CN111489865A - Preparation method of self-promoting antioxidant copper electrode - Google Patents

Preparation method of self-promoting antioxidant copper electrode Download PDF

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CN111489865A
CN111489865A CN202010244275.5A CN202010244275A CN111489865A CN 111489865 A CN111489865 A CN 111489865A CN 202010244275 A CN202010244275 A CN 202010244275A CN 111489865 A CN111489865 A CN 111489865A
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sintering
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copper electrode
oxide
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CN111489865B (en
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朱晓云
汪冲
朱梓瑜
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Kunming Guixinkai Technology Co ltd
Kunming University of Science and Technology
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Kunming Guixinkai Technology Co ltd
Kunming University of Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0016Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
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Abstract

The invention provides a preparation method of a self-promoting antioxidant copper electrode, which adopts the technical scheme that: and printing copper slurry, drying, printing an oil seal layer, drying, printing a self-promoting layer, sintering, reacting the self-promoting layer with solid components in the oil seal layer in the sintering process to generate a protective layer, and removing the protective layer to obtain the antioxidant copper electrode. The invention solves the technical problem of sintering the copper conductor slurry in the air, realizes the sintering in the air to obtain the copper electrode, and reduces the sintering cost of the copper conductor slurry and the requirement on sintering equipment. The method for preparing the copper electrode is simple to operate, low in cost and high in practicability.

Description

Preparation method of self-promoting antioxidant copper electrode
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a preparation method of a self-promoting antioxidant copper electrode.
Background
With the increasing demand and high performance requirements of electronic products, electronic components are inevitably developed to low cost, miniaturization, high performance and high density. In order to comply with and meet these new requirements and changes, electronic component manufacturers face huge challenges, and in order to share the market, reduce the production cost of electronic components and improve the performance of electronic components, the electronic components become problems that the manufacturers need to solve urgently.
The noble metal slurry has the advantages of good conductivity, simple process, good repeatability, stable performance after sintering and the like, and the conductive slurry used for producing electronic components is mostly the noble metal slurry. However, with the increasing demand of electronic products, the demand of conductive paste increases sharply, but due to the scarcity of precious metal resources, the price increase and the defects of the performance of the precious metal resources, base metal paste such as copper, nickel, aluminum and the like with low price and excellent performance is made out, wherein copper conductor paste is used as a representative and research application. Copper has more excellent high-frequency characteristics and conductivity than gold, and has no problem of silver electromigration, and the sintered copper electrode has good solderability and solderability. In addition to the above-mentioned performance advantages, copper conductor pastes have a huge price advantage. Therefore, under the dual advantages of performance and price, the copper conductor paste is more and more widely applied to electronic components.
The copper conductor slurry has electrode performance after being sintered, and the sintering process is an important process for preparing the copper electrode and directly determines the microstructure and the performance of the copper electrode. Copper conductor paste is easy to oxidize, and sintering must be carried out in nitrogen or other protective atmosphere, so that the phenomenon of 'buying cheap and using expensive' exists in the use of copper conductor paste. The sintering in the protective atmosphere has certain technical content, the sintering condition is sensitive, the stability is poor, the yield is low, and the factors increase the use cost of the copper conductor slurry. At present, although there are reports of direct sintering of copper electrodes in air, the copper electrodes are not applied in actual production.
Disclosure of Invention
Based on the problems of the copper conductor slurry in the sintering process, the invention provides the preparation method of the self-promoting oxidation resistant electrode, which solves the technical problem of sintering the copper conductor slurry in the air, and reduces the sintering cost of the copper conductor slurry and the performance requirement on sintering equipment.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a self-promoting oxidation resistant electrode comprises the following steps:
step 1: preparing an oil seal layer: weighing 30-50% of graphite and 50-70% of high-temperature grease according to the weight percentage, putting the weighed graphite and high-temperature grease into a closed container, heating and stirring the graphite and the high-temperature grease in a water bath at the temperature of 50-80 ℃ until the graphite and the high-temperature grease are completely and uniformly mixed, and preserving the heat for 0.5 hour for later use;
step 2: preparing a self-priming layer: weighing 20-50% of oxide and 50-80% of solvent according to the weight percentage, and dispersing the weighed oxide and solvent by using a three-roll mill until the fineness is 20-30 mu m for later use;
and step 3: printing: adopting screen printing according to the required pattern, wherein the mesh number of the screen is 200-300 meshes; firstly, printing copper conductor slurry and drying; printing an oil seal layer, drying, printing a self-priming layer, and sintering the obtained copper electrode at the drying temperature of 80-120 ℃;
and 4, step 4: and (3) sintering: putting the copper electrode obtained in the step (3) into a sintering furnace, reacting the self-promoting layer with solid components in the oil seal layer to generate a protective layer in the sintering process, wherein the sintering temperature is 450-900 ℃, the peak heat preservation time is 5-15min, and the sintering time is 30-70 min;
and 5: and after sintering, removing the protective layer by mechanical vibration to obtain the oxidation-resistant copper electrode.
Further, the high-temperature grease comprises one or a combination of several of organic silicon, inorganic silicon and imine.
Further, the oxide comprises one or more of aluminum oxide, zirconium oxide, silicon oxide, zinc oxide, calcium oxide, magnesium oxide and strontium oxide. The solvent comprises one or a combination of a plurality of silane coupling agents, isoamyl propionate, butyl acetate, isoamyl acetate, benzyl alcohol, glycerol, glycol and paraxylene.
Further, the thickness of the oil seal layer is 2-5 μm.
Furthermore, the area of the oil seal layer is larger than that of the electrode layer, and the area of the self-promoting layer is larger than that of the oil seal layer.
The invention provides a method for sintering a copper electrode in air, wherein in the sintering process, air enters an electrode layer from an oil seal layer during the sintering temperature of 60-300 ℃, so that the volatilization of butyl carbitol solvent and ethyl cellulose in slurry is facilitated; and the sintering temperature is 300-900 ℃, the self-promoting layer reacts with solid components in the oil seal layer to generate a protective layer, the protective layer prevents air from contacting the electrode layer, and the electrode layer is sintered in an oxygen-free environment. According to the invention, sintering in a protective atmosphere is not required, air sintering of the copper electrode is realized, the oil seal layer and the self-promoting layer are covered on the copper electrode layer, the self-promoting layer reacts with solid components in the oil seal layer in the sintering process to generate the protective layer to isolate air, the protective electrode layer is sintered in an oxygen-free atmosphere, the copper electrode is sintered in air, the performance requirement on a sintering furnace is reduced, and thus the sintering cost is saved. The method for preparing the copper electrode is simple to operate, low in cost and high in practicability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of the copper electrode preparation process of the present invention;
FIG. 2 is an exploded view of the electrode before sintering;
FIG. 3 is an exploded view of the sintered electrode;
FIG. 4 is a copper electrode made using the present invention;
FIG. 5 is an SEM image of the surface topography of a copper electrode.
The labels in the figures are: 1-electrode layer, 2-copper slurry layer, 3-oil seal layer, 4-self-priming layer and 5-protective layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Step 1: preparing an oil seal layer: weighing 30% of graphite and 70% of high-temperature grease; 80% of organic silicon and 20% of imine in the high-temperature grease. Putting the weighed graphite and high-temperature grease into a closed container, heating and stirring in a water bath at the temperature of 50 ℃ until the graphite and the high-temperature grease are completely and uniformly mixed, and preserving heat for 0.5 hour; and (5) standby.
Step 2: preparing a self-priming layer: weighing 10% of aluminum oxide, 5% of zinc oxide and 5% of zirconium oxide; 80% of solvent, wherein the silane coupling agent is 5%, the isoamyl propionate is 60%, and the isoamyl acetate is 15%. And dispersing the weighed oxide and the solvent by a three-roll mill to obtain a product with the fineness of 20 mu m for later use.
And step 3: adopting screen printing, printing according to the required pattern, wherein the mesh number of the screen is 200-300 meshes; and printing copper conductor slurry, drying, printing an oil seal layer, drying, and printing a self-priming layer to obtain the copper electrode. The drying temperature is 80 ℃, and sintering is carried out.
And 4, step 4: and (4) putting the electrode obtained in the step (3) into a belt type sintering furnace, wherein the self-promoting layer reacts with solid components in the oil seal layer to generate a protective layer in the sintering process, the sintering temperature is 850 ℃, the peak heat preservation time is 10min, and the sintering time is 50 min.
And 5: and after sintering, removing the protective layer by mechanical vibration to obtain the oxidation-resistant copper electrode.
Example 2
Step 1: preparing an oil seal layer: weighing 40% of graphite and 60% of high-temperature grease; 60% of organic silicon and 40% of imine in the high-temperature grease. Putting the weighed graphite and high-temperature grease into a closed container, heating and stirring in a water bath at the temperature of 50 ℃ until the graphite and the high-temperature grease are completely and uniformly mixed, and preserving heat for 0.5 hour; and (5) standby.
Step 2: preparing a self-priming layer: weighing 10% of aluminum oxide, 5% of zinc oxide, 5% of zirconium oxide and 3% of strontium oxide; 77% of solvent, wherein the silane coupling agent is 5%, the isoamyl propionate is 60% and the benzyl alcohol is 12%. And dispersing the weighed oxide and the solvent by using a three-roll mill to obtain the product with the fineness of 25 mu m for later use.
And step 3: adopting screen printing, printing according to the required pattern, wherein the mesh number of the screen is 200-300 meshes; and printing copper conductor slurry, drying, printing an oil seal layer, drying, and printing a self-priming layer to obtain the copper electrode. The drying temperature is 100 ℃, and sintering is carried out.
And 4, step 4: and (4) putting the electrode obtained in the step (3) into a belt type sintering furnace, wherein the self-promoting layer reacts with solid components in the oil seal layer to generate a protective layer in the sintering process, the sintering temperature is 900 ℃, the peak heat preservation time is 10min, and the sintering time is 60 min.
And 5: and after sintering, removing the protective layer by mechanical vibration to obtain the copper electrode.
Example 3
Step 1: preparing an oil seal layer: weighing 50% of graphite and 50% of high-temperature grease; 70% of inorganic silicon and 30% of imine in the high-temperature grease. Putting the weighed graphite and high-temperature grease into a closed container, heating and stirring in a water bath at the temperature of 50 ℃ until the graphite and the high-temperature grease are completely and uniformly mixed, and preserving heat for 0.5 hour; and (5) standby.
Step 2: preparing a self-priming layer: weighing 15% of silicon oxide and 5% of zirconium oxide; 80% of solvent, wherein the silane coupling agent is 5%, the isoamyl propionate is 40%, and the p-xylene is 35%. And dispersing the weighed oxide and the solvent by a three-roll mill to obtain a product with the fineness of 20 mu m for later use.
And step 3: adopting screen printing, printing according to the required pattern, wherein the mesh number of the screen is 200-300 meshes; and printing copper conductor slurry, drying, printing an oil seal layer, drying, and printing a self-priming layer to obtain the copper electrode. The drying temperature is 100 ℃, and sintering is carried out.
And 4, step 4: and (4) putting the electrode obtained in the step (3) into a belt type sintering furnace, wherein the self-promoting layer reacts with solid components in the oil seal layer to generate a protective layer in the sintering process, the sintering temperature is 800 ℃, the peak heat preservation time is 5min, and the sintering time is 30 min.
And 5: and after sintering, removing the protective layer by mechanical vibration to obtain the oxidation-resistant copper electrode.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A preparation method of a self-promoting oxidation-resistant copper electrode is characterized by comprising the following steps:
step 1: preparing an oil seal layer: weighing 30-50% of graphite and 50-70% of high-temperature grease according to the weight percentage, putting the weighed graphite and high-temperature grease into a closed container, heating and stirring the graphite and the high-temperature grease in a water bath at the temperature of 50-80 ℃ until the graphite and the high-temperature grease are completely and uniformly mixed, and preserving the heat for 0.5 hour for later use;
step 2: preparing a self-priming layer: weighing 20-50% of oxide and 50-80% of solvent according to the weight percentage, and dispersing the weighed oxide and solvent by using a three-roll mill until the fineness is 20-30 mu m for later use;
and step 3: printing: adopting screen printing according to the required pattern, wherein the mesh number of the screen is 200-300 meshes; firstly, printing copper conductor slurry and drying; printing an oil seal layer, drying, and finally printing a self-priming layer, wherein the drying temperature is 80-120 ℃, and the obtained copper electrode is to be sintered;
and 4, step 4: and (3) sintering: putting the copper electrode obtained in the step (3) into a sintering furnace, reacting the self-promoting layer with solid components in the oil seal layer to generate a protective layer in the sintering process, wherein the sintering temperature is 450-900 ℃, the peak heat preservation time is 5-15min, and the sintering time is 30-70 min;
and 5: and after sintering, removing the protective layer by mechanical vibration to obtain the oxidation-resistant copper electrode.
2. The method for preparing a self-triggering oxidation-resistant copper electrode according to claim 1, wherein: the high-temperature grease comprises one or a combination of more of organic silicon, inorganic silicon and imine.
3. The method for preparing a self-triggering oxidation-resistant copper electrode according to claim 1, wherein: the oxide comprises one or more of aluminum oxide, zirconium oxide, silicon oxide, zinc oxide, calcium oxide, magnesium oxide and strontium oxide.
4. The method for preparing a self-triggering oxidation-resistant copper electrode according to claim 1, wherein: the solvent comprises one or a combination of a plurality of silane coupling agents, isoamyl propionate, butyl acetate, isoamyl acetate, benzyl alcohol, glycerol, glycol and p-xylene.
5. The method for preparing a self-triggering oxidation-resistant copper electrode according to claim 1, wherein: the printing thickness of the oil seal layer is 2-5 mu m.
6. The method for preparing a self-triggering oxidation-resistant copper electrode according to claim 1, wherein: the area of the self-promoting layer is larger than that of the oil seal layer, and the area of the oil seal layer is larger than that of the electrode layer.
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CN102173648A (en) * 2011-01-11 2011-09-07 上海胜星树脂涂料有限公司 Water-based high-temperature-resistant oxidation-resistant inorganic paint and preparation method thereof
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CN106887268A (en) * 2017-01-07 2017-06-23 东莞易力禾电子有限公司 Silk-screen printing circuit electrode and preparation method thereof
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CN102173648A (en) * 2011-01-11 2011-09-07 上海胜星树脂涂料有限公司 Water-based high-temperature-resistant oxidation-resistant inorganic paint and preparation method thereof
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CN106887268A (en) * 2017-01-07 2017-06-23 东莞易力禾电子有限公司 Silk-screen printing circuit electrode and preparation method thereof
CN107731434A (en) * 2017-09-25 2018-02-23 江苏时瑞电子科技有限公司 A kind of thermistor copper electrode multifunctional protection film layer and preparation method thereof
CN109545424A (en) * 2018-11-30 2019-03-29 苏州晶银新材料股份有限公司 A kind of conductive silver paste and its preparation method and application

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