CN119008076A - Conductive silver paste for low-temperature co-fired ceramic matrix and preparation method thereof - Google Patents
Conductive silver paste for low-temperature co-fired ceramic matrix and preparation method thereof Download PDFInfo
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- CN119008076A CN119008076A CN202411418677.7A CN202411418677A CN119008076A CN 119008076 A CN119008076 A CN 119008076A CN 202411418677 A CN202411418677 A CN 202411418677A CN 119008076 A CN119008076 A CN 119008076A
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- deionized water
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 239000000919 ceramic Substances 0.000 title claims abstract description 46
- 239000011159 matrix material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 60
- 239000004332 silver Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 162
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 102
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 239000008367 deionised water Substances 0.000 claims description 67
- 229910021641 deionized water Inorganic materials 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 63
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 54
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000001914 filtration Methods 0.000 claims description 46
- AKEXVWKYUAMNKL-UHFFFAOYSA-N 2,2-dimethylpropanoic acid;silver Chemical compound [Ag].CC(C)(C)C(O)=O AKEXVWKYUAMNKL-UHFFFAOYSA-N 0.000 claims description 40
- RQZVTOHLJOBKCW-UHFFFAOYSA-M silver;7,7-dimethyloctanoate Chemical compound [Ag+].CC(C)(C)CCCCCC([O-])=O RQZVTOHLJOBKCW-UHFFFAOYSA-M 0.000 claims description 39
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 claims description 36
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 33
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 33
- 229940116411 terpineol Drugs 0.000 claims description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 229920002635 polyurethane Polymers 0.000 claims description 20
- 239000004814 polyurethane Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 229920005749 polyurethane resin Polymers 0.000 claims description 17
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical group CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 16
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 11
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- -1 silver resin acid salt Chemical class 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 7
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000013008 thixotropic agent Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002042 Silver nanowire Substances 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000003973 paint Substances 0.000 description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of conductive paste, in particular to conductive silver paste for a low-temperature co-fired ceramic matrix and a preparation method thereof, wherein the conductive silver paste comprises the following raw materials in parts by mass: the silver powder for the low-temperature co-fired ceramic matrix has the advantages that the silver powder content in the conductive silver paste for the low-temperature co-fired ceramic matrix is far lower than that of the conventional prior art, the production cost is greatly reduced, in addition, the performance reduction caused by the difference of affinities between the silver powder and the matrix in the sintering process is effectively reduced due to the introduction of silver resinate in the silver powder, and the sintering temperature of the conductive silver paste is reduced due to the fact that the silver nanowire, the silver nanosheet and the silver nanoparticle with different dimensions are compounded due to the introduction of the silver resinate, so that the finally prepared conductive silver paste has good hardness and adhesive force and good conductive performance.
Description
Technical Field
The invention relates to the technical field of conductive paste, in particular to conductive silver paste for a low-temperature co-fired ceramic matrix and a preparation method thereof.
Background
With the rapid development of modern information technology, demands are made on miniaturization, convenience, multifunction and high reliability of electronic products, and LTCC (Low Temperature Co-FIRED CERAMIC) technology, i.e., low-temperature co-fired ceramic technology, is an advanced passive integrated and hybrid circuit, which can package three passive components (including resistors, capacitors and inductors) and various passive components (such as filters, transformers, etc.) thereof in a multilayer wiring substrate and integrate the three passive components and active components (such as power MOS, transistors, IC circuit modules, etc.) together into a complete circuit system, and low-temperature co-fired ceramic technology is a remarkable integrated component technology developed in recent years, because the low-temperature co-fired ceramic technology can meet the above demands of electronic products and has become the first choice for integration and modularity of electronic components in the future. As the design basis of high-performance and low-energy-consumption devices, the development of LTCC technology and related materials has great application value. The conductive silver paste is a noble metal electronic paste, is formed by stirring and rolling silver powder, an organic carrier and an inorganic or high polymer binder, is the most important type of the current electronic paste and has the largest demand, has an irreplaceable position in the electronic field, and is widely applied to the fields of touch screens, solar cell electrodes, flexible sensors, multilayer ceramic capacitors, filters, packaging circuits and the like due to the characteristics of good conductivity, weldability, reliability and the like.
In order to reduce the sintering temperature, the ceramic is usually realized by doping low-melting-point oxide or low-melting-point glass, the traditional silver paste is difficult to match with the ceramic due to a complex system, even the basic use requirement cannot be met, in the cofiring process of the traditional conductive silver paste and a low-temperature cofiring ceramic matrix, the insulating resistance is reduced due to the fact that the silver powder excessively diffuses into the ceramic body due to the fact that the difference exists between the affinity of the ceramic and the silver powder and the affinity of the silver powder exist, the risk of electrical breakdown of a circuit exists, and more cavities are prone to occurring in a silver electrode layer after sintering; and the insufficient bonding force between the silver layer and the ceramic interface can cause serious consequences of cracking and layering in the device. In addition, in order to increase the conductivity of the conductive silver paste in the prior art, the use amount of silver powder is generally increased, but the production cost is also greatly increased due to the high price of silver powder.
Therefore, according to the related art, there is a need to develop a conductive silver paste for low-temperature co-fired ceramic substrates and a method for preparing the same.
Disclosure of Invention
In view of the above, the invention aims to provide a conductive silver paste for a low-temperature co-fired ceramic matrix and a preparation method thereof, so as to solve the problems that the conductive silver paste produced in the prior art is difficult to achieve both good conductivity and low cost.
Based on the above purpose, the invention provides a conductive silver paste for a low-temperature co-fired ceramic matrix and a preparation method thereof.
The conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following raw materials in parts by mass: 40-60 parts of composite silver powder, 26-55 parts of organic carrier, 2-5 parts of solvent, 0.5-5 parts of inorganic additive, 0.5-2 parts of plasticizer and 0.5-2 parts of thixotropic agent;
the composite silver powder is prepared from nano silver powder and silver resinate in a mass ratio of 32-51:8-9;
the nano silver powder is composed of nano silver wires, nano silver sheets and nano silver particles according to the mass ratio of 7-14: 23-33:2-4;
The silver resin acid salt is prepared from silver neodecanoate, silver pivalate and silver n-butyrate according to a mass ratio of 4-5:3.5-4: 0.5-1;
the organic carrier is obtained by mixing polyether polyurethane silver resin, aqueous polyurethane resin and aqueous acrylic resin according to a mass ratio of 12-22:10-20:4-13.
Preferably, the preparation method of the polyether polyurethane silver resin comprises the following steps:
adding 38-40mL of butyl acetate into 45-50g of polyether polyurethane resin, mechanically stirring for 20min, adding 1-1.5mL of aqueous solution of silver nitrate, and stirring for 30min to obtain polyether polyurethane silver resin.
Preferably, the aqueous solution of silver nitrate is prepared by adding 0.2-0.4g of silver nitrate to 1-1.5ml of deionized water at 75-80 ℃.
Preferably, the preparation method of the silver neodecanoate comprises the following steps:
Step A1, dissolving sodium hydroxide in deionized water to obtain a mixed solution A1;
a2, dissolving neodecanoic acid in methanol to obtain a mixed solution A2;
step A3, dissolving silver nitrate in deionized water to obtain a mixed solution A3;
A4, adding the mixed solution A1 into the mixed solution A2, stirring at room temperature for reaction for 30min, adding the mixed solution A3, stirring for 30min, filtering, washing with ethanol for 3-5 times, and drying in a vacuum oven at 60 ℃ in dark for 10-12h to obtain a silver neodecanoate precursor;
step A5. The xylene, terpineol and silver neodecanoate precursor are placed in a glass bottle, and finally the obtained solution is filtered by a 200 μm syringe filter to obtain silver neodecanoate.
Preferably, the dosage ratio of sodium hydroxide to deionized water in step A1 is 2-3g:45-55mL;
The dosage ratio of the neodecanoic acid to the methanol in the step A2 is 8-12g:45-55mL;
The dosage ratio of the silver nitrate to the deionized water in the step A3 is 9-10g:48-52mL;
The volume ratio of the mixed solution A1 to the mixed solution A2 to the mixed solution A3 in the step A4 is 45-55:45-55:48-52;
The mass ratio of the dimethylbenzene to the terpineol to the silver neodecanoate precursor in the step A5 is 2-3:2-3:5.5-6.5.
Preferably, the preparation method of the silver pivalate comprises the following steps:
Step B1, dissolving sodium hydroxide in deionized water to obtain a mixed solution B1;
B2, dissolving pivalic acid in methanol to obtain a mixed solution B2;
Step B3, dissolving silver nitrate in deionized water to obtain a mixed solution B3;
Step B4., adding the mixed solution A into the mixed solution B, stirring at room temperature for reaction for 30min, then adding the mixed solution C, stirring for 30min, filtering, washing with ethanol for 3-5 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 10-12h to obtain a silver pivalate precursor;
Step B5. placing xylene, terpineol and silver pivalate precursor in a glass bottle, and finally filtering the obtained solution by using a 200 μm syringe filter to obtain the silver pivalate.
Preferably, the dosage ratio of sodium hydroxide to deionized water in the step B1 is 2-3g:45-55mL;
The dosage ratio of the pivalic acid to the methanol in the step B2 is 8-12g:45-55mL;
the dosage ratio of the silver nitrate to the deionized water in the step B3 is 9-10g:48-52mL;
In the step B4, the volume ratio of the mixed solution B1 to the mixed solution B2 to the mixed solution B3 is 45-55:45-55:48-52;
The mass ratio of the dimethylbenzene to the terpineol to the silver pivalate precursor in the step B5 is 2-3:2-3:5.5-6.5.
Preferably, the preparation method of the silver n-butyrate comprises the following steps:
step C1, dissolving sodium hydroxide in deionized water to obtain a mixed solution C1;
Step C2., dissolving n-butyric acid in methanol to obtain a mixed solution C2;
Step C3., dissolving silver nitrate in deionized water to obtain a mixed solution C3;
Step C4, adding the mixed solution C1 into the mixed solution C2, stirring at room temperature for reaction for 30min, adding the mixed solution C3, stirring for 30min, filtering, washing with ethanol for 3-5 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 10-12h to obtain a silver n-butyrate precursor;
Step C5. placing xylene, terpineol and silver pivalate precursor in a glass bottle, and finally filtering the obtained solution by using a 200 μm syringe filter to obtain silver n-butyrate.
Preferably, the dosage ratio of sodium hydroxide to deionized water in step C1 is 2-3g:45-55mL;
The dosage ratio of the n-butyric acid to the methanol in the step C2 is 8-12g:45-55mL;
The dosage ratio of the silver nitrate to the deionized water in the step C3 is 9-10g:48-52mL;
the volume ratio of the mixed solution C1 to the mixed solution C2 to the mixed solution C3 in the step C4 is 45-55:45-55:48-52;
The mass ratio of the dimethylbenzene to the terpineol to the silver n-butyrate precursor in the step C5 is 2-3:2-3:5.5-6.5.
Preferably, the average diameter of the nano silver wire is 58-60nm, and the length-diameter ratio is 175;
the size of the nano silver flake is 2-3 mu m;
The average particle diameter of the nano silver particles is 3.8-4nm.
Preferably, the solvent is any one of diethylene glycol diethyl ether, diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate and terpineol;
The inorganic additive is any one of magnesium oxide, titanium dioxide, copper oxide, zinc oxide and aluminum oxide;
the plasticizer is tributyl citrate; the thixotropic agent is polyamide wax.
The preparation method of the conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following steps:
Mixing the composite silver powder, an organic carrier, a solvent, an inorganic additive, a plasticizer and a thixotropic agent, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature cofired ceramic matrix.
The invention has the beneficial effects that:
the content of silver powder in the conductive silver paste for the low-temperature co-fired ceramic matrix is far lower than that of the conventional prior art, so that the production cost is greatly reduced, and in addition, the performance degradation caused by the difference of affinity between the silver powder and the matrix in the sintering process is effectively reduced due to the introduction of silver resinate in the silver powder.
According to the silver powder provided by the invention, the silver resinate is introduced, the silver resinate is thermally decomposed in the sintering process, the thermal decomposition product is matched with the nano silver powder, and a conductive path is formed through stacking and fusion, so that the sintering temperature of the conductive silver paste is greatly reduced.
According to the silver resinate provided by the invention, the neodecanoate silver, the pivalate silver and the n-butyrate silver mixed in a specific proportion are introduced, wherein the compounding of the long-chain silver resinate and the short-chain silver resinate and the compounding of the straight-chain silver resinate and the branched-chain silver resinate enable an excellent sintering network and a larger grain size to be formed in the sintering process, and finally the conductivity of the conductive silver paste is further improved.
According to the organic carrier provided by the invention, through the compounding of the polyether polyurethane silver resin, the aqueous polyurethane resin and the aqueous acrylic resin, on one hand, the affinity between silver powder and a matrix can be effectively increased, and meanwhile, the adhesive force of conductive silver paste can be increased, the cracking and layering in a device caused by insufficient interfacial bonding force can be effectively reduced, and the potential safety hazard is further reduced.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The sources and properties of part of the raw materials used in the invention are as follows:
The polyether polyurethane resin is industrial pure and is purchased from the chemical auxiliary agent of warrior in Jiangyin city.
Example 1: the preparation method of the conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following steps:
s1, 2g of sodium hydroxide is dissolved in 45mL of deionized water to obtain a mixed solution A1;
s2, dissolving 8g of neodecanoic acid in 45mL of methanol to obtain a mixed solution A2;
s3, 9g of silver nitrate is dissolved in 48mL of deionized water to obtain a mixed solution A3;
s4, adding 45mL of mixed solution A1 into 45mL of mixed solution A2, stirring at room temperature for reaction for 30min, adding 48mL of mixed solution A3, stirring for 30min, filtering, washing with ethanol for 3 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 10h to obtain a silver neodecanoate precursor;
s5, placing 2g of dimethylbenzene, 2g of terpineol and 5.5g of silver neodecanoate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver neodecanoate;
s6, 2g of sodium hydroxide is dissolved in 45mL of deionized water to obtain a mixed solution B1;
s7, dissolving 8g of pivalic acid in 45mL of methanol to obtain a mixed solution B2;
s8, 9g of silver nitrate is dissolved in 48mL of deionized water to obtain a mixed solution B3;
s9, adding 45mL of mixed solution B1 into 45mL of mixed solution B2, stirring at room temperature for reaction for 30min, adding 48mL of mixed solution B3, stirring for 30min, filtering, washing with ethanol for 3 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 10h to obtain a silver pivalate precursor;
s10, placing 2g of dimethylbenzene, 2g of terpineol and 5.5g of silver pivalate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver pivalate;
S11, 2g of sodium hydroxide is dissolved in 45mL of deionized water to obtain a mixed solution C1;
S12, 8g of n-butyric acid is dissolved in 45mL of methanol to obtain a mixed solution C2;
S13, 9g of silver nitrate is dissolved in 48mL of deionized water to obtain a mixed solution C3;
S14, adding 45mL of mixed solution C1 into 45mL of mixed solution C2, stirring at room temperature for reaction for 30min, then adding 48mL of mixed solution C3, stirring for 30min, filtering, washing with ethanol for 3 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 10h to obtain a silver n-butyrate precursor;
s15, placing 2g of dimethylbenzene, 2g of terpineol and 5.5g of silver n-butyrate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver n-butyrate;
s16, mixing 4g of silver neodecanoate, 3.5g of silver pivalate and 0.5g of silver n-butyrate to obtain silver resinate;
S17, uniformly mixing 7g of nano silver wires with the average diameter of 58nm and the length-diameter ratio of 175, 23g of nano silver flakes with the size of 2 mu m and 2g of nano silver particles with the average particle diameter of 3.8nm to obtain nano silver powder;
s18, mixing 32g of nano silver powder and 8g of silver resinate to obtain composite silver powder;
S19, adding 0.2g of silver nitrate into 1mL of deionized water at 75 ℃ to prepare a silver nitrate aqueous solution, adding 38mL of butyl acetate into 45g of polyether polyurethane resin, mechanically stirring for 20min, adding 1mL of silver nitrate aqueous solution, and stirring for 30min to obtain polyether polyurethane silver resin;
s20, uniformly mixing 12g of polyether polyurethane silver resin, 10g of aqueous polyurethane resin and 4g of aqueous acrylic ester to obtain an organic carrier;
S21, mixing 40g of composite silver powder, 26g of organic carrier, 2g of diethylene glycol diethyl ether, 0.5g of magnesium oxide, 0.5g of tributyl citrate and 0.5g of polyamide wax, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature co-fired ceramic matrix.
Example 2: the preparation method of the conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following steps:
S1, dissolving 2.2g of sodium hydroxide in 49mL of deionized water to obtain a mixed solution A1;
s2, 9g of neodecanoic acid is dissolved in 47mL of methanol to obtain a mixed solution A2;
s3, 9.2g of silver nitrate is dissolved in 49mL of deionized water to obtain a mixed solution A3;
S4, adding 47mL of mixed solution A1 into 47mL of mixed solution A2, stirring at room temperature for reaction for 30min, adding 49mL of mixed solution A3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver neodecanoate precursor;
S5, placing 2.2g of dimethylbenzene, 2.2g of terpineol and 5.7g of silver neodecanoate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver neodecanoate;
S6, dissolving 2.2g of sodium hydroxide in 47mL of deionized water to obtain a mixed solution B1;
S7, 9g of pivalic acid is dissolved in 47mL of methanol to obtain a mixed solution B2;
S8, 9.2g of silver nitrate is dissolved in 49mL of deionized water to obtain a mixed solution B3;
s9, adding 47mL of mixed solution B1 into 47mL of mixed solution B2, stirring at room temperature for reaction for 30min, adding 49mL of mixed solution B3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver pivalate precursor;
S10, placing 2.2g of dimethylbenzene, 2.2g of terpineol and 5.7g of silver pivalate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver pivalate;
s11, dissolving 2.2g of sodium hydroxide in 47mL of deionized water to obtain a mixed solution C1;
s12, 9g of n-butyric acid is dissolved in 47mL of methanol to obtain a mixed solution C2;
S13, 9.2g of silver nitrate is dissolved in 49mL of deionized water to obtain a mixed solution C3;
S14, adding 47mL of mixed solution C1 into 47mL of mixed solution C2, stirring at room temperature for reaction for 30min, adding 49mL of mixed solution C3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver n-butyrate precursor;
S15, placing 2.2g of dimethylbenzene, 2.2g of terpineol and 5.7g of silver n-butyrate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver n-butyrate;
S16, mixing 4.2g of silver neodecanoate, 3.7g of silver pivalate and 0.7g of silver n-butyrate to obtain silver resinate;
S17, uniformly mixing 12.5g of nano silver wires with an average diameter of 59nm and an aspect ratio of 175, 32.5g of nano silver flakes with a size of 2.5 mu m and 3.5g of nano silver particles with an average particle size of 3.9nm to obtain nano silver powder;
s18, mixing 48g of nano silver powder and 8.2g of silver resinate to obtain composite silver powder;
s19, adding 0.25g of silver nitrate into 1.1mL of deionized water at 76 ℃ to prepare a silver nitrate aqueous solution, adding 39mL of butyl acetate into 46g of polyether polyurethane resin, mechanically stirring for 20min, adding 1.1mL of silver nitrate aqueous solution, and stirring for 30min to obtain polyether polyurethane silver resin;
S20, uniformly mixing 14g of polyether polyurethane silver resin, 12g of aqueous polyurethane resin and 6g of aqueous acrylic ester to obtain an organic carrier;
S21, mixing 56g of composite silver powder, 30g of organic carrier, 3g of diethylene glycol diethyl ether, 3g of magnesium oxide, 1.2g of tributyl citrate and 1.2g of polyamide wax, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature cofired ceramic matrix.
Example 3: the preparation method of the conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following steps:
S1, dissolving 2.4g of sodium hydroxide in 49mL of deionized water to obtain a mixed solution A1;
s2, dissolving 10g of neodecanoic acid in 49mL of methanol to obtain a mixed solution A2;
s3, 9.6g of silver nitrate is dissolved in 50mL of deionized water to obtain a mixed solution A3;
s4, adding 49mL of the mixed solution A1 into 49mL of the mixed solution A2, stirring at room temperature for reaction for 30min, adding 50mL of the mixed solution A3, stirring for 30min, filtering, washing with ethanol for 5 times, and drying in a vacuum oven at 60 ℃ in the dark for 11h to obtain a silver neodecanoate precursor;
s5, placing 2.5g of dimethylbenzene, 2.5g of terpineol and 6g of silver neodecanoate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver neodecanoate;
s6, dissolving 2.5g of sodium hydroxide in 50mL of deionized water to obtain a mixed solution B1;
s7, dissolving 10g of pivalic acid in 50mL of methanol to obtain a mixed solution B2;
S8, 9.5g of silver nitrate is dissolved in 50mL of deionized water to obtain a mixed solution B3;
s9, adding 50mL of mixed solution B1 into 50mL of mixed solution B2, stirring at room temperature for reaction for 30min, adding 50mL of mixed solution B3, stirring for 30min, filtering, washing with ethanol for 5 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver pivalate precursor;
S10, placing 2.5g of dimethylbenzene, 2.5g of terpineol and 6g of silver pivalate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver pivalate;
s11, dissolving 2.5g of sodium hydroxide in 50mL of deionized water to obtain a mixed solution C1;
s12, dissolving 10g of n-butyric acid in 50mL of methanol to obtain a mixed solution C2;
s13, 9.5g of silver nitrate is dissolved in 50mL of deionized water to obtain a mixed solution C3;
s14, adding 50mL of the mixed solution C1 into 50mL of the mixed solution C2, stirring at room temperature for reaction for 30min, adding 50mL of the mixed solution C3, stirring for 30min, filtering, washing with ethanol for 5 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver n-butyrate precursor;
S15, placing 2.5g of dimethylbenzene, 2.5g of terpineol and 6g of silver n-butyrate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver n-butyrate;
s16, mixing 4.5g of silver neodecanoate, 3.8g of silver pivalate and 0.7g of silver n-butyrate to obtain silver resinate;
s17, uniformly mixing 13g of nano silver wires with an average diameter of 59nm and an aspect ratio of 175, 32.5g of nano silver flakes with a size of 2.5 mu m and 3.5g of nano silver particles with an average particle size of 3.9nm to obtain nano silver powder;
S18, mixing 49g of nano silver powder and 8.5g of silver resinate to obtain composite silver powder;
s19, adding 0.3g of silver nitrate into 1.2mL of deionized water at 78 ℃ to prepare a silver nitrate aqueous solution, adding 39mL of butyl acetate into 47g of polyether polyurethane resin, mechanically stirring for 20min, adding 1.3mL of silver nitrate aqueous solution, and stirring for 30min to obtain polyether polyurethane silver resin;
S20, uniformly mixing 16g of polyether polyurethane silver resin, 14g of aqueous polyurethane resin and 8g of aqueous acrylic ester to obtain an organic carrier;
s21, mixing 57g of composite silver powder, 35g of organic carrier, 5g of diethylene glycol butyl ether acetate, 1.8g of copper oxide, 1.5g of tributyl citrate and 1.5g of polyamide wax, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature cofired ceramic matrix.
Example 4: the preparation method of the conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following steps:
s1, dissolving 2.6g of sodium hydroxide in 51mL of deionized water to obtain a mixed solution A1;
S2, dissolving 10g of neodecanoic acid in 51mL of methanol to obtain a mixed solution A2;
s3, 9.6g of silver nitrate is dissolved in 50mL of deionized water to obtain a mixed solution A3;
s4, adding 51mL of mixed solution A1 into 51mL of mixed solution A2, stirring at room temperature for reaction for 30min, adding 50mL of mixed solution A3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver neodecanoate precursor;
S5, placing 2.6g of dimethylbenzene, 2.6g of terpineol and 6.1g of silver neodecanoate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver neodecanoate;
s6, 2.6g of sodium hydroxide is dissolved in 51mL of deionized water to obtain a mixed solution B1;
S7, dissolving 10g of pivalic acid in 51mL of methanol to obtain a mixed solution B2;
s8, 9.6g of silver nitrate is dissolved in 50mL of deionized water to obtain a mixed solution B3;
S9, adding 51mL of mixed solution B1 into 51mL of mixed solution B2, stirring at room temperature for reaction for 30min, adding 50mL of mixed solution B3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver pivalate precursor;
S10, placing 2.6g of dimethylbenzene, 2.6g of terpineol and 6.1g of silver pivalate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver pivalate;
s11, dissolving 2.6g of sodium hydroxide in 51mL of deionized water to obtain a mixed solution C1;
S12, dissolving 10g of n-butyric acid in 51mL of methanol to obtain a mixed solution C2;
s13, 9.6g of silver nitrate is dissolved in 50mL of deionized water to obtain a mixed solution C3;
s14, adding 51mL of mixed solution C1 into 51mL of mixed solution C2, stirring at room temperature for reaction for 30min, then adding 50mL of mixed solution C3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver n-butyrate precursor;
S15, placing 2.6g of dimethylbenzene, 2.6g of terpineol and 6.1g of silver n-butyrate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver n-butyrate;
s16, mixing 4.6g of silver neodecanoate, 3.8g of silver pivalate and 0.8g of silver n-butyrate to obtain silver resinate;
S17, uniformly mixing 13g of nano silver wires with an average diameter of 59nm and an aspect ratio of 175, 32.8g of nano silver flakes with a size of 2.4 mu m and 3.6g of nano silver particles with an average particle size of 3.9nm to obtain nano silver powder;
S18, mixing 49g of nano silver powder and 8.6g of silver resinate to obtain composite silver powder;
S19, adding 0.35g of silver nitrate into 1.3mL of deionized water at 78 ℃ to prepare a silver nitrate aqueous solution, adding 39.2mL of butyl acetate into 48g of polyether polyurethane resin, mechanically stirring for 20min, adding 1.3mL of silver nitrate aqueous solution, and stirring for 30min to obtain polyether polyurethane silver resin;
s20.18g of polyether polyurethane silver resin, 16g of aqueous polyurethane resin and 9g of aqueous acrylic ester are uniformly mixed to obtain an organic carrier;
S21, mixing 58g of composite silver powder, 40g of organic carrier, 3g of diethylene glycol butyl ether acetate, 2.8g of copper oxide, 1.6g of tributyl citrate and 1.6g of polyamide wax, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature cofired ceramic matrix.
Example 5: the preparation method of the conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following steps:
S1, dissolving 2.8g of sodium hydroxide in 53mL of deionized water to obtain a mixed solution A1;
S2, dissolving 11g of neodecanoic acid in 53mL of methanol to obtain a mixed solution A2;
s3, 9.8g of silver nitrate is dissolved in 51mL of deionized water to obtain a mixed solution A3;
S4, adding 53mL of mixed solution A1 into 53mL of mixed solution A2, stirring at room temperature for reaction for 30min, adding 51mL of mixed solution A3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver neodecanoate precursor;
s5, placing 2.8g of dimethylbenzene, 2.8g of terpineol and 6.3g of silver neodecanoate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver neodecanoate;
S6, 2.8g of sodium hydroxide is dissolved in 53mL of deionized water to obtain a mixed solution B1;
s7, 11g of pivalic acid is dissolved in 53mL of methanol to obtain a mixed solution B2;
s8, 9.8g of silver nitrate is dissolved in 51mL of deionized water to obtain a mixed solution B3;
s9, adding 53mL of mixed solution B1 into 53mL of mixed solution B2, stirring at room temperature for reaction for 30min, adding 51mL of mixed solution B3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver pivalate precursor;
S10, placing 2.8g of dimethylbenzene, 2.8g of terpineol and 6.3g of silver pivalate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver pivalate;
s11, dissolving 2.8g of sodium hydroxide in 53mL of deionized water to obtain a mixed solution C1;
S12, dissolving 11g of n-butyric acid in 53mL of methanol to obtain a mixed solution C2;
S13, 9.8g of silver nitrate is dissolved in 51mL of deionized water to obtain a mixed solution C3;
S14, adding 53mL of mixed solution C1 into 53mL of mixed solution C2, stirring at room temperature for reaction for 30min, adding 51mL of mixed solution C3, stirring for 30min, filtering, washing with ethanol for 4 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 11h to obtain a silver n-butyrate precursor;
s15, placing 2.8g of dimethylbenzene, 2.8g of terpineol and 6.3g of silver n-butyrate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver n-butyrate;
S16, mixing 4.8g of silver neodecanoate, 3.9g of silver pivalate and 0.9g of silver n-butyrate to obtain silver resinate;
S17, uniformly mixing 13g of nano silver wires with an average diameter of 59nm and an aspect ratio of 175, 32.8g of nano silver flakes with a size of 2.5 mu m and 3.5g of nano silver particles with an average particle size of 3.9nm to obtain nano silver powder;
s18, mixing 50g of nano silver powder and 8.8g of silver resinate to obtain composite silver powder;
S19, adding 0.35g of silver nitrate into 1.4mL of deionized water at 79 ℃ to prepare a silver nitrate aqueous solution, adding 39mL of butyl acetate into 49g of polyether polyurethane resin, mechanically stirring for 20min, adding 1.4mL of silver nitrate aqueous solution, and stirring for 30min to obtain polyether polyurethane silver resin;
S20, uniformly mixing 20g of polyether polyurethane silver resin, 18g of aqueous polyurethane resin and 11g of aqueous acrylic ester to obtain an organic carrier;
S21, mixing 59g of composite silver powder, 50g of organic carrier, 4g of diethylene glycol diethyl ether acetate, 2.9g of zinc oxide, 1.8g of tributyl citrate and 1.8g of polyamide wax, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature cofired ceramic matrix.
Example 6: the preparation method of the conductive silver paste for the low-temperature co-fired ceramic matrix comprises the following steps:
s1, dissolving 3g of sodium hydroxide in 55mL of deionized water to obtain a mixed solution A1;
S2, dissolving 12g of neodecanoic acid in 55mL of methanol to obtain a mixed solution A2;
s3, dissolving 10g of silver nitrate in 52mL of deionized water to obtain a mixed solution A3;
S4, adding 55mL of the mixed solution A1 into 55mL of the mixed solution A2, stirring at room temperature for reaction for 30min, adding 52mL of the mixed solution A3, stirring for 30min, filtering, washing with ethanol for 5 times, and drying in a vacuum oven at 60 ℃ in a dark place for 12h to obtain a silver neodecanoate precursor;
S5, placing 3g of dimethylbenzene, 3g of terpineol and 6.5g of silver neodecanoate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver neodecanoate;
s6, dissolving 3g of sodium hydroxide in 55mL of deionized water to obtain a mixed solution B1;
s7, dissolving 12g of pivalic acid in 55mL of methanol to obtain a mixed solution B2;
S8, dissolving 10g of silver nitrate in 52mL of deionized water to obtain a mixed solution B3;
S9, adding 55mL of mixed solution B1 into 55mL of mixed solution B2, stirring at room temperature for reaction for 30min, adding 52mL of mixed solution B3, stirring for 30min, filtering, washing with ethanol for 5 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 12h to obtain a silver pivalate precursor;
S10, placing 3g of dimethylbenzene, 3g of terpineol and 6.5g of silver pivalate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver pivalate;
S11, dissolving 3g of sodium hydroxide in 55mL of deionized water to obtain a mixed solution C1;
S12, dissolving 12g of n-butyric acid in 55mL of methanol to obtain a mixed solution C2;
s13, dissolving 10g of silver nitrate in 52mL of deionized water to obtain a mixed solution C3;
S14, adding 55mL of the mixed solution C1 into 55mL of the mixed solution C2, stirring at room temperature for reaction for 30min, adding 52mL of the mixed solution C3, stirring for 30min, filtering, washing with ethanol for 5 times, and drying in a vacuum oven at 60 ℃ in a dark place for 12h to obtain a silver n-butyrate precursor;
S15, placing 3g of dimethylbenzene, 3g of terpineol and 6.5g of silver n-butyrate precursor into a glass bottle, and finally filtering the obtained solution by using a 200 mu m syringe type filter to obtain silver n-butyrate;
S16, mixing 5g of silver neodecanoate, 4g of silver pivalate and 1g of silver n-butyrate to obtain silver resinate;
S17, uniformly mixing 14g of nano silver wires with the average diameter of 60nm and the length-diameter ratio of 175, 33g of nano silver flakes with the size of 3 mu m and 4g of nano silver particles with the average particle diameter of 4nm to obtain nano silver powder;
s18, mixing 51g of nano silver powder and 9g of silver resinate to obtain composite silver powder;
S19, adding 0.4g of silver nitrate into 1.5mL of deionized water at 80 ℃ to prepare a silver nitrate aqueous solution, adding 40mL of butyl acetate into 50g of polyether polyurethane resin, mechanically stirring for 20min, adding 1.5mL of silver nitrate aqueous solution, and stirring for 30min to obtain polyether polyurethane silver resin;
s20, uniformly mixing 22g of polyether polyurethane silver resin, 20g of aqueous polyurethane resin and 13g of aqueous acrylic ester to obtain an organic carrier;
S21, mixing 60g of composite silver powder, 55g of organic carrier, 22g of terpineol, 5g of alumina, 2g of tributyl citrate and 2g of polyamide wax, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature cofired ceramic matrix.
Comparative example 1:
Compared with the embodiment 1, the comparative example has no silver neodecanoate added in the preparation process of the conductive silver paste, and the rest steps and parameters are the same, so that the comparative example is not repeated, and finally the conductive silver paste is obtained.
Comparative example 2:
compared with the embodiment 1, the comparative example has no silver pivalate added in the preparation process of the conductive silver paste, and the rest steps and parameters are the same, so that the comparative example is not repeated, and finally the conductive silver paste is obtained.
Comparative example 3:
Compared with the embodiment 1, the comparative example has no silver n-butyrate added in the preparation process of the conductive silver paste, and the rest steps and parameters are the same, so that the comparative example is not repeated, and finally the conductive silver paste is obtained.
Comparative example 4:
Compared with the embodiment 1, the comparative example only adjusts the dosage of the silver neodecanoate from 4g to 0.5g, adjusts the dosage of the n-butyric acid from 0.5g to 4g, and has the same other steps and parameters, and the comparative example does not repeat any more description, and finally the conductive silver paste is obtained.
Comparative example 5:
Compared with the embodiment 1, the comparative example has no silver resinate added in the preparation process of the conductive silver paste, and the rest steps and parameters are the same, so that the comparative example is not repeated, and finally the conductive silver paste is obtained.
Comparative example 6:
Compared with the embodiment 1, the comparative example has no nano silver wire and nano silver sheet added in the preparation process of the conductive silver paste, and the rest steps and parameters are the same, so that the comparative example is not repeated, and finally the conductive silver paste is obtained.
Comparative example 7:
the comparative example and the example 1 only adjust the dosage of the nano silver flake from 23g to 3g, adjust the dosage of the nano silver particle from 2g to 32g, and the other steps and parameters are the same, and the comparative example is not repeated, thus finally obtaining the conductive silver paste.
Comparative example 8:
The comparative example and the example 1 have the same steps and parameters as the other steps and parameters without adding polyether polyurethane silver resin in the preparation process of the conductive silver paste, and the comparative example is not repeated, so that the conductive silver paste is finally obtained.
Comparative example 9:
Compared with the embodiment 1, the comparative example only adjusts the dosage of the polyether polyurethane silver resin from 12g to 4g, adjusts the dosage of the water-based acrylic ester from 4g to 12g, and has the same steps and parameters, and the comparative example does not repeat any more description, and finally the conductive silver paste is obtained.
Performance test:
Resistivity test:
The resistivity is a physical quantity used for representing the conductivity of a substance, and the method for testing the related conductivity of the conductive silver paste comprises the following steps: firstly, coating prepared silver paste on a glass slide to prepare a conductive circuit, then carrying out vacuum curing for 2 hours at 160 ℃, and finally detecting the surface resistivity of the cured silver paste by adopting an RTS-9 type double-electric-measurement four-probe tester;
Adhesion test:
the adhesive force is an important index for representing and measuring the performance of the conductive silver paste, when the adhesive force is low, a silver paste paint film is easy to foam and fall off, and effective connection between electronic elements or devices is difficult to realize. First, the method includes the steps of. The glass substrate coated with silver paste was placed on a flat and hard object surface, and a vertical cut of 90 ° cross scratches was made using a hundred blade, which was formed into 10×10 lattice patterns at regular intervals on the coating layer with a uniform force and rate, and then gently brushed several times with a soft brush in a diagonal direction of the lattice, to remove paint chips. Finally, placing the center point of the standard 75mm transparent pressure-sensitive adhesive tape on a grid, enabling the direction to be parallel to a group of cutting lines, flattening the position of the adhesive tape on the grid by using fingers, and forcefully rubbing and pressing the adhesive tape by fingertips to ensure that the adhesive tape is in good contact with a coating, and smoothly peeling the adhesive tape within 5min at an angle close to 60 degrees within 0.5-1.0s, wherein the following table 1 is an adhesive force evaluation standard, and when the adhesive force grade of a sample is 0 grade and 1 grade, the hundred grid test is qualified, and recording the adhesive force when the curing temperature is 160 ℃ and 200 ℃;
Pencil hardness test:
Pencil hardness is the resistance that the conductive silver paste has to the intrusion of a foreign object into its surface, which is one of the important properties of the mechanical strength of the conductive silver paste. A hardness tester (QFH-A) of Quzhou Ai Pu metering instruments, inc. was used in this experiment, and the hardness test method was performed according to national standard GB/T6739-2006 paint and varnish pencil method to determine paint film hardness. First, the paint template is placed on a horizontally stable surface, the instrument is held horizontally, and the prepared pencil is inserted into the pencil hardness tester and fixed. Then, according to national standard requirements, a weight is loaded until the pencil load is (1.00+/-0.05 kg). Finally, the tip of the pencil is placed on the surface of the paint film to be tested, and after the tip of the pencil contacts the paint film coating, the test plate is pushed, and the test plate is pushed at a speed of 0.5-1mm/s to a distance of at least 7mm away from the direction of an operator. The hardness grade judgment standard is as follows: the pencil hardness of the paint film coating was expressed as the hardness of the hardest pencil that did not cause scratches of 3m and above to the paint film coating, and the hardness at curing temperatures of 160℃and 200℃were recorded;
The results are shown in Table 2 below:
TABLE 1 evaluation criteria for paint film adhesion
Table 2 summary of experimental results for example 1-example 6 and comparative example 1-comparative example 9
Data analysis:
As can be seen from tables 1 and 2, the conductive silver paste prepared by the invention has better conductive performance, higher hardness and better adhesive force.
The silver resinate and the organic carrier are compounded to form a conductive network in the system, meanwhile, the nano silver wires, the nano silver sheets and the silver nano particles with different dimensions in the nano silver powder are compounded, the conductive paths in the system can be increased, the conductive effect of the finally prepared conductive silver paste is improved, the introduction of the silver neodecanoate, the silver pivalate and the n-butyric acid in the silver resinate can be synergistically enhanced with the polyether polyurethane silver resin, and the organic carrier gradually starts to shrink in the curing and heating process along with the rising of the temperature component, so that a cross-linking network is formed in the system, the distance between the composite silver powder particles is reduced, the composite silver powder particles are closely contacted, the organic carrier is closely attached to equipment, and the finally prepared conductive silver paste has better conductive performance, and meanwhile, has better adhesive force and hardness.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (10)
1. The conductive silver paste for the low-temperature co-fired ceramic matrix is characterized by comprising the following raw materials in parts by mass: 40-60 parts of composite silver powder, 26-55 parts of organic carrier, 2-5 parts of solvent, 0.5-5 parts of inorganic additive, 0.5-2 parts of plasticizer and 0.5-2 parts of thixotropic agent;
the composite silver powder is prepared from nano silver powder and silver resinate in a mass ratio of 32-51:8-9;
the nano silver powder is composed of nano silver wires, nano silver sheets and nano silver particles according to the mass ratio of 7-14: 23-33:2-4;
The silver resin acid salt is prepared from silver neodecanoate, silver pivalate and silver n-butyrate according to a mass ratio of 4-5:3.5-4: 0.5-1;
the organic carrier is obtained by mixing polyether polyurethane silver resin, aqueous polyurethane resin and aqueous acrylic resin according to a mass ratio of 12-22:10-20:4-13.
2. The conductive silver paste for low-temperature co-fired ceramic substrates according to claim 1, wherein the preparation method of the silver neodecanoate is as follows:
Step A1, dissolving sodium hydroxide in deionized water to obtain a mixed solution A1;
a2, dissolving neodecanoic acid in methanol to obtain a mixed solution A2;
step A3, dissolving silver nitrate in deionized water to obtain a mixed solution A3;
A4, adding the mixed solution A1 into the mixed solution A2, stirring at room temperature for reaction for 30min, adding the mixed solution A3, stirring for 30min, filtering, washing with ethanol for 3-5 times, and drying in a vacuum oven at 60 ℃ in dark for 10-12h to obtain a silver neodecanoate precursor;
step A5. The xylene, terpineol and silver neodecanoate precursor are placed in a glass bottle, and finally the obtained solution is filtered by a 200 μm syringe filter to obtain silver neodecanoate.
3. The conductive silver paste for low-temperature co-fired ceramic substrates according to claim 2, wherein the usage ratio of sodium hydroxide to deionized water in step A1 is 2-3g:45-55mL;
The dosage ratio of the neodecanoic acid to the methanol in the step A2 is 8-12g:45-55mL;
The dosage ratio of the silver nitrate to the deionized water in the step A3 is 9-10g:48-52mL;
The volume ratio of the mixed solution A1 to the mixed solution A2 to the mixed solution A3 in the step A4 is 45-55:45-55:48-52;
The mass ratio of the dimethylbenzene to the terpineol to the silver neodecanoate precursor in the step A5 is 2-3:2-3:5.5-6.5.
4. The conductive silver paste for low-temperature co-fired ceramic substrates according to claim 1, wherein the silver pivalate is prepared by the following method:
Step B1, dissolving sodium hydroxide in deionized water to obtain a mixed solution B1;
B2, dissolving pivalic acid in methanol to obtain a mixed solution B2;
Step B3, dissolving silver nitrate in deionized water to obtain a mixed solution B3;
Step B4., adding the mixed solution B1 into the mixed solution B2, stirring at room temperature for reaction for 30min, then adding the mixed solution B3, stirring for 30min, filtering, washing with ethanol for 3-5 times, and drying in a vacuum oven at 60 ℃ in a dark place for 10-12h to obtain a silver pivalate precursor;
Step B5. placing xylene, terpineol and silver pivalate precursor in a glass bottle, and finally filtering the obtained solution by using a 200 μm syringe filter to obtain the silver pivalate.
5. The conductive silver paste for low temperature co-fired ceramic substrates according to claim 4, wherein the usage ratio of sodium hydroxide to deionized water in step B1 is 2 to 3g:45-55mL;
The dosage ratio of the pivalic acid to the methanol in the step B2 is 8-12g:45-55mL;
the dosage ratio of the silver nitrate to the deionized water in the step B3 is 9-10g:48-52mL;
In the step B4, the volume ratio of the mixed solution B1 to the mixed solution B2 to the mixed solution B3 is 45-55:45-55:48-52;
The mass ratio of the dimethylbenzene to the terpineol to the silver pivalate precursor in the step B5 is 2-3:2-3:5.5-6.5.
6. The conductive silver paste for low-temperature co-fired ceramic substrates according to claim 1, wherein the preparation method of the silver n-butyrate is as follows:
step C1, dissolving sodium hydroxide in deionized water to obtain a mixed solution C1;
Step C2., dissolving n-butyric acid in methanol to obtain a mixed solution C2;
Step C3., dissolving silver nitrate in deionized water to obtain a mixed solution C3;
Step C4, adding the mixed solution C1 into the mixed solution C2, stirring at room temperature for reaction for 30min, adding the mixed solution C3, stirring for 30min, filtering, washing with ethanol for 3-5 times, and drying in a vacuum oven at 60 ℃ in the absence of light for 10-12h to obtain a silver n-butyrate precursor;
Step C5. placing xylene, terpineol and silver pivalate precursor in a glass bottle, and finally filtering the obtained solution by using a 200 μm syringe filter to obtain silver n-butyrate.
7. The conductive silver paste for low temperature co-fired ceramic substrates according to claim 4, wherein the usage ratio of sodium hydroxide to deionized water in step C1 is 2 to 3g:45-55mL;
The dosage ratio of the n-butyric acid to the methanol in the step C2 is 8-12g:45-55mL;
The dosage ratio of the silver nitrate to the deionized water in the step C3 is 9-10g:48-52mL;
the volume ratio of the mixed solution C1 to the mixed solution C2 to the mixed solution C3 in the step C4 is 45-55:45-55:48-52;
The mass ratio of the dimethylbenzene to the terpineol to the silver n-butyrate precursor in the step C5 is 2-3:2-3:5.5-6.5.
8. The conductive silver paste for low-temperature co-fired ceramic matrix according to claim 1, wherein the average diameter of the nano silver wires is 58-60nm and the aspect ratio is 175;
the size of the nano silver flake is 2-3 mu m;
The average particle diameter of the nano silver particles is 3.8-4nm.
9. The conductive silver paste for low-temperature co-fired ceramic substrates according to claim 1, wherein the solvent is any one of diethylene glycol diethyl ether, diethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate and terpineol;
The inorganic additive is any one of magnesium oxide, titanium dioxide, copper oxide, zinc oxide and aluminum oxide;
the plasticizer is tributyl citrate; the thixotropic agent is polyamide wax.
10. The method for preparing the conductive silver paste for the low-temperature co-fired ceramic matrix according to any one of claims 1 to 9, comprising the steps of:
Mixing the composite silver powder, an organic carrier, a solvent, an inorganic additive, a plasticizer and a thixotropic agent, grinding, and collecting materials with fineness less than 10 mu m to obtain the conductive silver paste for the low-temperature cofired ceramic matrix.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108735339A (en) * | 2018-05-25 | 2018-11-02 | 重庆邦锐特新材料有限公司 | A kind of high performance sintered conductive silver paste and preparation method thereof and sintering method |
| US20190304619A1 (en) * | 2018-03-30 | 2019-10-03 | Soltrium Advanced Meterials Technology, Ltd Suzhou | Conductive paste for semiconductor device and preparation method |
| CN112712913A (en) * | 2020-12-15 | 2021-04-27 | 陕西彩虹新材料有限公司 | Silver oxide slurry for electronic component and preparation method thereof |
| CN115274180A (en) * | 2022-08-30 | 2022-11-01 | 上海宝银电子材料有限公司 | Conductive silver paste for solid fuel cell and preparation method thereof |
| CN117497224A (en) * | 2023-11-23 | 2024-02-02 | 深圳先进电子材料国际创新研究院 | Sintered silver paste, sintered silver film preformed sheet and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190304619A1 (en) * | 2018-03-30 | 2019-10-03 | Soltrium Advanced Meterials Technology, Ltd Suzhou | Conductive paste for semiconductor device and preparation method |
| CN108735339A (en) * | 2018-05-25 | 2018-11-02 | 重庆邦锐特新材料有限公司 | A kind of high performance sintered conductive silver paste and preparation method thereof and sintering method |
| CN112712913A (en) * | 2020-12-15 | 2021-04-27 | 陕西彩虹新材料有限公司 | Silver oxide slurry for electronic component and preparation method thereof |
| CN115274180A (en) * | 2022-08-30 | 2022-11-01 | 上海宝银电子材料有限公司 | Conductive silver paste for solid fuel cell and preparation method thereof |
| CN117497224A (en) * | 2023-11-23 | 2024-02-02 | 深圳先进电子材料国际创新研究院 | Sintered silver paste, sintered silver film preformed sheet and application thereof |
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