CN103578607A - Base metal electrode structure and preparing method thereof - Google Patents
Base metal electrode structure and preparing method thereof Download PDFInfo
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- CN103578607A CN103578607A CN201210261654.0A CN201210261654A CN103578607A CN 103578607 A CN103578607 A CN 103578607A CN 201210261654 A CN201210261654 A CN 201210261654A CN 103578607 A CN103578607 A CN 103578607A
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Abstract
The invention provides a base metal electrode structure. A ceramic substrate 1 is coated with base metal conductor paste through a carrier connecting portion 4 and a carrier connecting portion 5 according to a coating technology so that a base metal layer 2 with a certain thickness and a base metal layer 3 with a certain thickness can be formed, namely base metal electrode structures can be formed. The coating technology comprises the steps that materials are selected, the materials are blended according to a certain ratio, the blended base metal paste is placed in a ball-milling tank, and after ball-milling is conducted, standing of the paste is conducted for three hours and the paste is placed in a cooler for standby use; a capacitor ceramic substrate is selected to serve as an experiment base material, the base material is placed in a tool, copper paste is evenly painted on the surface of the base material through a screen printing press, the dried base material is placed in a sintering furnace for sintering, and finally the base metal structure is obtained. The base metal electrode structure relates to electronic elements such as a ceramic capacitor, piezoelectric ceramics, a sensitive element and a printed circuit and through electrode preparation, the high electrode conductivity rate (0.9*10<-6> omega*cm) and a relatively complete connecting network are obtained, the good performance of good weldability, adhesive force and the like are achieved, and it is well founded that the phenomenon that the base metal replaces noble metal to serve as the electrodes is the inevitable trend of the development of the component industry.
Description
Technical field
Metal electrode structure the present invention relates to and preparation method thereof, particularly a kind of preparation method of electrodes in base metal structure.
Background technology
Known electrode structure at home, to take noble metal as main flow, base metal is auxiliary, common composition, especially in electron trade, Resistor-Capacitor Unit, senser is in order to guarantee necessary some electrical properties, have to adopt noble silver as the material of main part of electrode structure, from the seventies in last century du pont company, take the lead in adopting copper to lead the research as electrode structure to base metal all over the world as electrode structure, after reform and opening-up, the electron trade of China is advanced by leaps and bounds, along with improving constantly of electron trade technology, also be the constantly soaring of noble metal price in the last few years, for base metal, the needs as electrode structure also strengthen electron trade day by day, find that after deliberation some base metal material has the performance more more excellent than noble metal at some aspect electrical, as copper has the characteristic of good anti-electromagnetic interference, the EMI shield technology of namely conventionally saying, and have than the more superior high frequency characteristics of metal and conductivity.
Aluminium and silicon can form PN doubly, to there is long-wave response feature, aluminium is as coating material of mono-crystalline silicon solar substrate etc., but the base metal as electrode structure also has the bottleneck that is difficult to overcome, current domestic electron trade is Resistor-Capacitor Unit, pressure cell etc. especially, the electrodes in base metal structure running into, subject matter is:
The electrode structure forming under a, oxygen easily produces and partly leads effect base material, and its insulating properties is declined rapidly;
B, majority adopt resin solidification method, are difficult to overcome the difference of the coefficient of expansion, under high temperature, low temperature, easily split, and are difficult to form long-term electrical requirement;
C, microcosmic are difficult to form interconnection network, local cavity in surface, have a strong impact on electrical property;
D, technological requirement are high, as stated former oxygen content≤the 3ppm requiring under atmosphere, thereby cause the significantly increase of operation cost;
The oxidation of e, base metal.
The above is known, if electrodes in base metal structure can overcome above problem, prints electrode so or the technical process of circuit also can be simplified greatly, thereby meets the requirement of electrical property, to relevant enterprise, brings significant economic benefit.
Summary of the invention
The object of the invention is to propose a kind of electrodes in base metal structure and preparation method thereof:
A structure, connects 4,5 by base metal conductor paste by carrier by coating processes and is coated on the ceramic substrate 1 with certain electrical property, forms the base metal layer 2,3 of certain thick film, is base metal structure electrode;
Use the composition of base metal to comprise aluminium, tin, zinc, copper, nickel, chromium, molybdenum etc. and alloy thereof;
Described electrode structure, being attached thing surface base metal thick film coating thickness is 0.1 μ m-30 μ m;
Described electrode structure, is attached the arbitrary shape that is shaped as of thing surface base metal thick film coating;
Described electrode structure, is attached thing surface base metal thick film multiple coating.
Described preparation method is: the painting method that base metal conductor paste is coated in ceramic substrate 1 and other non-metal base plates comprises: solid precipitation method, chemical vapour deposition technique, sputter (magnetic control) and vapour deposition method, metallikon.
Technical process is as follows:
1, the material of base metal structure is prepared in choosing; For copper and alloy thereof, a kind of organic solvent, glass carrier, flux material, anti-reduction-oxidation material, levelling agent, wetting agent form.And the selection of material copper powder; Be generally electrolytic copper powder, and copper powder to be made flake copper;
2, the above-mentioned various materials that prepare are allocated according to a certain percentage:
Copper powder (75%--85%)+GPL (3%--5%)+organic solvent+antioxidant+levelling agent+wetting agent;
3, the base metal slurry after allotment is inserted 3L ball grinder, adds to be greater than slurry weight 15% zirconium ball or stainless steel ball turns min8h with rotating speed 300;
4, after completing, the parked 3H of slurry to be put into refrigerating box standby for ball milling;
5, select condenser ceramics substrate as experiment base material, base material is inserted in frock, by screen process press, copper slurry is evenly printed on to substrate surface, controlling serous coat thickness is 0.15mm 0.2mm, enters dryer copper slurry is dried with 240 degree speed 200min/m;
6, the base material of having dried being inserted to Temperature Setting curve in sintering furnace is 100-250-350-500600, and controlling every temperature range time is 0.5h, and 600 are incubated 0.2h cooling while spending can open ventilation unit until room temperature by being naturally cooled to 150 while spending;
7, the base metal structure obtaining.
The invention has the advantages that:
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
Fig. 2 is various electrode electromigration lab diagrams;
Fig. 3 is the graph of a relation of temperature and resistance.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described:
Referring to accompanying drawing, in figure, 1 (C) is ceramic substrate; 2,3 (A1, B1) are base metal layer; 4,5 (A2, B2) are carrier coupling part.By the technique applying, base metal conductor paste is connected to 4,5 by carrier and be coated on ceramic substrate 1, form certain thickness base metal layer 2,3, be electrodes in base metal structure.
Concrete preparation process of the present invention is as follows:
The material that first-selection is prepared base metal structure is copper and alloy thereof, and a kind of organic solvent, glass carrier, flux material, anti-reduction-oxidation material, levelling agent, wetting agent form.
Selection as main body base metal material material copper powder, be generally electrolytic copper powder, that with regard to market, grasps at present has spherical with regard to its pattern, sheet and irregular pattern, first we select flake copper, its granularity should be controlled at 0.5mm-1.2mm, specific area is 2.5m/g, granularity ∠ 1um-1.5um generally, more easily preparation, making flake copper will be by electrolytic copper powder flaking, will be with completing by ball-milling technology, general applicable 3L ball grinder is equipped with 3mm stainless steel ball, ball milling adds 5% dispersant preventing agglomeration and is equipped with other lubricants, rotational speed of ball-mill should be controlled at 300-500r/min, time is 5h, copper powder after ball milling also needs secondary ball milling, use 1mm or 1.5mm aluminium ball, rotating speed is 500r/min, carry out again after 3h ball milling, be prepared into desirable flake copper.
Be equivalent to a unit of measurement copper powder and should account for (75-85) wt%, wherein the copper powder after ball milling (70-80) wt%.Ultra-fine (0.1mm-0.5mm) spherical copper powder 5wt%, in order to improve conductance, should suitably control copper powder ratio, during copper powder ratio ∠ 75wt% that experiment is found to the present invention relates to, electrode coating ∠ 5um, the continuity of interconnection network can be subject to certain destruction, electric conductivity is declined, now suitably regulate the ratio of superfine spherical and copper powder can alleviate electrical property decline problem, but coating layer thickness should be adjusted to some extent.
Tin, as low melting point base metal, help solubilization, and the copper powder the present invention relates to also has the existence of a certain amount of ultra-fine gun-metal.
Most of electrodes in base metal structures, when solid phase high temperature (700-900 ℃) reduces, capital presents oxidative phenomena, the present invention is to this narration emphatically, the copper powder that this case just relates to (1083 ℃ of molten points) sintering under bulk state air, there is document announcement, can stand 800 ℃ even higher temperature lower surface be not oxidized, after we corrode Copper Powder Surface through experiment ordinary organic solvents, do not accomplish reduction test at temperature, 100 ℃--during 300 ℃ of 10/min, have no Copper Powder Surface oxidation, 300 ℃--during 400 ℃ of 10/min, present moderate oxidation, resistance value sharply increases, while surpassing 700 ℃ of 10/min, complete oxidation, surface black shape, find after deliberation if make copper powder under end oxygen content ∠ 100ppm, reduce the molten point of copper powder, form continuous linked network, just likely realize, guarantee that coating is not oxidized and can makes coating surface serialization, the method of head it off is mainly to realize in N2 atmosphere at present both at home and abroad, but there is significant limitation in the method, as to being attached having relatively high expectations of thing ceramic base material, (base material is when N2 atmosphere sintering for common barium titanate, originally be difficult for forming semiconducting theory on porcelain body surface, insulation resistance is declined to a great extent, when ZnO varistor is carried out cu slurry sintering through being coated with under N2 atmosphere for another example, V2 can cement out the O2 in ZnO, that non linear coefficient decline even approaches linearity, namely X value declines, greatly affect its electrical property, with at present domestic and international electrodes in base metal structure, in preparation, cannot meet the complexity that technique was wanted or increased to various basic material electrical properties in sum, make base metal not low-priced, how utilizing ripe noble metal electrode structural paste preparation technology to meet every electrical performance indexes with base metal is successful part of the present invention.
In example through lot of experiments, we select silicon+boron+antioxidant by a certain proportion of ball milling (batch mixing)---calcining----secondary ball milling make glass dust carrier (GPL), through 350 eye mesh screens, sieve, now antioxidant and silicon, the ratio of boron and sintering temperature are the keys that determines coating paste reduction temperature, also determine the size of base metal and substrate adhesive force simultaneously, thereby affect the key of electrical property, the ratio of well-known regulation and control frit cosolvent is as bismuth oxide, or add certain mutual oxidation two phosphorus etc., have the fusing point of controlling glass carrier, 480 ℃--580 ℃, but electrode structure is now discontinuous in microstructure, can cause increasing of resistivity thus, also can affect the electrical property of base material, when more approach the electrode structure of its generation of base metal fusing point with regard to reduction temperature, more can become continuous surface, but consider the tolerance of base material, resistance to oxidation with base metal, can not realize, can only realize assurance adhesive force at lower temperature so, continuity with base metal structure, low temperature also makes base metal under the interpolation of peculiar material simultaneously, the index of determining technique becomes above-mentioned purpose can to separate, by great many of experiments, we give in formula and add a certain amount of low base metal adding to be a little equipped with antioxidant and cosolvent, make to be difficult for the copper powder in low temperature thawing, base metal by low melting point connects, thereby can make electrode structure form a complete continuous structure, and a certain amount of antioxidant can make copper powder at low temperatures, not oxidizable when common industrial bell jar furnace reduction.
Embodiment 1:
Specific embodiment is:
1, the material of base metal structure is prepared in choosing; For copper and alloy thereof, a kind of organic solvent, glass carrier, flux material, anti-reduction-oxidation material, levelling agent, wetting agent form.And the selection of material copper powder; Be generally electrolytic copper powder, and copper powder to be made flake copper;
2, the above-mentioned various materials that prepare are allocated according to a certain percentage:
Copper powder (75% :)+GPL (3%)+organic solvent+antioxidant+levelling agent+wetting agent;
3, the base metal slurry after allotment is inserted 3L ball grinder, adds to be greater than slurry weight 15% zirconium ball or stainless steel ball turns min8h with rotating speed 300;
4, after completing, the parked 3H of slurry to be put into refrigerating box standby for ball milling;
5, select condenser ceramics substrate as experiment base material, base material is inserted in frock, by screen process press, copper slurry is evenly printed on to substrate surface, controlling serous coat thickness is 0.15mm, enters dryer copper slurry is dried with 240 degree speed 200min/m;
6, the base material of having dried being inserted to Temperature Setting curve in sintering furnace is 100-250-350-500-600, and controlling every temperature range time is 0.5h, and 600 are incubated 0.2h cooling while spending can open ventilation unit until room temperature by being naturally cooled to 150 while spending;
7, the base metal structure obtaining.
Embodiment 2:
1, the material of base metal structure is prepared in choosing; For copper and alloy thereof, a kind of organic solvent, glass carrier, flux material, anti-reduction-oxidation material, levelling agent, wetting agent form.And the selection of material copper powder; Be generally electrolytic copper powder, and copper powder to be made flake copper;
2, the above-mentioned various materials that prepare are allocated according to a certain percentage:
Copper powder (85%)+GPL (5%)+organic solvent+antioxidant+levelling agent+wetting agent;
3, the base metal slurry after allotment is inserted 3L ball grinder, adds to be greater than slurry weight 15% zirconium ball or stainless steel ball turns min8h with rotating speed 300;
4, after completing, the parked 3H of slurry to be put into refrigerating box standby for ball milling;
5, select condenser ceramics substrate as experiment base material, base material is inserted in frock, by screen process press, copper slurry is evenly printed on to substrate surface, controlling serous coat thickness is 0.2mm, enters dryer copper slurry is dried with 240 degree speed 200min/m;
6, the base material of having dried being inserted to Temperature Setting curve in sintering furnace is 100-250-350-500-600, and controlling every temperature range time is 0.5h, and 600 are incubated 0.2h cooling while spending can open ventilation unit until room temperature by being naturally cooled to 150 while spending;
7, the base metal structure obtaining.
Embodiment 3:
1, the material of base metal structure is prepared in choosing; For copper and alloy thereof, a kind of organic solvent, glass carrier, flux material, anti-reduction-oxidation material, levelling agent, wetting agent form.And the selection of material copper powder; Be generally electrolytic copper powder, and copper powder to be made flake copper;
2, the above-mentioned various materials that prepare are allocated according to a certain percentage:
Copper powder (80%)+GPL (4%)+organic solvent+antioxidant+levelling agent+wetting agent;
3, the base metal slurry after allotment is inserted 3L ball grinder, adds to be greater than slurry weight 15% zirconium ball or stainless steel ball turns min8h with rotating speed 300;
4, after completing, the parked 3H of slurry to be put into refrigerating box standby for ball milling;
5, select condenser ceramics substrate as experiment base material, base material is inserted in frock, by screen process press, copper slurry is evenly printed on to substrate surface, controlling serous coat thickness is 0.18mm, enters dryer copper slurry is dried with 240 degree speed 200min/m;
6, the base material of having dried being inserted to Temperature Setting curve in sintering furnace is 100-250-350-500-500, and controlling every temperature range time is 0.5h, and 600 are incubated 0.2h cooling while spending can open ventilation unit until room temperature by being naturally cooled to 150 while spending;
7, the base metal structure obtaining.
Electrode is prepared needed capital equipment;
1. screen process press
2. drying oven 380V 50HZ (power requirement)
Power: heating 7X2KW transmits 0.6KW
Maximum temperature: 400 degree
Speed: 95310Min practical application 166.7MM/min
Heating head of district 4500mm turnover part 2500mm
3. sintering furnace (clock hood type furnace)
380v/220,50hz three-phase alternating current
Power supply capacity: 100KVA
Temperature uniformity: 0.3%
In sum, technology key point of the present invention is, low temperature, hypoxemia amount, electrical property control, and key point is the continuity of electrode structure face, high adhesion force, good solderability and non-oxidizability.
Claims (7)
1. an electrodes in base metal structure, is characterized in that; By coating processes, base metal conductor paste layer is connected to 4,5 by carrier and be coated on the ceramic substrate 1 with certain electrical property, form the base metal layer (2,3) of certain thick film, be electrodes in base metal structure.
2. the electrode structure requiring as described in right 1, is characterized in that using the composition of base metal to comprise aluminium, tin, zinc, copper, nickel, chromium, molybdenum etc. and alloy thereof.
3. electrode structure as described in right 1, it is characterized in that being attached thing surface base metal thick film coating thickness is 0.1 μ m-30 μ m.
4. electrode structure as described in right 1,5, is characterized in that being attached the arbitrary shape that is shaped as of thing surface base metal thick film coating.
5. electrode structure as described in claim 1,5, is characterized in that being attached thing surface base metal thick film multiple coating.
6. a preparation method for electrodes in base metal structure, is characterized in that: the painting method that its described base metal conductor paste is coated in ceramic substrate 1 and other non-metal base plates comprises: solid precipitation method, chemical vapour deposition technique, sputter (magnetic control) and vapour deposition method, metallikon.
7. painting method as claimed in claim 6, technical process is as follows:
the material of base metal structure is prepared in choosing; For copper and alloy thereof, a kind of organic solvent, glass carrier, flux material, anti-reduction-oxidation material, levelling agent, wetting agent form.And the selection of material copper powder; Be generally electrolytic copper powder, and copper powder to be made flake copper;
Copper powder (75%--85%)+GPL (3%--5%)+organic solvent+antioxidant+levelling agent+wetting agent;
it is 100-250-350-500600 that the base material of having dried is inserted to Temperature Setting curve in sintering furnace, and controlling every temperature range time is 0.5h, and 600 are incubated 0.2h cooling while spending can open ventilation unit until room temperature by being naturally cooled to 150 while spending;
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN108169286A (en) * | 2018-01-08 | 2018-06-15 | 中国电子科技集团公司第二十四研究所 | A kind of preparation method and product for trichloroethylene solvent conductivity test probe |
| CN110469787A (en) * | 2019-08-19 | 2019-11-19 | 深圳市百柔新材料技术有限公司 | A kind of production method for printing LED backlight plate |
| CN113380440A (en) * | 2021-06-18 | 2021-09-10 | 福建瑞升电子科技有限公司 | Low-temperature copper electrode slurry and preparation method thereof |
| WO2024031500A1 (en) * | 2022-08-11 | 2024-02-15 | 李文熙 | Method for high-temperature sintering of base metal electrode or alloy in air |
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2012
- 2012-07-26 CN CN201210261654.0A patent/CN103578607A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108169286A (en) * | 2018-01-08 | 2018-06-15 | 中国电子科技集团公司第二十四研究所 | A kind of preparation method and product for trichloroethylene solvent conductivity test probe |
| CN110469787A (en) * | 2019-08-19 | 2019-11-19 | 深圳市百柔新材料技术有限公司 | A kind of production method for printing LED backlight plate |
| CN113380440A (en) * | 2021-06-18 | 2021-09-10 | 福建瑞升电子科技有限公司 | Low-temperature copper electrode slurry and preparation method thereof |
| CN113380440B (en) * | 2021-06-18 | 2023-03-10 | 福建瑞升电子科技有限公司 | Low-temperature copper electrode slurry and preparation method thereof |
| WO2024031500A1 (en) * | 2022-08-11 | 2024-02-15 | 李文熙 | Method for high-temperature sintering of base metal electrode or alloy in air |
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Application publication date: 20140212 |