CN112750551B - Electrode paste, electrode, ceramic electronic component including the same, and method of manufacturing the component - Google Patents
Electrode paste, electrode, ceramic electronic component including the same, and method of manufacturing the component Download PDFInfo
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Abstract
The invention provides an electrode paste, an electrode, a ceramic electronic component containing the electrode paste and a preparation method of the component, wherein the electrode paste comprises the following components: conductive particles, a composite sintering aid, a resin, and an organic solvent; wherein, the composite sintering aid comprises: copper-containing compounds, barium salts, calcium salts, and manganese salts. In addition, the invention also provides an electrode formed by burning the electrode paste, a ceramic electronic component containing the electrode as an external electrode and a preparation method thereof. The outer electrode of the ceramic electronic component has good conductivity and good bonding property with the ceramic body, so that the yield of the ceramic electronic component is improved.
Description
Technical Field
The present invention relates to an electrode paste, particularly to an electrode paste for a ceramic electronic component, an electrode formed by firing the electrode paste, a ceramic electronic component including the electrode, and a method for manufacturing the ceramic electronic component.
Background
With the increasing demand for portable electronic products, electric vehicles, and automotive electronics, the application area of passive components is also expanding. Common passive components include resistors, capacitors and inductors, and a multi-layer ceramic capacitor (MLCC) is most popular among them, which can resist high voltage and high heat, has a wide operating temperature range and a low loss rate in high frequency use. Generally, a ceramic electronic component such as a multilayer ceramic capacitor includes a ceramic body formed by overlapping a plurality of dielectric materials and internal electrodes, and external electrodes covering the surface of the ceramic body; the external electrode is generally formed by firing an electrode paste containing conductive metal, glass frit, resin, and solvent at a high temperature.
In the electrode paste, the glass powder is mainly used for providing a liquid phase in the sintering process, so that the conductive metal can be sintered into a metal layer at a lower temperature and reacts with the interface of the ceramic body to generate bonding, and the bonding property of the conductive metal and the ceramic body is further improved. However, the glass component is easy to gather at the interface, so that the connection between the inner electrode and the outer electrode is poor, and the glass is compatible and easy to discharge, so that poor weldability can occur when the second outer electrode is formed by electroplating; furthermore, the glass frit usually generates bubbles during the sintering process, which causes the obtained external electrode to have air holes and affects the conductivity thereof. Particularly, in recent years, driven by the demands of miniaturization, high performance and high reliability of products, it is important to improve the electrical conductivity of the ceramic electronic device to reduce the device reliability due to transmission loss and heat generation, and to improve the interface bonding force between the external electrode and the ceramic body to prevent the device from failing due to the peeling of the external electrode during use.
In order to solve the above problems, U.S. Pat. No. 8675343 discloses an electrode paste for external electrodes, which must include a special conductive amorphous metallic glass, denoted by a (Cu, ni) -bZr-c (Al, sn); wherein the sum of a to c is 100 weight percent (wt%), a is between 20 and 60, b is between 20 and 60, and c is between 2 and 25. Although the conductive amorphous metallic glass can solve the problem that the common glass floats in the burning process to cause the subsequent electroplating defect, the manufacturing cost of the conductive amorphous metallic glass is high, and the conductive amorphous metallic glass is not beneficial to industrial utilization.
Also, for example, the chinese patent application publication No. 101658929 discloses a copper-nickel alloy powder for preparing an MLCC external electrode, which is prepared by forming a spherical copper-nickel alloy by a vapor deposition method after melting a copper-nickel alloy raw material; wherein, a part of the spherical copper-nickel alloy is ground into sheet copper-nickel alloy, thereby increasing the contact area between the outer electrode and the surface of the ceramic body to improve the bonding strength of the outer electrode and the ceramic body; however, the cu — ni alloy powder is manufactured through complicated processes, and the high cost of the vapor deposition method is included, which still hinders the possibility of commercial development.
Disclosure of Invention
In view of the technical drawbacks of the electrode paste, the present invention provides an electrode paste that can avoid the problem of glass overflow from a predetermined coating surface during the baking process of the electrode paste.
Another object of the present invention is to provide an electrode paste, which can prevent the generation of bubbles during the burning process of the electrode paste, and improve the bonding property and conductivity between the formed external electrode and the ceramic body.
Another objective of the present invention is to provide an electrode paste, which has good adhesion between the external electrode formed by sintering and the ceramic body, and can improve the peeling problem of the external electrode during the use process and the yield of the ceramic electronic device.
Another object of the present invention is to provide an electrode paste which does not require a complicated process, can solve the problem of increased manufacturing costs due to the use of special materials, has the advantage of lower costs, and thus has a better commercial product development potential.
To achieve the above object, the present invention provides an electrode paste, comprising: conductive particles, a composite sintering aid, a resin, and an organic solvent; wherein, the composite sintering aid comprises: copper-containing compounds, barium salts, calcium salts, and manganese salts.
According to the invention, the copper-containing compound, the barium salt, the calcium salt and the manganese salt contained in the composite sintering aid and the metal oxide existing on the surface of the conductive particle generate eutectic reaction, and the obtained eutectic substance can help the conductive particle to diffuse in the sintering process, so that the structure of the electrode formed by the electrode paste is densified; when the electrode is used as an outer electrode of a ceramic electronic component, the interface bonding property with the ceramic body can be improved. In addition, the eutectic compound only forms a thin layer on the surface of the electrode paste, and a large amount of glass is not gathered at the interface of the electrode paste and the ceramic body, so that the resistivity of the outer electrode can be reduced, the conductivity of the outer electrode can be improved, and the problem that the glass overflows the predetermined coating surface can be solved.
Preferably, the copper-containing compound contained in the composite sintering aid can contain copper oxide (CuO), copper acetate (Cu (CH) 3 COO) 2 ) Or copper oxalate (CuC) 2 O 4 ) But are not limited thereto; the barium salt contained in the composite sintering aid comprises barium carbonate (BaCO) 3 ) Barium acetate (Ba (CH) 3 COO) 2 ) Or barium oxalate (BaC) 2 O 4 ) But are not limited thereto; the calcium salt contained in the composite sintering aid contains calcium carbonate (CaCO) 3 ) Calcium acetate (Ca (CH)) 3 COO) 2 ) Or calcium oxalate (CaC) 2 O 4 ) But are not limited thereto; the manganese salt contained in the composite sintering aid comprises manganese carbonate (MnCO) 3 ) Manganese acetate (Mn (CH) 3 COO) 2 ) Or manganese oxalate (MnC) 2 O 4 ) But is not limited thereto.
In order to form an electrode having better compactness by using the electrode paste containing the composite sintering aid, the copper-containing compound is preferably used in an amount of 0.5wt% to 65wt%, based on the total weight of the composite sintering aid.
In order to form an external electrode having a low specific resistance with respect to the ceramic body, the barium salt is preferably used in an amount of 4.9wt% to 89wt%, based on the total weight of the composite sintering aid.
In order to provide a stronger bonding force between the external electrode formed from the electrode paste containing the composite sintering aid and the ceramic body, preferably, the calcium salt is used in an amount of 0.5wt% to 30wt%, based on the total weight of the composite sintering aid; the calcium salt can interdiffuse with the components contained in the ceramic body to form chemical bonding, so that the connectivity of the outer electrode and the ceramic body can be improved.
In order to provide better connectivity between the external electrode formed by the electrode paste containing the composite sintering aid and the internal electrode in the ceramic body, the manganese salt is preferably used in an amount of 0.1wt% to 10wt%, based on the total weight of the composite sintering aid. Because the melting point of the manganese salt is lower, the melting temperature of the composite sintering aid can be reduced by adding the manganese salt.
In order to further reduce the sintering temperature of the electrode paste during the sintering process, preferably, the composite sintering aid further comprises a modifier, and the modifier comprises lithium carbonate (Li) 2 CO 3 ) Sodium carbonate (Na) 2 CO 3 ) Or potassium carbonate (K) 2 CO 3 ) But is not limited thereto. Preferably, the modifier is used in an amount of 0.1wt% to 0.5wt%, based on the total weight of the composite sintering aid.
In some embodiments, when the total of the conductive particles, the composite sintering aid, the resin, and the organic solvent is 100wt%, the content of the conductive particles is 58wt% to 75wt%, the content of the composite sintering aid is 0.5wt% to 7wt%, the content of the resin is 0.5wt% to 11wt%, and the content of the organic solvent is 10wt% to 25wt%.
Preferably, the conductive particles are copper (Cu), silver (Ag), or copper-silver (Cu-Ag alloy), but not limited thereto.
According to the present invention, the term "average particle size" as used herein refers to a particle size value corresponding to a cumulative particle size distribution percentage of the particles of 50%, i.e., D50. Specifically, the average particle diameter of the conductive particles and the appearance form of the particles are not particularly limited; preferably, the conductive particles may be spherical conductive particles having an average particle size of 0.5 micrometers (μm) to 10 μm, flake conductive particles having an average particle size of 2 μm to 10 μm, or a combination thereof. When the particle diameter of the conductive particles is within the aforementioned range, it is less likely to cause a phenomenon of severe powder agglomeration.
According to the present invention, in the composite sintering aid, the average particle size of the copper-containing compound is 10 to 500 nanometers (nm), the average particle size of the barium salt is 10 to 500nm, the average particle size of the calcium salt is 10 to 500nm, and the average particle size of the manganese salt is 10 to 500nm. When the particle size of each component in the composite sintering aid is in the range, the components are not easy to cause serious powder agglomeration.
According to the present invention, the resin may be an acrylic resin, an ethyl cellulose resin, or a combination thereof. For example, the acrylic resin may be acrylates such as poly (methyl acrylate), PMA), poly (ethyl acrylate), PEA, or derivatives thereof, methacrylates such as poly (methyl methacrylate), PMMA, poly (ethyl methacrylate), PEMA, or derivatives thereof, but is not limited thereto; the ethyl cellulose resin may be ethyl cellulose (ethyl cellulose) or derivatives thereof, but is not limited thereto. In some embodiments, if the ceramic body is subsequently coated by roll coating or dip coating, the ceramic body may be optionally coated with polymethyl methacrylate; in other embodiments, if printing is used for subsequent coating on the ceramic body, ethyl cellulose may be used.
According to the present invention, the organic solvent is not particularly limited; specifically, the organic solvent may comprise alcohols, ethers, esters, or combinations thereof. For example, the alcohol may be terpineol (terpineol), hydrogenated terpineol (hydrogenated terpineol), benzyl alcohol (benzyl alcohol), 2-ethylhexanol (2-ethyl-1-hexanol), n-octanol (1-octanol), etc., but is not limited thereto; the ether can be ethylene glycol monobutyl ether (ethylene glycol monobutyl ether), diethylene glycol monobutyl ether (diethylene glycol monobutyl ether), diethylene glycol ethyl ether (diethylene glycol monobutyl ether, also known as carbitol), etc., but is not limited thereto; the ester may be terpinyl dihydroacetate, terpinyl acetoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate [2- (2-ethoxyyethoxy) ethyl acetate ], etc., but is not limited thereto.
The electrode paste may further contain a thixotropic agent, a dispersing agent, a defoaming agent, and a leveling agent as required within a range not affecting the effects of the present invention. For example, the thixotropic agent can be polyamide wax, and the viscosity of the electrode paste can be adjusted to meet the requirements of process operation; the dispersant can be polyether phosphate, and the viscosity of the electrode paste can be adjusted to meet the requirements of process operation; the defoaming agent can be ethylene polymer, which can provide the self-defoaming capability of the electrode paste and improve the possibility of air bubbles entrained in the electrode paste in the process; the leveling agent may be a siloxane assistant having an alkyl aromatic group, which improves the surface flatness of the electrode paste after application, but is not limited thereto.
According to the invention, when preparing the electrode paste, the conductive particles, the composite sintering aid, the resin and the organic solvent can be added and mixed in any order, and can be added simultaneously or sequentially, the components with the same weight are added in one time or added in several times, and are stirred and dispersed uniformly until the preparation of the electrode paste is completed.
In addition, the invention also provides an electrode which is formed by sintering the electrode paste.
Another object of the present invention is to provide a ceramic electronic component including an electrode fired from the electrode paste and a ceramic substrate, the electrode and the ceramic substrate having excellent bondability. For example, the ceramic electronic component can be used as a chip resistor, but is not limited thereto.
To achieve the above object, the present invention further provides a ceramic electronic component, which includes: a ceramic body having a first end and a second end opposite to the first end; a plurality of internal electrodes arranged in the ceramic body, wherein two adjacent internal electrodes are respectively connected with the first end and the second end of the ceramic body; the two outer electrodes are respectively coated on the surface of the first end and the surface of the second end of the ceramic body and are electrically connected with the inner electrodes; the external electrodes include electrodes formed by baking the electrode paste.
In a specific embodiment, as shown in fig. 1, the ceramic electronic component 1 includes a ceramic body 10, the ceramic body 10 having a first end 101 and a second end 102 opposite to the first end 101; the ceramic body 10 further has a plurality of internal electrodes 103A, 103B disposed in the ceramic body 10, and two adjacent internal electrodes 103A and 103B are respectively connected to the first end 101 and the second end 102 of the ceramic body 10; in addition, the ceramic electronic component 1 further includes two external electrodes (i.e., first external electrodes 20A, 20B) respectively covering the surface of the first end 101 and the surface of the second end 102 of the ceramic body 10 and electrically connected to the internal electrodes 103A and 103B.
The invention also provides a method for manufacturing the ceramic electronic component, which comprises the following steps: step (a): preparing a ceramic body comprising a plurality of internal electrodes, wherein the internal electrodes are arranged in the ceramic body, and the ceramic body is provided with a first end and a second end opposite to the first end; step (b): preparing the electrode paste as described above; and step (c): coating the electrode paste on the surface of the first end and the surface of the second end of the ceramic body and carrying out a sintering step to obtain the ceramic electronic component; the ceramic electronic component comprises two outer electrodes, and the outer electrodes are respectively coated on the surface of the first end and the surface of the second end of the ceramic body and are electrically connected with the inner electrodes.
According to the present invention, the electrode paste used therefor contains a specific composite sintering aid which obtains an eutectic compound by causing an eutectic reaction of a copper-containing compound, barium salt, calcium salt, and manganese salt with conductive particles; the eutectic substance can replace glass powder in the existing electrode paste in the sintering process, can avoid the problem that a large amount of glass is gathered and even overflows from the contact interface between the electrode paste and the ceramic body, and can improve the interface bonding property between an outer electrode formed by the electrode paste and the ceramic body. In addition, because the electrode paste containing the specific composite sintering aid is used, glass powder does not need to be treated by steps of high-temperature hot melting, quenching, grinding and the like or conductive particles are manufactured by a vapor deposition method when the ceramic electronic element is manufactured, so that the manufacturing method of the ceramic electronic element can be simplified, special raw materials do not need to be used, the problem of high manufacturing cost is avoided, and the ceramic electronic element has commercial value.
Specifically, the coating means in step (c) may be applied using any coating means known in the art; for example, the coating method may be knife coating (dipping), roll coating, printing coating, etc. applied on the surface of the ceramic body.
Specifically, the viscosity of the electrode paste is 20 kilo-centipoise (kcps) to 165kcps. When the viscosity of the electrode paste is within the above range, the electrode paste has good operability, and is less likely to cause appearance abnormality, sagging, or sticking. In some embodiments, when the electrode paste is coated on the surface of the ceramic body by dipping, the viscosity of the electrode paste is preferably 40 to 80kcps; when the electrode paste is coated on the surface of the ceramic body in a roller mode, preferably, the viscosity of the electrode paste is 25-40 kcps; when the electrode paste is coated on the surface of the ceramic body by a printing method, the viscosity of the electrode paste is preferably 20 to 165kcps.
Specifically, the sintering temperature in the step (c) is not particularly limited, and preferably 780 ℃ to 1000 ℃, so that the obtained external electrode has a denser structure.
In some embodiments, when the metal of the conductive particles contained in the electrode paste is copper or a copper-silver alloy, the firing step in the step (c) may be performed in a nitrogen atmosphere; preferably, the nitrogen atmosphere contains not more than 100ppm of oxygen, so as to prevent oxidation of the surface of the obtained external electrode. In other embodiments, when the metal of the conductive particles contained in the electrode paste is silver, the firing step is performed in an atmospheric atmosphere.
In some embodiments, the step (c) may comprise steps (c 1) to (c 3). Step (c 1): coating the electrode paste on the surface of the first end and the surface of the second end of the ceramic body and performing a sintering step to obtain two first outer electrodes; step (c 2): plating two second external electrodes on the first external electrodes respectively; and step (c 3): and respectively plating two third external electrodes on the second external electrodes to obtain the ceramic electronic element. Therefore, the external electrodes of the ceramic electronic component comprise two first external electrodes, two second external electrodes and two third external electrodes which are formed by sintering the electrode paste; the first external electrodes are coated on the surface of the first end and the surface of the second end of the ceramic body and are electrically connected with the internal electrodes, and the second external electrodes are respectively formed between the first external electrodes and the third external electrodes. For example, the second outer electrodes may be nickel metal layers, but are not limited thereto; the third external electrode may be a tin metal layer, but is not limited thereto.
The ceramic electronic component can be applied to a tablet personal computer, a smart phone, an electric vehicle, a vehicle-mounted entertainment system, a vehicle-mounted driving safety auxiliary system and the like, but is not limited thereto.
In the specification, a range represented by "a small value to a large value" means a range from greater than or equal to the small value to less than or equal to the large value, if not specifically indicated. For example: 0.1 to 10% by weight, i.e. it means that the range thereof is "greater than or equal to 0.1 to less than or equal to 10% by weight".
Drawings
FIG. 1 is a schematic side sectional view of a ceramic electronic component according to the present invention.
FIG. 2 is a schematic sectional side view of ceramic electronic components according to examples 1-1 to 30-1.
FIG. 3 is a SEM image of the first external electrode of example 22-2.
FIG. 4 is a SEM image of the first external electrode of comparative example 2-2.
FIG. 5 is a scanning electron microscope image of the ceramic electronic component of comparative example 4-2.
Detailed Description
The following examples and comparative examples are given to illustrate embodiments of the present invention, and those skilled in the art will readily appreciate from the disclosure of the present invention that various modifications and changes can be made to the embodiments without departing from the spirit of the present invention.
Raw materials
1. Conductive particles A: spherical copper metal particles having an average particle diameter of 4 μm;
2. conductive particles B: flaky copper metal particles having an average particle diameter of 8 μm;
3. conductive particles C: spherical silver metal particles having an average particle diameter of 4 μm;
4. conductive particles D: spherical copper-silver alloy particles having an average particle diameter of 4 μm, wherein the content of silver is 80wt% and the content of copper is 20wt%, based on the total weight of the copper-silver alloy;
5. conductive particles E: spherical copper-silver alloy particles having an average particle diameter of 4 μm, wherein the silver content is 50wt% and the copper content is 50wt%, based on the total weight of the copper-silver alloy;
6. conductive particles F: spherical copper-silver alloy particles having an average particle diameter of 4 μm, wherein the silver content is 20wt% and the copper content is 80wt%, based on the total weight of the copper-silver alloy;
7. copper oxide: the average particle size is 50nm;
8. barium carbonate: the average particle size is 50nm;
9. calcium carbonate: the average particle size is 50nm;
10. manganese carbonate: the average particle size is 50nm;
11. barium acetate: the average particle size is 50nm;
12. copper acetate: the average particle size is 50nm;
13. calcium acetate: the average particle size is 50nm;
14. manganese acetate: the average particle size is 50nm;
15. barium oxalate: the average particle size is 50nm;
16. copper oxalate: the average particle size is 50nm;
17. calcium oxalate: the average particle size is 50nm;
18. manganese oxalate: the average particle size is 50nm;
19. resin A: polymethyl methacrylate;
20. resin B: ethyl cellulose;
21. organic solvent: terpineol;
22. a ceramic body: comprising BaTiO 3 The ceramic structure of (1);
23. alumina substrate (for printing and roll processing).
Preparation examples 1 to 18, comparative preparation examples 1 and 2: composite sintering aid
Composite combustion improvers of production examples 1 to 18 (hereinafter referred to as SA 1 to SA 18) and comparative production examples 1 to 2 (hereinafter referred to as CSA 1 and CSA 2) were prepared, respectively, in accordance with the compounding ratios (in wt%) shown in tables 1-1 and 1-2.
Preparation of electrode pastes of examples 1 to 30
Electrode pastes (abbreviated as E1 to E30) of examples 1 to 30 were obtained by mixing according to the compounding ratios shown in table 2, respectively. The differences between the electrode pastes of examples 1 to 30 are mainly the changes in the composite sintering aid (i.e., the composition and amount of the composite sintering aid) selected and the contents of the composite sintering aid and the conductive particles in the electrode paste.
Preparation of ceramic electronic Components of examples 1-1 to 30-1
As shown in fig. 2, the electrode pastes of examples 1 to 30 are sequentially applied to the surface of the first end 101 and the surface of the second end 102 of the ceramic body 10 in a dipping manner; then, a firing step was performed in a nitrogen atmosphere containing 10ppm of oxygen at firing temperatures listed in table 2 below, respectively, to obtain electrodes formed of the electrode paste, i.e., first external electrodes 20A, 20B; then, nickel metal layers having an average thickness of 5 μm are respectively plated on the outer side surfaces of the first external electrodes 20A and 20B as second external electrodes 30A and 30B, and then, tin metal layers having an average thickness of 10 μm are respectively plated on the outer side surfaces of the second external electrodes 30A and 30B as third external electrodes 40A and 40B, thereby finally obtaining the ceramic electronic components 1' (hereinafter, referred to as E1-1 to E30-1) of examples 1-1 to 30-1 as shown in fig. 2.
Preparation of electrode pastes of comparative examples 1 to 4
Electrode pastes (hereinafter referred to as C1 to C4) of comparative examples 1 to 4 were obtained according to the compounding ratios shown in table 2, respectively. The difference between the electrode pastes of comparative examples 1 to 4 and the previous examples is mainly that the composite sintering aid used in comparative examples 1 to 4 is a glass powder (component B-Ba-Zn-Si-Al-Na) with an average particle size of 3 μm, which is prepared by melting raw materials such as diboron trioxide, barium carbonate, zinc oxide, silicon dioxide, aluminum oxide, and sodium carbonate at a high temperature of 1200 ℃ and then pouring cold water of 25 ℃ for quenching; then, the glass powder with the average grain diameter of 3 mu m is prepared by the steps of cleaning, screening, grinding and the like.
Preparation of electrode pastes for comparative examples 5 and 6
Electrode pastes of comparative examples 5 and 6 (hereinafter referred to as C5 and C6) were obtained according to the formulation shown in Table 2. The difference between the electrode pastes of comparative examples 5 and 6 and the previous examples is mainly that the composite sintering aids selected in comparative examples 5 and 6 are composite sintering aids of CSA 1 and CSA 2, respectively.
Preparation of ceramic electronic Components of comparative examples 1-1 to 6-1
Sequentially applying the electrode pastes of comparative examples 1 to 6 to the surface of the first end and the surface of the second end of the ceramic body in a dipping manner; then, a firing step was performed in a nitrogen atmosphere containing 10ppm of oxygen at firing temperatures respectively listed in table 2 to obtain the first external electrode; then, a nickel metal layer having an average thickness of 5 μm was plated on the first external electrode as a second external electrode, and a tin metal layer having an average thickness of 10 μm was plated on the second external electrode as a third external electrode, thereby obtaining ceramic electronic components (hereinafter referred to as C1-1 to C6-1) of comparative examples 1-1 to 6-1.
Characteristic analysis of ceramic electronic component
Analysis 1: resistivity testing of the first outer electrode
After forming first external electrodes from the electrode pastes of examples 1 to 30 and comparative examples 1 to 6, the resistivity of the first external electrodes was measured using a four-point probe apparatus (model number PII-QT 5601Y), and the experimental results are shown in table 2.
Analysis 2: evaluation of denseness of first external electrode
After forming the first external electrodes from the electrode pastes of examples 1 to 30 and comparative examples 1 to 6, the degree of densification of the first external electrodes was evaluated by fluorescence permeation destructive physical analysis, and the evaluation results are listed in table 2. If the fluorescence permeation amount of the cross section of the first outer electrode is 0%, the compactness of the first outer electrode is judged to be good and is represented as 'good' in table 2; if the fluorescence permeation quantity of the cross section of the first outer electrode is more than 0% and less than or equal to 5%, the compactness is judged to be medium, and the cross section is represented as 'shangkong' in table 2; if the fluorescence permeation amount of the cross section of the first external electrode is greater than 5%, it is judged that the denseness is not good, and it is represented as "poor" in table 2. In addition, referring to fig. 3 and 4, it can be seen that the electrode paste of the present invention can actually form an electrode having a more compact structure than an electrode formed using a general glass frit as a sintering aid, taking the first outer electrode of the ceramic electronic device of example 22-2 and comparative example 2-2 as an example.
Analysis 3: observation of interface form of first external electrode and ceramic body
After forming the first external electrodes from the electrode pastes of examples 1 to 30 and comparative examples 1 to 6, whether or not there is a phenomenon of glass floating was observed with a Secondary Electron Microscope (SEM), and whether or not there is a bubble existing at the interface of the first external electrode and the ceramic body was confirmed with a cross-section of the first external electrode observed with destructive analysis, and the observation results were as follows:
1. the first external electrodes of the ceramic electronic components of examples 1-1 to 30-1 were found to have no glass floating;
2. the first external electrodes of the ceramic electronic components of comparative example 1-1, comparative example 1-2, comparative example 5-1 and comparative example 6-1 were found to have no glass floating; however, the first external electrodes of the ceramic electronic components of comparative examples 2-1 to 4-2 all had a phenomenon of glass floating;
3. the first external electrode and the ceramic body of the ceramic electronic components of examples 1-1 to 30-1 were found to have no bubbles at their interfaces;
4. the first external electrodes of the ceramic electronic components of comparative examples 1-1 to 3-2, 5-1 and 6-1 were found to have no bubbles at the interface with the ceramic body; however, the first external electrodes of the ceramic electronic components of comparative examples 4-1 and 4-2 (see FIG. 5) were found to have bubbles at the interface with the ceramic body.
Analysis 4: tension test
On the third outer electrodes at opposite ends of the ceramic electronic components of examples 1-1 to 30-1 and comparative examples 1-1 to 6-1, iron wires were soldered with lead-free solder paste, respectively, and the iron wires were sandwiched by a universal drawing machine, the two iron wires were drawn in opposite directions, and the ultimate tensile forces thereof were measured, and the experimental results are shown in table 2.
Preparation of electrode pastes for examples 22-I to 22-VI
Electrode pastes (E22-I to E22-VI for short) of examples 22-I to 22-VI were obtained according to the compounding ratios shown in Table 3, respectively; the electrode pastes of embodiments 22-I to 22-VI, in which the conductive particles are made of copper, mainly change the types of the conductive particles included in the electrode pastes and the ratio of the types of the conductive particles to the total conductive particles. The total content of the conductive particles A and the conductive particles B is 72wt%, the content of the composite sintering aid (SA 6) is 3wt%, the content of the resin A is 7wt%, and the content of the organic solvent is 18wt%, based on 100wt% of the total of the conductive particles, the composite sintering aid, the resin, and the organic solvent.
Preparation of ceramic electronic Components of example 22-I-1 to example 22-VI-1
The ceramic electronic components of example 22-I-1 to example 22-VI-1 were produced by the same production method as that of example 1-1 to example 30-1. The main difference is that only the calcination temperature of 920 ℃ is used in examples 22-I-1 to 22-VI-1. The method mainly comprises the following steps: sequentially coating the electrode pastes of examples 22-I to 22-VI on the surface of the first end and the surface of the second end of the ceramic body in a dipping mode respectively; next, a firing step was performed at a firing temperature of 920 ℃ in a nitrogen atmosphere containing 10ppm of oxygen to obtain first external electrodes, and the ceramic electronic components of examples 22-I-1 to 22-VI-1 were finally obtained. Further, the characteristics were analyzed by the above-mentioned analyses 1, 2 and 4 as in the ceramic electronic components of examples 1-1 to 30-1, and the results of the experiments are shown in Table 3.
Preparation of electrode pastes for examples 31 to 39
Electrode pastes (abbreviated as E31 to E39) of examples 31 to 39 were obtained according to the compounding ratios shown in table 4, respectively; in the electrode pastes of examples 31 to 39, the kind of resin contained in the electrode paste and the contents of the resin and the organic solvent contained in the electrode paste are mainly changed.
Analysis 5: observation of appearance after application of electrode paste
The electrode pastes of example 31 and example 32 were applied to an alumina substrate by roll coating; the electrode pastes of examples 32 to 34 were coated on the ceramic body by dipping, respectively; the electrode pastes of examples 35 and 39 were applied to the alumina substrate by printing. After the electrode pastes of the foregoing examples 31 to 39 were applied to the surface of the alumina substrate or the ceramic body in different coating manners, the surface appearance of the applied electrode pastes was observed and confirmed by an optical microscope. If the surface of the coated electrode paste shows the phenomena of sagging, uneven thickness or cusp, the electrode paste is judged to be 'poor'; on the other hand, if the above-mentioned vertical flow, thickness unevenness, or cusp phenomenon does not occur, it is judged to be "flat", and the observation results thereof are shown in table 4.
Preparation of electrode pastes for examples 40 to 43 and comparative examples 7 to 10
According to the compounding ratios shown in table 5, electrode pastes of examples 40 to 43 (abbreviated as E40 to E43) and electrode pastes of comparative examples 7 to 10 (abbreviated as C7 to C10) were obtained, respectively; in the electrode pastes of embodiments 40 to 43, the material type of the conductive particles included in the electrode paste is mainly changed. The difference between the electrode pastes of comparative examples 7 to 10 and 40 to 43 is mainly that the composite sintering aids used in comparative examples 7 to 10 are the same as those of comparative examples 1 to 4, and are glass powders (component B-Ba-Zn-Si-Al-Na) with an average particle size of 3 μm.
Preparation of ceramic electronic Components of example 40-1 to example 43-1, and comparative example 7-1 to comparative example 10-1
The ceramic electronic components of example 40-1 to example 43-1 and comparative example 7-1 to comparative example 10-1 were produced by the same production method as that of example 22-2. The manufacturing method is mainly different from that of example 22-2 in that the kind of conductive particles in the electrode paste, and the firing temperature and firing environment were changed. Among them, the ceramic electronic components of example 40-1 and comparative example 7-1 were mainly prepared as follows: sequentially applying the electrode pastes of example 40 and comparative example 7 to the surface of the first end and the surface of the second end of the ceramic body in a dipping manner; then, carrying out a sintering step at the sintering temperature of 800 ℃ in the atmosphere to obtain the first outer electrode; then, nickel metal layers having an average thickness of 5 μm were respectively plated on the first external electrodes as second external electrodes, and then, tin metal layers having an average thickness of 10 μm were respectively plated on the second external electrodes as third external electrodes, thereby finally obtaining ceramic electronic components (hereinafter referred to as E40-1 and C7-1) of example 40-1 and comparative example 7-1. In addition, the ceramic electronic components of example 41-1 to example 43-1 and comparative example 8-1 to comparative example 10-1 were mainly prepared as follows: sequentially applying the electrode pastes of example 41 to example 43 and comparative example 8 to comparative example 10 to the surface of the first end and the surface of the second end of the ceramic body in a dipping manner; then, a sintering step is carried out in a nitrogen atmosphere containing 10ppm of oxygen at a sintering temperature of 800 ℃ to obtain the first external electrode; then, a nickel metal layer having an average thickness of 5 μm was plated on the first external electrodes as second external electrodes, and then a tin metal layer having an average thickness of 10 μm was plated on the second external electrodes as third external electrodes, thereby finally obtaining ceramic electronic components (hereinafter referred to as E41-1 to E43-1 and C8-1 to C10-1) of examples 41-1 to 43-1 and comparative examples 8-1 to 10-1. The ceramic electronic components of example 40-1 to example 43-1 and comparative example 7-1 to comparative example 10-1 were subjected to characteristic analyses as in the above analyses 1, 2 and 4, and the experimental results are set forth in table 5.
In addition, after forming the first external electrodes from the electrode pastes of examples 40 to 43 and the electrode pastes of comparative examples 7 to 10, whether or not the glass was floated was observed by SEM, and the observation results were as follows: the first external electrodes of the ceramic electronic components of examples 40-1 to 43-1 were found to have no glass floating; however, the first external electrodes of the ceramic electronic components of comparative examples 7-1 to 10-1 all exhibited the phenomenon of glass floating.
Preparation of ceramic electronic Components of examples 22-3 and 22-4
The production methods used for the ceramic electronic components of examples 22-3 and 22-4 were carried out in the same manner as the production method for the ceramic electronic component of example 22-2. The main difference is that the amount of oxygen contained in the nitrogen atmosphere at the time of calcination was changed in examples 22-3 and 22-4. The method mainly comprises the following steps: sequentially coating the electrode paste of example 22 on the surface of the first end and the surface of the second end of the ceramic body in a dipping manner; next, a firing step was performed at a firing temperature of 920 ℃ in a nitrogen atmosphere containing different oxygen partial pressures as described in Table 6 below to obtain first external electrodes, and finally ceramic electronic components of examples 22-3 and 22-4 were obtained. And characteristic analyses were performed in the above-described analyses 1 to 4 as in the ceramic electronic components of example 22-1 and example 22-2, and the experimental results are set forth in table 6.
Preparation of ceramic electronic Components of examples 22-5 and 22-6
The ceramic electronic components of examples 22-5 and 22-6 were produced by the same production method as that of example 22-2. The main difference is that examples 22-5 and 22-6 change the sintering temperature at the time of sintering. The method mainly comprises the following steps: sequentially coating the electrode paste of example 22 on the surface of the first end and the surface of the second end of the ceramic body in a dipping manner; next, firing steps were carried out in a nitrogen atmosphere containing 10ppm of oxygen at firing temperatures respectively described in Table 7 below to obtain first external electrodes, and finally ceramic electronic components of examples 22-5 and 22-6 were obtained. And characteristic analyses were conducted in the above-described analyses 1 to 4 as in the ceramic electronic components of example 22-1 and example 22-2, and the experimental results are set forth in table 7.
Preparation of electrode pastes of examples 44 to 52
Electrode pastes (abbreviated as E44 to E52) of examples 44 to 52 were obtained by mixing the components in the ratios shown in table 8. The differences between the electrode pastes of examples 44 to 52 are mainly the composition and content of the selected composite sintering aid.
Preparation of ceramic electronic Components of example 44-1 to example 52-1
Sequentially coating the electrode pastes of examples 44 to 52 on the surface of the first end and the surface of the second end of the ceramic body in a dipping manner; then, a firing step was performed in a nitrogen atmosphere containing 10ppm of oxygen at firing temperatures listed in table 8, respectively, to obtain the first external electrode; then, a nickel metal layer having an average thickness of 5 μm was plated on the first external electrodes as second external electrodes, and then a tin metal layer having an average thickness of 10 μm was plated on the second external electrodes as third external electrodes, so that ceramic electronic components (hereinafter, referred to as E44-1 to E52-1) of examples 44-1 to 52-1 were finally obtained, and characteristic analyses were performed by the above-mentioned analyses 1, 2, and 4 as with the ceramic electronic component of example 22-2, and the experimental results are shown in table 8.
Discussion of Experimental results
The analysis results of table 2 are summarized to show that, when the conductive particles are made of the same material, the electrode pastes of examples 1 to 30 include the specific composite sintering aid, and thus the first external electrodes formed from the electrode pastes of examples 1 to 30 all have better compactness, lower resistivity, and greater ultimate tensile force than those formed from the electrode pastes of comparative examples 1 to 6; accordingly, it can be confirmed that the external electrode formed by the electrode paste of the present invention has good conductivity and good bonding property with the ceramic body. Similarly, the analysis results in table 5 also show that, in the case of selecting the same conductive particles, the electrode pastes of examples 40 to 43 have better compactness, lower resistivity and greater ultimate tensile strength of the first outer electrode formed from the electrode paste of example 40 than the first outer electrode formed from the electrode paste of comparative example 7 because the electrode pastes include the specific composite sintering aid; in addition, the first external electrodes formed by the electrode pastes of example 41, example 42 and example 43 respectively had better compactness, lower resistivity and greater ultimate tensile force than those of comparative example 10 and example 9 and 8, respectively; it was again demonstrated that the external electrodes formed from the electrode pastes of the present invention indeed may have good conductivity and may have good bondability to ceramic bodies.
In addition, the electrode pastes of examples 1 to 30 and 40 to 43 do not generate bubbles during the firing process, and the first external electrodes formed by the electrode pastes do not have the problem of glass floating; therefore, the electrode paste can avoid the defects of bubble generation and glass aggregation interface in the manufacturing method of the ceramic electronic element, thereby improving the weldability and ensuring that the electroplated layer formed by subsequent electroplating has good continuity.
When the first external electrodes formed by the electrode pastes of comparative examples 1 to 4 and 7 to 10 are increased to a level of 3wt% of the total weight of the electrode pastes (e.g., the electrode pastes of comparative examples 2 and 7 to 10), the glass is floated, and the continuity of the second external electrode formed by the subsequent plating is reduced. When the content of the glass frit was further increased to 7wt% based on the total weight of the electrode paste (as in comparative example 4), bubbles were significantly generated even at the interface of the first external electrode and the ceramic body, and the continuity of the second external electrode formed by the subsequent plating was considerably deteriorated.
Furthermore, as can be seen from the results in table 6, if the sintering step is performed at a lower oxygen partial pressure, the first outer electrode formed can also have better conductivity, and the first outer electrode can have stronger bonding property with the interface of the ceramic body. Because the oxygen content in the burning process is reduced, the chance of forming oxide on the surface of the first external electrode can be reduced, the conductivity of the first external electrode can be obviously improved, the interface of the ceramic body has stronger bonding property, and the yield of the final product of the ceramic electronic element is improved.
In addition, as shown in the results of table 7, if the sintering is performed at a higher sintering temperature (e.g., 920 ℃), the first outer electrode with better compactness can be formed, so the first outer electrode has better conductivity, and the interface reactivity between the first outer electrode and the ceramic body can be improved, so the first outer electrode can have stronger bonding property with the ceramic body, thereby improving the yield of the final product of the ceramic electronic component.
Furthermore, as can be seen from the results in Table 8, when the composite sintering aid further comprises a modifier, such as lithium carbonate, sodium carbonate or potassium carbonate, the resistivity and ultimate tensile strength equivalent to those of the external electrode obtained by high-temperature sintering (920 ℃) can be obtained at a lower sintering temperature (i.e., less than 920 ℃); at the same firing temperature (i.e., 920 c), the external electrode made from the electrode paste containing the modifier can have a lower resistivity than the external electrode made from the electrode paste not containing the modifier. Therefore, when the composite sintering aid further comprises a modifier, the electrode paste can be sintered at a lower sintering temperature, or the electrode has better conductive characteristics or better bonding property with the ceramic body or the ceramic substrate at the same sintering temperature.
Furthermore, since the electrode paste and the ceramic electronic component of the present invention do not require a complicated process for preparing glass frit in advance during the preparation process, the present invention can be carried out in a simple and efficient manner. Therefore, the manufacturing method of the ceramic electronic element of the invention has the advantages of time efficiency and cost, and further improves the application value of the invention.
Table 1-1 composition of composite sintering aids of preparation examples 1 to 9 and comparative preparation examples 1 to 2 and amount thereof (wt%)
Table 1-2 composition of composite sintering aid of preparation examples 10 to 18 and amount thereof (wt%)
TABLE 2 results of characteristic analysis of the electrode pastes of examples 1 to 30, comparative examples 1 to 6, and ceramic electronic components of examples 1-1 to 30-1, and comparative examples 1-1 to 6-1 including the same
TABLE 3 electrode pastes of example 22, example 22-I to example 22-V, and examples 22-2, 2,
Results of characteristic analysis of ceramic electronic Components of examples 22-I-1 to 22-V-1
TABLE 4 formulation of electrode pastes of examples 31 to 39, application method thereof and appearance thereof after application
TABLE 5 results of characteristic analysis of the electrode pastes of examples 40 to 43 and comparative examples 7 to 10 and the ceramic electronic components of examples 40-1 to 43-1 and comparative examples 7-1 to 10-1 containing the same
TABLE 6 analysis results of the numbers of ceramic electronic components, oxygen partial pressures at the time of firing, and characteristics thereof in examples 22-2 to 22-4
TABLE 7 number, burning temperature and characteristic analysis results of ceramic electronic components of example 22-1, example 22-2, example 22-5 and example 22-6
TABLE 8 formulation ratios of the electrode pastes of examples 44 to 52, numbers of the ceramic electronic components of examples 44-1 to 52-1 including the same, and results of characteristic analysis thereof
It should be understood that the above description is only exemplary of the invention, and is not intended to limit the scope of the invention, so that the replacement of equivalent elements or equivalent changes and modifications made in the present invention should be included within the scope of the present invention. In addition, the technical features and the technical inventions of the present invention, the technical features and the technical inventions, and the technical inventions can be freely combined and used.
Claims (15)
1. An electrode paste, comprising: conductive particles, a composite sintering aid, a resin, and an organic solvent; wherein the composite sintering aid is mixed powder containing copper-containing compounds, barium salt, calcium salt and manganese salt;
wherein the manganese salt comprises manganese carbonate, manganese acetate, or manganese oxalate;
wherein the average particle size of the copper-containing compound is 10 to 500nm, the average particle size of the barium salt is 10 to 500nm, the average particle size of the calcium salt is 10 to 500nm, and the average particle size of the manganese salt is 10 to 500 nm;
wherein, based on the total weight of the composite sintering aid, the copper-containing compound is used in an amount of 0.5-65 wt%, the barium salt is used in an amount of 4.9-89 wt%, the calcium salt is used in an amount of 0.5-30 wt%, and the manganese salt is used in an amount of 0.1-10 wt%.
2. The electrode paste of claim 1, wherein the content of the conductive particles is 58 to 75wt%, the content of the composite sintering aid is 0.5 to 7wt%, the content of the resin is 0.5 to 11wt%, and the content of the organic solvent is 10 to 25wt%, based on 100wt% of the total of the conductive particles, the composite sintering aid, the resin, and the organic solvent.
3. The electrode paste according to claim 1 or 2, wherein the conductive particles are copper, silver, or a copper-silver alloy.
4. The electrode paste of claim 3, wherein the conductive particles are spherical conductive particles having an average particle size of 0.5 to 10 microns, flake conductive particles having an average particle size of 2 to 10 microns, or a combination thereof.
5. The electrode paste of claim 1 or 2, wherein the copper-containing compound comprises copper oxide, copper acetate, or copper oxalate; the barium salt comprises barium carbonate, barium acetate, or barium oxalate; the calcium salt comprises calcium carbonate, calcium acetate, or calcium oxalate.
6. The electrode paste of claim 1 or 2, wherein the composite sintering aid further comprises a modifier comprising lithium carbonate, sodium carbonate, or potassium carbonate.
7. The electrode paste of claim 6, wherein the modifier is used in an amount of 0.1 to 0.5wt% based on the total weight of the composite sintering aid.
8. An electrode fired from the electrode paste of any one of claims 1 to 7.
9. A ceramic electronic component comprising a ceramic substrate, and an electrode according to claim 8; wherein the electrode is formed on the ceramic substrate.
10. A ceramic electronic component, comprising:
a ceramic body having a first end and a second end opposite to the first end;
a plurality of internal electrodes arranged in the ceramic body, wherein two adjacent internal electrodes are respectively connected with the first end and the second end of the ceramic body; and
two external electrodes respectively coated on the surface of the first end and the surface of the second end of the ceramic body and electrically connected with the internal electrodes; two of the outer electrodes comprise the electrode of claim 8.
11. The ceramic electronic component of claim 10, wherein the two external electrodes comprise two first external electrodes, two second external electrodes, and two third external electrodes; the ceramic electronic component according to claim 8, wherein the two first external electrodes are the electrodes as defined in claim 8, the two first external electrodes are coated on the surface of the first end and the surface of the second end of the ceramic body and electrically connected to the plurality of internal electrodes, and the two second external electrodes are respectively formed between the two first external electrodes and the two third external electrodes.
12. A method for manufacturing a ceramic electronic component includes the steps of:
a step (a): preparing a ceramic body comprising a plurality of internal electrodes, wherein the plurality of internal electrodes are arranged in the ceramic body, and the ceramic body is provided with a first end and a second end opposite to the first end;
step (b): preparing an electrode paste according to any one of claims 1 to 7; and
a step (c): coating the electrode paste on the surface of the first end and the surface of the second end of the ceramic body and carrying out sintering to obtain the ceramic electronic element; the ceramic electronic component comprises two outer electrodes, wherein the two outer electrodes are respectively coated on the surface of the first end and the surface of the second end of the ceramic body and are electrically connected with the plurality of inner electrodes.
13. The method of manufacturing a ceramic electronic component as claimed in claim 12, wherein, when the metal of the conductive particles contained in the electrode paste is copper or a copper-silver alloy, the step (c) is carried out in a nitrogen atmosphere containing not more than 100ppm of oxygen; wherein, when the metal of the conductive particles contained in the electrode paste is silver, the firing step is performed in an atmospheric atmosphere.
14. The method of manufacturing a ceramic electronic component as claimed in claim 12, wherein the firing temperature of the step (c) is 780 ℃ to 1000 ℃.
15. The method of manufacturing a ceramic electronic component as claimed in any one of claims 12 to 14, wherein the step (c) comprises:
step (c 1): coating the electrode paste on the surface of the first end and the surface of the second end of the ceramic body and carrying out a sintering step to obtain two first outer electrodes;
step (c 2): respectively plating two second external electrodes on the two first external electrodes; and
step (c 3): respectively plating two third external electrodes on the two second external electrodes to obtain the ceramic electronic component; the two outer electrodes include two of the first outer electrodes, two of the second outer electrodes, and two of the third outer electrodes.
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