for short) are one of the most widely used electronic components. The conventional multilayer ceramic capacitor generally includes a plurality of ceramic dielectric layers and a ceramic body alternately laminated with a plurality of inner electrode layers, and the multilayer ceramic capacitor generally further includes two external electrodes electrically connected to the alternately laminated inner electrode layers, respectively.
In the prior art, the external electrode of the multilayer ceramic capacitor is generally a copper layer, a nickel layer and a tin layer from inside to outside, and the preparation process of the external electrode comprises the following steps: adhering copper paste, burning the copper paste, electroplating nickel and tin, thereby forming an external electrode.
Because the copper paste comprises copper powder, glass and resin, the resin in the copper paste is easy to volatilize from the surface of the copper paste to form a cavity in the process of burning the copper paste, and in the subsequent nickel electroplating process, the electroplating solution has acidity and is easy to erode a metallic glass phase of a copper layer and invade the inside of the cavity of the copper layer, so that a small amount of nickel metal and the electroplating solution exist inside the copper layer. In the subsequent application process of the finished product of the multilayer ceramic capacitor, for example, when the multilayer ceramic capacitor is welded on a circuit board, the multilayer ceramic capacitor is subjected to a reflow soldering process (SMT tin climbing), the heating temperature of the product is not equal to 260-320 ℃, and the internal stress generated by the difference of the thermal expansion coefficients or the thermal shrinkage coefficients of copper and nickel acts on the ceramic body due to the residual nickel metal in the copper metal layer, so that the ceramic body is cracked, and the performance is reduced.
Disclosure of Invention
The application aims to provide a multilayer ceramic capacitor and a preparation method thereof, which are used for solving the problems that nickel metal remains in a copper layer and a ceramic body is cracked due to different heat shrinkage rates of nickel and copper.
The application adopts the following technical scheme:
a multilayer ceramic capacitor comprising:
the ceramic body comprises a first inner electrode, a second inner electrode and a dielectric layer, wherein the first inner electrode and the second inner electrode are arranged in a stacked mode;
the first external electrode is electrically connected with the first internal electrode, and the second external electrode is electrically connected with the second internal electrode;
the first external electrode and/or the second external electrode comprises a first copper layer, a second copper layer or a second silver layer, a nickel layer and a tin layer which are sequentially laminated from inside to outside of the ceramic body.
In an alternative, the first copper layer is a fired copper layer comprising copper and glass, a plurality of voids are formed in the first copper layer, and the second copper layer or the second silver layer fills a portion of the voids.
In an alternative, the first copper layer has a thickness of 10-15 μm.
In an alternative, the inner and outer surfaces of the first copper layer have a higher glass content than the rest of the first copper layer.
In an alternative scheme, copper oxide is formed in the first copper layer, the content of copper oxide on the outer surface of the first copper layer is higher than that of copper oxide on the rest of the first copper layer, and the oxygen content on the outer surface of the first copper layer is higher than that of copper oxide on the rest of the first copper layer.
In an alternative, the first copper layer has a copper oxide content and an oxygen content that gradually increase in a thickness direction from the inner surface to the outer surface.
In one alternative, the second copper layer is a fired copper layer comprising copper and glass, or the second silver layer is a fired silver layer comprising silver and glass.
In an alternative, the second copper layer or the second silver layer has a thickness of 3-5 μm.
In an alternative, the glass content of the inner and outer surfaces of the second copper layer or second silver layer is higher than the glass content of the remaining locations of the second copper layer or second silver layer.
In an alternative, the glass content at the interface of the outer surface of the first copper layer and the inner surface of the second copper layer or the second silver layer is higher than the glass content at the rest of the first copper layer and the second copper layer or the second silver layer.
In an alternative scheme, copper oxide or silver oxide is formed in the second copper layer or the second silver layer, the content of copper oxide or silver oxide on the outer surface of the second copper layer or the second silver layer is higher than that of copper oxide or silver oxide on the rest of the second copper layer or the second silver layer, and the oxygen content on the outer surface of the second copper layer or the second silver layer is higher than that of copper oxide or silver oxide on the rest of the second copper layer or the second silver layer.
In an alternative, the second copper layer or the second silver layer has a content of copper oxide or silver oxide and an oxygen content gradually increasing in a thickness direction from the inner surface to the outer surface.
In an alternative, the second copper layer or second silver layer has a higher denseness than the first copper layer.
In an alternative, the particle size of copper in the second copper layer is smaller than the particle size of copper in the first copper layer, or the sintering temperature of the second copper layer is greater than the sintering temperature of the first copper layer.
In an alternative, the second copper layer is an electroplated copper layer comprising pure copper, or the second silver layer is an electroplated silver layer comprising pure silver, the second copper layer or second silver layer being more dense than the first copper layer.
In an alternative, the second copper layer or the second silver layer has a thickness of 1-2 μm.
In an alternative, the particle size of copper in the second copper layer is smaller than the particle size of copper in the first copper layer, further making the compactness of the second copper layer higher than the compactness of the first copper layer.
In an alternative scheme, the first external electrode and/or the second external electrode further comprises a first silver layer, and the first silver layer is arranged between the ceramic body and the first copper layer and electrically connects the corresponding first internal electrode and the second internal electrode.
The application also provides a preparation method of the multilayer ceramic capacitor, which comprises the following steps:
providing a ceramic body comprising a first internal electrode, a second internal electrode, and a dielectric layer between the first internal electrode and the second internal electrode;
and forming a first external electrode and a second external electrode on the ceramic body, wherein the first external electrode is electrically connected with the first internal electrode, the second external electrode is electrically connected with the second internal electrode, and the first external electrode and/or the second external electrode comprises a first copper layer, a second copper layer or a second silver layer, a nickel layer and a tin layer which are sequentially laminated from inside to outside from the ceramic body.
In an alternative, the first copper layer is formed by: adhering copper paste on the ceramic body, and forming the first copper layer through burning;
the second copper layer or the second silver layer is formed by the following method: and adhering copper paste or silver paste on the first copper layer, and forming the second copper layer or the second silver layer by burning.
In one alternative, the copper pastes used to form the first and second copper layers each include copper powder, glass, and resin, with the copper powder including spherical copper powder and/or flake copper powder, and the copper powder used to form the second copper layer having a smaller size than the copper powder used to form the first copper layer.
In an alternative, the copper flake used to form the first copper layer is 7-9 μm in size and the copper flake used to form the second copper layer is 2-3 μm in size.
In an alternative, the first copper layer is formed by: adhering copper paste on the ceramic body, forming the first copper layer through burning, wherein the copper paste for forming the first copper layer comprises copper powder, glass and resin;
the second copper layer or the second silver layer is formed by the following method: and forming the second copper layer or the second silver layer on the first copper layer by an electroplating method, wherein the second copper layer or the second silver layer formed by electroplating is pure copper or pure silver.
In an alternative, the method for preparing the first external electrode and/or the second external electrode further includes: first, forming a first silver layer electrically connected with a first inner electrode and a second inner electrode on the ceramic body in a burning mode, and then forming a first copper layer, a second copper layer or a second silver layer, a nickel layer and a tin layer on the first silver layer.
Compared with the prior art, the application has the beneficial effects that at least:
the external electrode of the multilayer ceramic capacitor adopts a double-layer copper structure, namely, a second copper layer is added between the first copper layer and the nickel layer to form the double-layer copper structure, copper of the second copper layer fills most or even all of the cavities formed by the first copper layer during preparation, the second copper layer effectively isolates the first copper layer from the nickel layer, so that the problem that nickel liquid of a subsequent electroplating process permeates into the first copper layer is solved, the first copper layer and the second copper layer have better compatibility during the subsequent application process of the multilayer ceramic capacitor, and even if nickel metal is remained in the second copper layer, the thermal expansion coefficient or the thermal shrinkage rate of copper and the nickel layer are different, the generated internal stress cannot act on the ceramic body due to the isolation effect of the second copper layer, thereby effectively reducing the internal stress of the first copper layer and the ceramic body, reducing the thermal shrinkage stress (thermal stress) of materials in the soldering process, and avoiding cracks of the ceramic body due to overlarge residual stress.
Drawings
Fig. 1 is a schematic perspective view of a multilayer ceramic capacitor according to an embodiment of the present application.
Fig. 2 is a schematic cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present application.
Fig. 3 is a partial enlarged view at the dotted circle of fig. 2.
Fig. 4 is a partially exploded schematic view of a multilayer ceramic capacitor according to an embodiment of the present application.
Fig. 5 is a partially exploded schematic view of a multilayer ceramic capacitor according to another embodiment of the present application.
Fig. 6 is a schematic cross-sectional view of the multilayer ceramic capacitor of the embodiment of fig. 5.
Fig. 7 is a partial enlarged view at the dotted circle of fig. 6.
Fig. 8 is an SEM image of a portion of the first copper layer in embodiment 1 of the present application.
Fig. 9 is an SEM image of a portion of the second copper layer in embodiment 1 of the present application.
Fig. 10 is an SEM image of a portion of the second copper layer of example 2 of the present application.
In the figure: 1. a ceramic body; 2. a first internal electrode; 3. a second internal electrode; 4. a dielectric layer; 5. a first external electrode; 6. a second external electrode; 7. a first copper layer; 8. a second copper layer; 9. a nickel layer; 10. a tin layer; 11. a first silver layer.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the exemplary embodiments can be embodied in many forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus a repetitive description thereof will be omitted.
The words expressing the positions and directions described in the present application are described by taking the drawings as an example, but can be changed according to the needs, and all the changes are included in the protection scope of the present application.
Referring to fig. 1 to 4, the present application provides a multilayer ceramic capacitor comprising: a ceramic body 1, a first external electrode 5 and a second external electrode 6.
The ceramic body 1 includes a plurality of first internal electrodes 2, a plurality of second internal electrodes 3 and a plurality of dielectric layers 4 between the first internal electrodes 2 and the second internal electrodes 3, the plurality of first internal electrodes 2 and the plurality of second internal electrodes 3 are alternately exposed to both end surfaces of the ceramic body 1, the material of the first internal electrodes 2 and the second internal electrodes 3 is, for example, nickel, silver, copper or other conductive materials or combinations, and the material of the dielectric layers 4 may be a ceramic material having a high dielectric constant including, but not limited to, barium titanate, strontium titanate, and the uppermost and lowermost layers of the ceramic body 1 are upper and lower protective layers in which the dielectric layers 4 are stacked.
A first external electrode 5 and a second external electrode 6 are disposed on the ceramic body 1, the first external electrode 5 is electrically connected to the first internal electrode 2, and the second external electrode 6 is electrically connected to the second internal electrode 3.
The first external electrode 5 and/or the second external electrode 6 comprises a first copper layer 7, a second copper layer 8, a nickel layer 9 and a tin layer 10 which are laminated in order from the inside to the outside of the ceramic body 1.
According to the structure, the second copper layer 8 is added between the first copper layer 7 and the nickel layer 9 to form the double-layer copper external electrode structure, most of cavities formed by the first copper layer 7 during preparation and even all cavities are filled with copper of the second copper layer 8, the second copper layer 8 effectively isolates the first copper layer 7 from the nickel layer 9, so that the problem that nickel liquid of a subsequent electroplating process permeates into the first copper layer 7 is solved, the first copper layer 7 and the second copper layer 8 have better compatibility in the subsequent application process of the multilayer ceramic capacitor, even though nickel metal remains in the second copper layer 8, the thermal expansion coefficients or the thermal shrinkage rates of copper and nickel are different, due to the isolation effect of the second copper layer 8, the generated internal stress cannot act on the ceramic body 1, and therefore the internal stress of the first copper layer 7 and the ceramic body 1 is effectively reduced, the material thermal shrinkage stress (thermal stress) caused in the soldering process is reduced, and cracks of the ceramic body 1 due to overlarge residual stress are avoided.
In a specific embodiment, the first copper layer 7 is a fired copper layer containing copper and glass, the thickness of the first copper layer 7 is preferably 10-15 μm, the copper paste used for preparing the first copper layer 7 may include copper powder, glass and resin, wherein the copper powder is used as a main component of a copper terminal electrode, the copper powder is sintered at high temperature to form a conductive function, the main component of the glass is silicon dioxide, the main function is to engage the first copper layer 7 with the ceramic body 1 for reliable connection, and the copper powder is melted at high temperature to wet at the same time to promote the copper powder to realize the conductive function, and the resin is used for adjusting the viscosity of the copper paste, so that the copper powder and the glass are uniformly distributed in the copper paste, and the copper paste can be adhered to the end part of the ceramic body 1. The sintering (also called sintering) method is mature in process for preparing the copper layer and low in cost. During the firing process, the resin volatilizes and voids (see fig. 8) are formed in the first copper layer 7, which voids are for example distributed on and inside the outer surface of the first copper layer 7, the second copper layer 8 fills a part of the voids, and the second copper layer 8 for example fills the voids distributed on the outer surface of the first copper layer 7. Part of the hollows are filled by the second copper layer 8, the first copper layer 7 and the nickel layer 9 are effectively isolated, and the hollows of the first copper layer 7 are prevented from being permeated by nickel liquid in an electroplating process, so that cracks of the ceramic body 1 in the subsequent application process are prevented.
When the first copper layer 7 is a fired copper layer comprising copper and glass, the glass content of the inner surface and the outer surface of the first copper layer 7 is higher than the glass content of the rest of the first copper layer 7, the inner surface of the first copper layer 7 is the surface facing the ceramic body 1, the outer surface of the first copper layer 7 is the surface facing the second copper layer 8, because when the first copper layer 7 is prepared by firing, the glass tends to move to the inner and outer boundaries of the copper paste due to the effect of high temperature, the glass content of the inner surface and the outer surface of the first copper layer 7 is higher, more glass is clearly arranged on the inner surface and the outer surface of the first copper layer 7 by means of SEM (scanning electron microscope), and the glass arrangement of the inner surface of the first copper layer 7 is more orderly than the rest of the glass arrangement of the first copper layer 7, and the bonding force between the first copper layer 7 and the ceramic body 1 can be increased by the glass on the inner surface and the ceramic body 1.
When the first copper layer 7 is prepared by sintering, copper oxide is formed in the first copper layer 7, the content of copper oxide on the outer surface of the first copper layer 7 is higher than that of copper oxide on the rest of the first copper layer 7, and the oxygen content on the outer surface of the first copper layer 7 is higher than that of the rest of the first copper layer 7. The copper oxide content and the oxygen content of the first copper layer 7 gradually increase in the thickness direction from the inner surface to the outer surface, and the copper oxide or oxygen content in the first copper layer 7 can be measured by an instrument such as an energy spectrometer.
In a specific embodiment, the second copper layer 8 is a fired copper layer containing copper and glass, the thickness of the second copper layer 8 is preferably 3-5 μm, the copper paste used for preparing the second copper layer 8 may include copper powder, glass and resin, the process for preparing the copper layer by the firing method is mature, the cost is low, the thickness of the second copper layer 8 can be reduced because the second copper layer 8 mainly plays a role in isolation, thereby reducing the cost, reducing the size of the whole multilayer ceramic capacitor, and the second copper layer 8 with the thickness of 3-5 μm can have better isolation.
When the second copper layer 8 is a fired copper layer containing copper and glass, although voids are generated in the firing process of the second copper layer 8, due to the isolation of the second copper layer 8, even if nickel metal remains in the voids of the second copper layer 8, the generated internal stress cannot act on the ceramic body 1. The glass content of the inner surface and the outer surface of the second copper layer 8 is higher than that of the rest positions of the second copper layer 8, the inner surface of the second copper layer 8 faces the first copper layer 7, the outer surface of the second copper layer 8 faces the first copper layer 7, when the second copper layer 8 is prepared by burning, due to the effect of high temperature, the glass tends to move to the inner boundary and the outer boundary of copper paste, the glass content of the inner surface and the outer surface of the second copper layer 8 is higher, the inner surface and the outer surface of the second copper layer 8 are clearly seen to be provided with more glass by means of SEM (scanning electron microscope), the glass arrangement of the inner surface of the second copper layer 8 is more regular than that of the rest positions, the glass content of the inner surface of the second copper layer 8 is higher through the glass located on the inner surface and the first copper layer 7, the bonding force between the second copper layer 8 and the first copper layer 7 can be increased, the bonding force between the second copper layer 8 and the nickel layer 8 can be increased through the bonding force between the glass located on the outer surface and the subsequent nickel layer.
The glass content at the junction of the outer surface of the first copper layer 7 and the inner surface of the second copper layer 8 is higher than the glass content at the rest of the first copper layer 7 and the second copper layer 8, and since the first copper layer 7 and the second copper layer 8 are formed by burning, the glass tends to move to the inner and outer boundaries of the copper paste, so that the glass content at the junction of the outer surface of the first copper layer 7 and the inner surface of the second copper layer 8 is the highest.
When the second copper layer 8 is prepared by sintering, copper oxide is formed in the second copper layer 8, the content of copper oxide on the outer surface of the second copper layer 8 is higher than that of copper oxide on the rest of the second copper layer 8, and the oxygen content on the outer surface of the second copper layer 8 is higher than that of copper oxide on the rest of the second copper layer 8. The copper oxide content and the oxygen content of the second copper layer 8 gradually increase in the thickness direction from the inner surface to the outer surface, and the copper oxide or oxygen content in the second copper layer 8 can also be measured by an energy spectrometer instrument.
In a specific embodiment, the second copper layer 8 has a higher compactness than the first copper layer 7, which refers to the tightness of the particles in the first copper layer 7 and the second copper layer 8. The densification of the second copper layer 8 may be achieved by the particle size of the copper in the second copper layer 8 being smaller than the particle size of the copper in the first copper layer 8 or by the sintering temperature of the second copper layer 8 being greater than the sintering temperature of the first copper layer 7. The higher the compactness is, the fewer voids are in the first copper layer 7 and the second copper layer 8, and by controlling the compactness of the second copper layer 8 to be higher than that of the first copper layer 7, the voids in the second copper layer 8 can be reduced, and when the nickel layer 9 is prepared by an electroplating process, nickel liquid of the electroplating process permeates the second copper layer 8, so that the thermal shrinkage stress of materials of the second copper layer 8 and the nickel layer 9 caused by soldering tin operation in the subsequent application process is reduced. In addition, the compactness of the second copper layer 8 is controlled to be higher than that of the first copper layer 7, so that the outer surface of the second copper layer 8 is smoother, the nickel liquid infiltration of an electroplating process is reduced, the residual liquid on the rough surface of the second copper layer 8 is reduced, the phenomenon of tin spraying caused by gasification of cavities generated by high temperature of soldering tin is avoided when the multilayer ceramic capacitor is applied, and the phenomenon of short circuit of a circuit board applied to the multilayer ceramic capacitor caused by tin spraying is further avoided.
In a preferred embodiment, the second copper layer 8 is an electroplated copper layer containing pure copper, the thickness of the second copper layer 8 is preferably 1-2 μm, the compactness of the second copper layer 8 is higher than that of the first copper layer 7, the copper purity of the electroplated copper layer is higher, and the electroplated copper layer does not contain resin, glass and other components, so that the flattened compactness can be achieved, the second copper layer 8 is a flattened copper layer, the surface residual liquid can be avoided, the compactness of the second copper layer 8 prepared by an electroplating mode can be obviously improved, the compactness of the second copper layer can be far higher than that of the first copper layer 7, and therefore the material thermal shrinkage stress of the second copper layer 8 and the nickel layer 9 caused by soldering tin operation in the subsequent application process is reduced, and the phenomenon of tin spraying caused by cavity gasification generated by high temperature of soldering tin is avoided.
The second copper layer 8 prepared by adopting the electroplating mode, the particle size of copper in the second copper layer 8 is smaller than that of copper in the first copper layer 7, so that the compactness of the second copper layer 8 is further higher than that of the first copper layer 7, the material heat shrinkage stress of the second copper layer 8 and the nickel layer 9 caused by soldering tin operation in the subsequent application process is further reduced, and the phenomenon of tin spraying caused by cavity gasification generated by high temperature of soldering tin is avoided.
In a preferred embodiment, referring to fig. 5-7, the first external electrode 5 and/or the second external electrode 6 further includes a first silver layer 11, where the first silver layer 11 is disposed between the ceramic body 1 and the first copper layer 7 and electrically connects the corresponding first internal electrode 2 and the second internal electrode 3, the conductivity of silver is higher, the first silver layer 11 can be better electrically connected with the first internal electrode 2 and the second internal electrode 3, the first silver layer 11 can be formed by sintering, and the first silver layer 11 can play a role of buffering due to the softer texture of the first silver layer 11, so that the bending force of the substrate attached to or welded to the multilayer ceramic capacitor is dispersed during the application process of the multilayer ceramic capacitor. The first silver layer 11 is formed only on the end face of the ceramic body 1, and the thickness of the first silver layer 11 is greater than that of the first copper layer 7, so that a better buffering effect can be achieved.
The application also provides a preparation method of the multilayer ceramic capacitor, which comprises the following steps: steps S1-S2.
Step S1: a ceramic body 1 is provided comprising a first internal electrode 2, a second internal electrode 3, and a dielectric layer 4 between said first internal electrode 2 and said second internal electrode 3, arranged in a stack.
The ceramic body 1 may be formed by known methods and will not be described in detail herein.
Step S2: a first external electrode 5 and a second external electrode 6 are formed on the ceramic body 1, the first external electrode 5 is electrically connected with the first internal electrode 2, the second external electrode 6 is electrically connected with the second internal electrode 3, and the first external electrode 5 and/or the second external electrode 6 comprise a first copper layer 7, a second copper layer 8, a nickel layer 9 and a tin layer 10 which are sequentially laminated from inside to outside from the ceramic body 1.
In the first external electrode 5 and/or the second external electrode 6 of the multilayer ceramic capacitor prepared by the method, the second copper layer 8 is added between the first copper layer 7 and the nickel layer 9 to form a double-layer copper external electrode structure, copper of the second copper layer 8 fills most of cavities formed by the first copper layer 7 during preparation, even all cavities are formed, the second copper layer 8 effectively isolates the first copper layer 7 from the nickel layer 9, so that the problem that nickel liquid of a subsequent electroplating process permeates into the first copper layer 7 is solved, various performances of the first copper layer 7 and the second copper layer 8 are basically the same and have better compatibility in the subsequent application process of the multilayer ceramic capacitor, even if the thermal expansion coefficient or the thermal shrinkage rate of the second copper layer 8 and the nickel layer 9 are different, due to the isolation effect of the second copper layer 8, the generated internal stress cannot act on the ceramic body 1, thereby effectively reducing the internal stress of the first copper layer 7 and the ceramic body 1, reducing the thermal shrinkage stress (thermal stress) of materials in the process, and avoiding cracks caused by overlarge residual stress of the ceramic body 1.
In one embodiment, the first copper layer 7 is formed by the following method: copper paste is adhered to the ceramic body 1, and the first copper layer 7 is formed by firing. The second copper layer 8 is formed by the following method: copper paste is adhered to the first copper layer 7, and the second copper layer 8 is formed by firing.
Wherein the copper pastes for forming the first copper layer 7 and the second copper layer 8 each comprise copper powder, glass and resin, wherein the copper powder comprises spherical copper powder and/or flake copper powder, the flake copper powder for forming the second copper layer 8 is smaller in size than the flake copper powder for forming the first copper layer 7, and the spherical copper powder for forming the second copper layer 8 is smaller in size than the spherical copper powder for forming the first copper layer 7. Preferably, the size of the flake copper powder used for forming the first copper layer 7 is 7-9 μm, the size of the flake copper powder used for forming the second copper layer 8 is 2-3 μm, the size of the flake copper powder is the size of the flake copper powder before sintering, after sintering, the size of the flake copper powder becomes smaller, but the size of the flake copper powder in the second copper layer 8 is still smaller than the size of the flake copper powder in the first copper layer 7, thereby obviously improving the compactness of the second copper layer 8, reducing the thermal shrinkage stress of the materials of the second copper layer 8 and the nickel layer 9 caused by soldering operation in the subsequent application process, enabling the outer surface of the second copper layer 8 to be smoother, reducing the infiltration of nickel liquid in the electroplating process, reducing the residual liquid on the rough surface of the second copper layer 8, and avoiding the phenomenon of tin spraying caused by the gasification of cavities generated by the high temperature of soldering tin during the application of the multilayer ceramic capacitor.
In another embodiment, the first copper layer 7 is formed by the following method: copper paste is adhered to the ceramic body 1, and the first copper layer 7 is formed by firing. The second copper layer 8 is formed by the following method: the second copper layer 8 is formed on the first copper layer 7 by an electroplating method. Wherein the copper paste for forming the first copper layer 7 comprises copper powder, glass and resin, and the second copper layer 8 for electroplating is pure copper. The copper purity of the electroplated copper layer is better, components such as resin and glass are not contained, so that the smooth compactness can be achieved, the second copper layer 8 is a smooth copper layer, residual liquid on the surface can be avoided, the compactness of the second copper layer 8 prepared in an electroplating mode can be obviously improved, the compactness of the second copper layer can be far higher than that of the first copper layer 7, the thermal shrinkage stress of materials of the second copper layer 8 and the nickel layer 9 caused by soldering tin operation in the subsequent application process is reduced, and the phenomenon of tin spraying caused by cavity gasification generated by high temperature of soldering tin is avoided.
In a specific embodiment, step S2 further includes: first, a first silver layer 11 which is electrically connected with a first inner electrode 2 and a second inner electrode 3 is formed on the ceramic body 1 in a burning manner, then a first copper layer 7, a second copper layer 8, a nickel layer 9 and a tin layer 10 are formed on the first silver layer 11, the inner surface of the first silver layer 11 faces the ceramic body 1, the outer surface of the first silver layer 11 faces the first copper layer 7, and the first silver layer 11 has a soft texture, so that the first silver layer 11 can play a buffering role in the application process of the multilayer ceramic capacitor, and the bending force of a substrate attached to or welded with the multilayer ceramic capacitor is dispersed.
For a further understanding of the technical solution of the present application, the following detailed description will be given in connection with more specific examples.
Example 1
In the multilayer ceramic capacitor of the present embodiment, the first copper layer 7 is a fired copper layer containing copper and glass, and the second copper layer 8 is also a fired copper layer containing copper and glass.
The method for manufacturing the multilayer ceramic capacitor of the present embodiment includes the following steps.
Step S11: the ceramic body 1 is provided and a copper paste is prepared, the copper paste for forming the first copper layer 7 including particulate copper powder, flake copper powder (size range of 7 to 9 μm), glass and resin, and the copper paste for forming the second copper layer 88 including particulate copper powder, flake copper powder (size range of 2 to 3 μm), glass and resin.
Step S21: the copper paste for forming the first copper layer 7 is adhered to the ceramic body 1, wherein the resin plays a role of adhesion, and then the copper paste is once baked, the adhesion force is increased by increasing the engagement of glass with the ceramic body 1, the resin in the copper paste volatilizes from the surface of the copper paste during the sintering process to form voids, and when the copper paste is once baked, the glass tends to flow to the inner and outer boundaries of the copper paste, and finally the first copper layer 7 with the thickness of 15 μm is formed.
Step S31: a copper paste for forming the second copper layer 8 was adhered to the first copper layer 7, and then the copper paste was secondarily burned to finally form the second copper layer 8 having a thickness of 5 μm.
Step S41: electroplating nickel on the second copper layer 8 to finally form a nickel layer 9 with a thickness of 5 μm;
step S51: tin was electroplated on the nickel layer 9, and finally a tin layer 10 having a thickness of 2 μm was formed.
In this embodiment, in the process of preparing the multilayer ceramic capacitor, SEM (scanning electron microscope) is adopted to scan the outer surfaces of the first copper layer 7 and the second copper layer 8 to obtain SEM images shown in fig. 8-9, as can be seen from fig. 8 and 9, voids are formed on the outer surface of the prepared first copper layer 7, the compactness of the prepared second copper layer 8 is obviously higher than that of the first copper layer 7, copper of the second copper layer 8 can fill the voids formed during the preparation of the first copper layer 7, the problem that nickel liquid of the subsequent electroplating process permeates into the first copper layer 7 is solved, and in the subsequent application process of the multilayer ceramic capacitor, the generated internal stress cannot act on the ceramic body 1 due to the isolation effect of the second copper layer 8, so that the internal stress of the first copper layer 7 and the ceramic body 1 is effectively reduced, the thermal shrinkage stress of the material in the soldering process is reduced, and cracks of the ceramic body 1 due to overlarge residual stress are avoided.
Example 2
In the multilayer ceramic capacitor of the present embodiment, the first copper layer 7 is a fired copper layer containing copper and glass, and the second copper layer 8 is an electroplated copper layer containing pure copper.
The method for manufacturing the multilayer ceramic capacitor of the present embodiment includes the following steps.
Step S11: the ceramic body 1 is provided and the copper paste used to form the first copper layer 7 comprises particulate copper powder, flake copper powder (size range 7-9 μm), glass and resin.
Step S21: the copper paste for forming the first copper layer 7 is adhered to the ceramic body 1, wherein the resin plays a role of adhesion, and then the copper paste is once baked, the adhesion force is increased by increasing the engagement of glass with the ceramic body 1, the resin in the copper paste volatilizes from the surface of the copper paste during the sintering process to form voids, and when the copper paste is once baked, the glass tends to flow to the inner and outer boundaries of the copper paste, and finally the first copper layer 7 with the thickness of 15 μm is formed.
Step S31: copper was electroplated on the first copper layer 7, eventually forming a second copper layer 8 having a thickness of 2 μm.
Step S41: electroplating nickel on the second copper layer 8 to finally form a nickel layer 9 with a thickness of 5 μm;
step S51: tin was electroplated on the nickel layer 9, and finally a tin layer 10 having a thickness of 2 μm was formed.
In this embodiment, in the process of manufacturing the multilayer ceramic capacitor, scanning is performed on the outer surface of the second copper layer 8 by using an SEM (scanning electron microscope) to obtain an SEM image shown in fig. 10, and as can be seen from fig. 10, compared with the second copper layer 8 of embodiment 1, the compactness of the second copper layer 8 obtained by the electroplating method in this embodiment is further improved, so that the second copper layer 8 can be smooth, the second copper layer 8 can be made to be a smooth copper layer, and the surface residual liquid can be avoided, thereby reducing the thermal shrinkage stress of the materials of the second copper layer 8 and the nickel layer 9 caused by the soldering operation in the subsequent application process, and avoiding the phenomenon of tin spraying caused by the gasification of voids generated by the high temperature of the soldering tin.
Example 3
The production method of the multilayer ceramic capacitor of this example is substantially the same as that of example 1, except that: the first external electrode 5 and the second external electrode 6 further comprise a first silver layer 11, and the first silver layer 11 is disposed between the ceramic body 1 and the first copper layer 7 and electrically connects the corresponding first internal electrode 2 and the second internal electrode 3.
The method for manufacturing the multilayer ceramic capacitor of the present embodiment includes the following steps.
Step S11: as in example 1.
Step S61: a silver paste is prepared, the silver paste comprises granular silver powder, glass and resin, the silver paste is adhered on the ceramic body 1, and then the silver paste is burnt to finally form a first silver layer 11 with the thickness of 2 mu m.
Step S21: the difference from example 1 is that: a copper paste for forming the first copper layer 7 is adhered to the first silver layer 11.
Steps S31-S51: as in example 1.
In this embodiment, by disposing the first silver layer 11 with a softer texture between the ceramic body 1 and the first copper layer 7, the first silver layer 11 can play a role of buffering during the application process of the multilayer ceramic capacitor, and disperse the bending force of the substrate attached or soldered to the multilayer ceramic capacitor.
In all the above embodiments, the second copper layer 8 may be replaced by a second silver layer, and the related structure and preparation method thereof are substantially the same as those of the embodiments, and will not be described herein. It is emphasized that, because the conductivity of silver is higher than that of copper, better electrical connection performance can be achieved with silver; because the density of silver is greater than that of copper, the compactness of the second silver layer under the same conditions is higher than that of the first copper layer 7, so that the cavity left by the first copper layer 7 can be better filled, and the better effect of preventing tin liquid or water vapor from penetrating is achieved; the second silver layer after being burnt has better ductility, when the multilayer ceramic capacitor is subjected to external mechanical stress, the second silver layer can generate elastic or plastic deformation to play a better buffering role, so that the stress generated by the outside can be better dispersed, and the protection effect can be better formed on the first copper layer. In addition, when the first external electrode 5 and the second external electrode 6 further include the first silver layer 11, the first silver layer 11 and the second silver layer may be formed on the inner surface and the outer surface of the first copper layer 7, respectively, so that a double-layer buffer effect may be formed, and the effect is better.
While embodiments of the present application have been shown and described, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that changes, modifications, substitutions and alterations may be made therein by those of ordinary skill in the art without departing from the spirit and scope of the application, all such changes being within the scope of the appended claims.

Claims (23)

1. A multilayer ceramic capacitor, comprising:
the ceramic body comprises a first inner electrode, a second inner electrode and a dielectric layer, wherein the first inner electrode and the second inner electrode are arranged in a stacked mode;
the first external electrode is electrically connected with the first internal electrode, and the second external electrode is electrically connected with the second internal electrode;
the first external electrode and/or the second external electrode comprises a first copper layer, a second copper layer or a second silver layer, a nickel layer and a tin layer which are sequentially laminated from inside to outside from the ceramic body;
and a plurality of holes are formed in the first copper layer, part of the holes are filled with the second copper layer or the second silver layer, and the compactness of the second copper layer or the second silver layer is higher than that of the first copper layer.
2. The multilayer ceramic capacitor of claim 1, wherein the first copper layer is a fired copper layer comprising copper and glass.
3. The multilayer ceramic capacitor according to claim 2, wherein the thickness of the first copper layer is 10-15 μm.
4. The multilayer ceramic capacitor of claim 2, wherein the inner and outer surfaces of the first copper layer have a higher glass content than the remaining locations of the first copper layer.
5. The multilayer ceramic capacitor according to claim 2, wherein copper oxide is formed in the first copper layer, and the copper oxide content of the outer surface of the first copper layer is higher than the copper oxide content of the remaining position of the first copper layer, and the oxygen content of the outer surface of the first copper layer is higher than the oxygen content of the remaining position of the first copper layer.
6. The multilayer ceramic capacitor according to claim 5, wherein the first copper layer has a copper oxide content and an oxygen content gradually increasing in a thickness direction from the inner surface to the outer surface.
7. The multilayer ceramic capacitor of claim 2, wherein the second copper layer is a fired copper layer comprising copper and glass or the second silver layer is a fired silver layer comprising silver and glass.
8. The multilayer ceramic capacitor according to claim 7, wherein the thickness of the second copper layer or the second silver layer is 3-5 μm.
9. The multilayer ceramic capacitor of claim 7, wherein the glass content of the inner and outer surfaces of the second copper or silver layer is higher than the glass content of the remaining locations of the second copper or silver layer.
10. The multilayer ceramic capacitor of claim 9, wherein the glass content at the interface of the outer surface of the first copper layer and the inner surface of the second copper layer or second silver layer is higher than the glass content at the rest of the first copper layer and second copper layer or second silver layer.
11. The multilayer ceramic capacitor according to claim 7, wherein copper oxide or silver oxide is formed in the second copper layer or the second silver layer, and the copper oxide or silver oxide content of the outer surface of the second copper layer or the second silver layer is higher than the copper oxide or silver oxide content of the remaining portion of the second copper layer or the second silver layer, and the oxygen content of the outer surface of the second copper layer or the second silver layer is higher than the oxygen content of the remaining portion of the second copper layer or the second silver layer.
12. The multilayer ceramic capacitor according to claim 11, wherein the second copper layer or the second silver layer gradually increases in copper oxide or silver oxide content and oxygen content in a thickness direction from the inner surface to the outer surface.
13. The multilayer ceramic capacitor of claim 7, wherein the particle size of copper in the second copper layer is smaller than the particle size of copper in the first copper layer or the sintering temperature of the second copper layer is greater than the sintering temperature of the first copper layer.
14. The multilayer ceramic capacitor according to claim 2, wherein the second copper layer is an electroplated copper layer containing pure copper or the second silver layer is an electroplated silver layer containing pure silver.
15. The multilayer ceramic capacitor according to claim 14, wherein the thickness of the second copper layer or the second silver layer is 1-2 μm.
16. The multilayer ceramic capacitor of claim 14, wherein the particle size of copper in the second copper layer is smaller than the particle size of copper in the first copper layer, further rendering the second copper layer more dense than the first copper layer.
17. The multilayer ceramic capacitor of claim 1, wherein the first and/or second external electrodes further comprise a first silver layer disposed between the ceramic body and the first copper layer and electrically connecting the corresponding first and second internal electrodes.
18. A method for manufacturing a multilayer ceramic capacitor, comprising:
providing a ceramic body comprising a first internal electrode, a second internal electrode, and a dielectric layer between the first internal electrode and the second internal electrode;
forming a first external electrode and a second external electrode on the ceramic body, wherein the first external electrode is electrically connected with the first internal electrode, the second external electrode is electrically connected with the second internal electrode, and the first external electrode and/or the second external electrode comprises a first copper layer, a second copper layer or a second silver layer, a nickel layer and a tin layer which are sequentially laminated from inside to outside from the ceramic body;
and a plurality of holes are formed in the first copper layer, part of the holes are filled with the second copper layer or the second silver layer, and the compactness of the second copper layer or the second silver layer is higher than that of the first copper layer.
19. The method of manufacturing a multilayer ceramic capacitor according to claim 18, wherein the first copper layer is formed by: adhering copper paste on the ceramic body, and forming the first copper layer through burning;
the second copper layer or the second silver layer is formed by the following method: and adhering copper paste or silver paste on the first copper layer, and forming the second copper layer or the second silver layer by burning.
20. The method for producing a multilayer ceramic capacitor according to claim 19, wherein copper pastes for forming the first copper layer and the second copper layer each include copper powder, glass, and resin, and wherein the copper powder includes spherical copper powder and/or flake copper powder, and wherein the copper powder for forming the second copper layer has a smaller size than the copper powder for forming the first copper layer.
21. The method of manufacturing a multilayer ceramic capacitor according to claim 20, wherein the size of the copper flake used for forming the first copper layer is 7-9 μm and the size of the copper flake used for forming the second copper layer is 2-3 μm.
22. The method of manufacturing a multilayer ceramic capacitor according to claim 18, wherein the first copper layer is formed by: adhering copper paste on the ceramic body, forming the first copper layer through burning, wherein the copper paste for forming the first copper layer comprises copper powder, glass and resin;
the second copper layer or the second silver layer is formed by the following method: and forming the second copper layer or the second silver layer on the first copper layer by an electroplating method, wherein the second copper layer or the second silver layer formed by electroplating is pure copper or pure silver.
23. The method of manufacturing a multilayer ceramic capacitor according to claim 18, wherein the method of manufacturing the first external electrode and/or the second external electrode further comprises: first, forming a first silver layer electrically connected with a first inner electrode and a second inner electrode on the ceramic body in a burning mode, and then forming a first copper layer, a second copper layer or a second silver layer, a nickel layer and a tin layer on the first silver layer.
CN202210950501.0A 2022-08-09 2022-08-09 Multilayer ceramic capacitor and method for manufacturing the same Active CN115223792B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210950501.0A CN115223792B (en) 2022-08-09 2022-08-09 Multilayer ceramic capacitor and method for manufacturing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210950501.0A CN115223792B (en) 2022-08-09 2022-08-09 Multilayer ceramic capacitor and method for manufacturing the same

Publications (2)

Publication Number Publication Date
CN115223792A CN115223792A (en) 2022-10-21
CN115223792B true CN115223792B (en) 2023-08-11

Family

ID=83615216

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210950501.0A Active CN115223792B (en) 2022-08-09 2022-08-09 Multilayer ceramic capacitor and method for manufacturing the same

Country Status (1)

Country Link
CN (1) CN115223792B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115762995B (en) * 2022-11-04 2023-08-08 广东泛瑞新材料有限公司 Ceramic magnetic core and preparation method and application thereof
CN116721864A (en) * 2023-07-26 2023-09-08 广东微容电子科技有限公司 Embedded chip type multilayer ceramic capacitor and preparation method thereof
CN116741534A (en) * 2023-07-26 2023-09-12 广东微容电子科技有限公司 Chip type multilayer ceramic capacitor and preparation method thereof
CN116884766A (en) * 2023-07-26 2023-10-13 广东微容电子科技有限公司 Chip three-terminal capacitive filter and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000049034A (en) * 1998-07-28 2000-02-18 Murata Mfg Co Ltd Ceramic electronic component and manufacture of the same
CN103680663A (en) * 2012-09-03 2014-03-26 三星电机株式会社 Conductive paste composition for external electrode, multilayered ceramic component including the same and manufacturing method thereof
CN104538157A (en) * 2014-12-19 2015-04-22 广东风华高新科技股份有限公司 Terminal electrode of chip inductor, manufacturing method thereof and chip inductor
CN110880413A (en) * 2018-09-06 2020-03-13 三星电机株式会社 Multilayer ceramic electronic component
CN114373633A (en) * 2022-01-22 2022-04-19 池州昀冢电子科技有限公司 Multilayer ceramic capacitor and method for manufacturing the same
CN217061779U (en) * 2021-09-28 2022-07-26 广东风华高新科技股份有限公司 Multilayer ceramic capacitor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000049034A (en) * 1998-07-28 2000-02-18 Murata Mfg Co Ltd Ceramic electronic component and manufacture of the same
CN103680663A (en) * 2012-09-03 2014-03-26 三星电机株式会社 Conductive paste composition for external electrode, multilayered ceramic component including the same and manufacturing method thereof
CN104538157A (en) * 2014-12-19 2015-04-22 广东风华高新科技股份有限公司 Terminal electrode of chip inductor, manufacturing method thereof and chip inductor
CN110880413A (en) * 2018-09-06 2020-03-13 三星电机株式会社 Multilayer ceramic electronic component
CN217061779U (en) * 2021-09-28 2022-07-26 广东风华高新科技股份有限公司 Multilayer ceramic capacitor
CN114373633A (en) * 2022-01-22 2022-04-19 池州昀冢电子科技有限公司 Multilayer ceramic capacitor and method for manufacturing the same

Also Published As

Publication number Publication date
CN115223792A (en) 2022-10-21

Similar Documents

Publication Publication Date Title
CN115223792B (en) Multilayer ceramic capacitor and method for manufacturing the same
US9275804B2 (en) Ceramic electronic component and method for producing the same
JP5420060B2 (en) Capacitor
JP5099609B2 (en) Multilayer electronic components
KR102426098B1 (en) Chip-type ceramic electronic component
JP2006186316A (en) Ceramic electronic component and laminated ceramic capacitor
US7211533B2 (en) Oxide porcelain composition, ceramic multilayer substrate, and ceramic electronic component
WO1993008672A1 (en) Manufacture of multilayer ceramic part, and multilayer ceramic part
US20150179340A1 (en) Multilayer ceramic capacitor and method of fabricating the same
KR20130065199A (en) Conductive paste for external electrode, multi-layered ceramic electronic parts fabricated by using the same and fabricating method thereof
JP2021022723A (en) Multilayer electronic component
KR970009772B1 (en) Multi-layer capacitor & manufacturing method for the same
JP2013110372A (en) Chip type electronic component
JP2000216046A (en) Laminated ceramic electronic component
JPH10135073A (en) Composite ceramic electronic part and its manufacture
KR100800509B1 (en) Conductive paste and multi-layer ceramic substrate
CN115910602A (en) Multilayer ceramic capacitor and preparation method thereof
JP2012079864A (en) Ceramic electronic component
JP2001338830A (en) Conductive paste and laminated ceramic capacitor using the same
JP4442135B2 (en) Manufacturing method of ceramic electronic component
JP2000077260A (en) Laminated ceramic electronic component and its manufacture
JP2017147430A (en) Multilayer capacitor and manufacturing method for the same
JP2002329638A (en) Laminated type electronic component and its manufacturing method
JP2555638B2 (en) Method for manufacturing multilayer ceramic substrate
JP3554957B2 (en) Multilayer ceramic electronic component and method of manufacturing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant