CN116435007B - Low-temperature pressureless sintering silver paste, preparation method, application method and packaging structure - Google Patents
Low-temperature pressureless sintering silver paste, preparation method, application method and packaging structure Download PDFInfo
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- CN116435007B CN116435007B CN202310693240.3A CN202310693240A CN116435007B CN 116435007 B CN116435007 B CN 116435007B CN 202310693240 A CN202310693240 A CN 202310693240A CN 116435007 B CN116435007 B CN 116435007B
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- copper
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 152
- 239000004332 silver Substances 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 9
- 238000001272 pressureless sintering Methods 0.000 title claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 48
- -1 short-chain fatty acid copper salt Chemical class 0.000 claims abstract description 42
- 238000005245 sintering Methods 0.000 claims abstract description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 16
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000002562 thickening agent Substances 0.000 claims description 11
- 239000000080 wetting agent Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- 150000004666 short chain fatty acids Chemical class 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 238000007790 scraping Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000004203 carnauba wax Substances 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 230000001070 adhesive effect Effects 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 19
- 150000001879 copper Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 7
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000002344 surface layer 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
- H01B1/20—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
-
- 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
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- 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
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Thermal Sciences (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses low-temperature pressureless sintered silver paste, a preparation method, an application method and a packaging structure, wherein the low-temperature pressureless sintered silver paste comprises short-chain fatty acid copper salt, flake silver powder, glycol and an auxiliary agent. The scheme has low organic residue, good electric conductivity and heat conductivity, and decomposition temperature below 250 ℃, thereby avoiding damage to components and integrated circuit boards caused by overhigh sintering temperature; in the sintering process, copper crystals can better fill gaps between silver powder and gaps between the conductive paste and the surface of the metal substrate, so that the compactness of the silver paste and the adhesive force of the silver paste on the surface of the metal substrate are improved; after sintering, copper crystals are generated at gaps of silver powder to form a conductive path with a copper-silver network structure, and the structure can ensure compactness of silver paste and avoid copper oxidation without complex preparation treatment while improving conductive performance.
Description
Technical Field
The invention relates to the field of conductive materials, in particular to low-temperature pressureless sintering silver paste, a preparation method, an application method and a packaging structure.
Background
At present, integrated circuits are miniaturized, developed in a functional way, and packaging materials are required to have the characteristics of high power density, high integration, high working voltage resistance and the like. The traditional chip packaging material comprises tin soldering paste and conductive adhesive, wherein the tin soldering paste is formed into alloy with metal plating layers on a substrate and components through tin melting so as to achieve the packaging effect; however, tin itself has heat conduction and electrical conduction properties inferior to those of metals such as silver and copper, and the heat conduction coefficient of the traditional solder paste is often lower than 60W/m.k; in addition, tin also has the reliability problems of holes, low bonding performance and the like caused by high and low temperature circulation, and can not meet the requirements of high pressure resistance, environmental temperature difference resistance, high bonding performance and high precision in an integrated circuit. The conductive adhesive is an adhesive with certain conductive performance after solidification or drying, and generally needs organic resin as a bonding phase, conductive filler particles as conductors, the conductive particles are combined together through the bonding action of matrix resin, a molecular skeleton structure of the conductive adhesive is formed after solidification, and the conductive filler particles form conductive paths to realize conductive connection of the adhered materials; however, since the organic resin is used as the adhesive phase, the organic residue is high, and the movement of electrons between silver particles is hindered, so that the coefficient of thermal conductivity of the conductive adhesive is often difficult to exceed 20W/m·k, and particularly in some photo-curing conductive adhesives, the resin is difficult to be completely cured due to the good light-shielding property of the conductive filler, and the adhesive property between the conductive adhesive and the substrate is deteriorated. Therefore, the conductive paste with low organic residue and high electric and heat conductivity is an ideal substitute for soldering paste and epoxy conductive adhesive.
Because the conductivity of silver and copper is better, silver powder and copper powder are usually used as conductive phases in conductive paste, a silver/copper layer is arranged on the surface of a common substrate, the conductive paste is usually sintered on the silver/copper layer, and single silver paste or copper paste can only be applied to the surface layer of the substrate consistent with the material under the condition that no organic phase is added to increase the bonding force, and particularly, the conductive silver paste has poor bonding property on the surface of the copper substrate and the conductive copper paste has poor bonding property on the surface of the silver substrate.
Secondly, copper powder is extremely easy to oxidize in a high-temperature environment, and oxidized copper oxide does not have conductivity, so that stability is poor, in order to solve the problem that copper powder is easy to oxidize, silver-coated copper particles are generally adopted to replace single copper powder in the prior art, and the preparation of the silver-coated copper particles mainly comprises two types: firstly, carrying out surface pretreatment on copper powder, and then coating silver outside copper particles in a silver deposition or silver salt crystallization mode; the other is silver-coated copper powder with a spherical shell structure of inner copper and outer silver formed by electroplating silver outside copper particles; the silver-coated copper structure not only maintains the physical properties of the original metal copper core, but also has the excellent metal characteristics of the silver coating, improves the oxidation resistance and the thermal stability of pure copper powder, and maintains the high conductivity of copper and silver. However, on one hand, the manner of plating the silver salt on the surface of copper powder generally requires pretreatment of copper powder, stannous chloride is generally used as a sensitizer to activate and sensitize the copper powder, after the sensitization treatment, the copper powder needs to be cleaned, if the sensitizer is not thoroughly cleaned, chloride ions are easy to remain, so that substitution reaction between silver and copper is easy to be initiated during silver deposition, thereby leading to that silver cannot be well deposited on the surface of copper, even leading to copper blackening, and affecting the conductivity, such as the application publication number of CN1176234C, the patent name of the composition is high-temperature-resistant oxidation-resistant base metal, and the production method thereof, and the copper powder needs to be repeatedly cleaned for three times after the sensitization treatment, and the process is complex; on the other hand, because silver is wrapped outside copper, silver is usually used as a bonding phase, if the conductive paste is applied to a copper substrate, an organic phase needs to be additionally added, for example, the application publication number is CN114639500A, the patent name is the patent of the invention of a silver-doped silver-copper-clad two-component sintering type conductive paste and a preparation method thereof, and the silver-doped silver-copper-clad organic phase is used for preparing the conductive paste, so that the organic residue of the conductive paste is increased, and the conductive performance is weakened; meanwhile, the preparation process of the silver-coated copper powder is complex, and the process is complex.
In addition, the melting points of silver and copper are above 900 ℃, and the traditional micron silver powder and copper powder need to be heated to at least 700 ℃ to be melted for packaging and bonding, however, a large number of components and integrated circuit boards cannot resist the high temperature of above 250 ℃. The existing solution is to adopt nanoscale metal particles, and the nano silver paste and the nano copper paste can be sintered and melted at the temperature of as low as 250 ℃. However, when the metal size is reduced to nanometer, the metal surface energy is obviously improved, and the chemical activity is obviously improved, so that the metal nanometer powder is extremely easy to oxidize in the sintering process, and in addition, the problems of high price of the metal nanometer powder, silver migration, easy oxidation of nanometer copper in air due to heating, easy agglomeration of the metal nanometer powder at room temperature, poor process stability at room temperature and the like limit the application of nanometer copper slurry and nanometer silver slurry.
Disclosure of Invention
Accordingly, in order to solve the above problems, the present invention provides a low-temperature pressureless sintered silver paste, a preparation method, an application method, and a package structure.
The invention is realized by the following technical scheme:
a low temperature pressureless sintered silver paste comprising by weight:
17-24 parts of short-chain fatty acid copper salt;
69-76 parts of silver powder;
3-7 parts of ethylene glycol;
0-0.2 parts of auxiliary agent;
the particle size range of the short-chain fatty acid copper salt is 2um-5um in the D50, and the decomposition temperature is less than or equal to 300 ℃; the silver powder is flake silver powder, the particle size of the silver powder is 2um-5um in the D50 range, and D max <15um, tap density>4.0g/cm 3 。
Preferably, the short-chain fatty acid copper salt is copper salt with short-chain fatty acid and/or short-chain fatty acid salt bonded on the surface, and the carbon number of the short-chain fatty acid in the short-chain fatty acid copper salt is less than or equal to 4.
Preferably, the short-chain fatty acid copper salt is one of short-chain fatty acid copper oxalate/copper acetate/copper formate tetrahydrate.
Preferably, the auxiliary agent comprises a wetting agent and a thickening agent, wherein the mass ratio of the thickening agent to the wetting agent is 1:3 to 1:5.
preferably, the wetting agent comprises one or more of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid.
Preferably, the thickener comprises one or more of polyethylene wax, polypropylene wax, and palm wax.
Preferably, the viscosity of the low-temperature pressureless sintered silver paste is less than or equal to 80Kcps, the scraper fineness is less than 10um, and the decomposition temperature is less than or equal to 250 ℃.
The preparation method of the low-temperature pressureless sintered silver paste comprises the following steps of:
step S1: heating, stirring and dispersing ethylene glycol and an auxiliary agent uniformly at the temperature of 90 ℃ to form a first mixed solution;
step S2: and (3) cooling the first mixed solution to room temperature, adding silver powder and short-chain fatty acid copper salt into the first mixed solution, grinding until the fineness of the scraping plate is less than 10um, and preparing the low-temperature pressureless sintered silver paste.
The application method of the low-temperature pressureless sintered silver paste comprises the following steps:
step one: coating the low temperature pressureless sintered silver paste according to any one of claims 1 to 7 on the surface of a substrate plated with copper or silver layer;
step two: placing the substrate coated with the silver paste into an oven, and heating the substrate to 150 ℃ from room temperature at a heating rate of 15 ℃/min;
step three: the substrate coated with the silver paste is kept at the temperature of 150 ℃ for 45min;
step four: and continuously heating the substrate coated with the silver paste to 200-250 ℃ at a heating rate of 25 ℃/min to finish sintering the silver paste.
The packaging structure comprises a base material and a silver paste layer sintered on the base material, wherein the silver paste layer is prepared according to the application method of the low-temperature pressureless sintered silver paste, a copper-silver conductive network structure is formed in the silver paste layer, the copper-silver conductive network structure comprises silver powder areas and copper crystallization areas formed between the silver powder areas, and the copper crystallization areas of the silver paste layer are bonded with the base material.
The technical scheme of the invention has the beneficial effects that:
1. by adopting the short-chain fatty acid copper salt, on one hand, the short-chain fatty acid is easy to volatilize, and after silver paste is sintered, the short-chain fatty acid is completely volatilized, so that no organic residue is ensured; on the other hand, the decomposition temperature of the selected short-chain fatty acid copper salts is lower than 300 ℃, and after glycol is added, the decomposition temperature of the low-temperature pressureless sintered silver paste during sintering can be further reduced to below 250 ℃, so that the silver paste can be effectively bonded with a base material in a low-temperature pressureless state, and the damage to components and an integrated circuit board caused by the overhigh sintering temperature is avoided.
2. The short-chain fatty acid copper salt is decomposed and reduced in the sintering process to obtain eutectic of metal copper simple substance on the surfaces of the micron silver powder and the metal substrate, and the eutectic can be well bonded on the surfaces of the substrate, so that the eutectic can be simultaneously applied to the silver substrate and the copper substrate, the application range is wider, and the problem that copper particles are directly sintered and easily oxidized is effectively avoided; in addition, in the sintering process, continuous crystallization extends, gaps between silver powder and gaps between the conductive paste and the surface of the metal substrate can be filled well, the compactness of the conductive paste is improved, meanwhile, the adhesive force of the conductive paste on the surface of the metal substrate is improved, and the coating after sintering is avoided from falling off.
3. The flake silver powder with high tap density is adopted, and the dispersing performance of the silver powder can be better improved by combining with an auxiliary agent, so that a large amount of aggregation of the silver powder in the mixing process is effectively avoided, the scraper fineness of the slurry is controlled below 10um, and the viscosity of the slurry is controlled below 80 Kcps; meanwhile, the flake silver powder is good in extensibility, in the preparation process of the coating, the extensibility, leveling property and fineness of the slurry are ensured while the dispersibility is improved by controlling the fineness of copper salt and silver powder and further processing, in addition, small-particle copper salt can be subjected to full reduction reaction in the sintering process, the filling rate of copper crystals in gaps of the silver powder is further improved, and the high-precision requirement of an integrated circuit can be met.
4. After the sintering of the low-temperature pressureless sintering silver paste is completed and the organic phase volatilizes, copper crystals are generated at gaps of the silver powder, so that a copper-silver network structure conductive path is formed in the silver paste, and on one hand, the copper-silver network structure can improve the overall conductivity of the silver paste; on the other hand, compared with the existing silver-coated copper ball shell structure, the silver-coated copper ball shell structure does not need to be subjected to complicated preparation treatment, and copper oxidation can be avoided while silver paste compactness is ensured.
5. The auxiliary agent comprises a wetting agent and a thickening agent, and the proportion between the wetting agent and the thickening agent is controlled, so that the filler is dispersed, the uniformity of the silver paste after sintering is good, the temperature difference resistance effect is good, and the stability of the silver paste is ensured; meanwhile, the organic aid is easy to volatilize in the silver paste sintering process, organic residues are not formed, and the conductivity of the silver paste can be further improved.
6. The sectional sintering solidification is adopted, the sintering temperature, the heating rate and the heat preservation time of each stage are strictly controlled, on one hand, gradient volatilization of the auxiliary agent is facilitated, and cracking of the silver bonding layer is avoided, and the bonding performance is influenced; on the other hand, after the auxiliary agent volatilizes, the short-chain fatty acid copper salt fully undergoes a reduction reaction to fill gaps between silver powder and between the conductive paste and the surface of the metal substrate, so that the compactness of the conductive paste and the adhesive force of the conductive paste on the surface of the metal substrate are further increased.
Drawings
Fig. 1a is an enlarged view of a partial surface state of the low temperature pressureless sintered silver paste of the present invention after sintering and curing;
FIG. 1b shows the use of a tap density of 3.5g/cm 3 An enlarged view of the local surface state of the silver paste prepared from the silver powder after sintering and solidification;
FIG. 1c is an enlarged view of the partial surface state of the silver paste prepared in comparative example 4 after sintering and curing;
FIG. 2a is a DSC curve of the low temperature pressureless sintered silver paste prepared in example 2;
FIG. 2b is a DSC curve of a silver paste prepared by replacing the copper salt of example 2 with an equivalent mass portion of nano silver powder;
FIG. 3a is a scanning electron microscope image of a plate-like silver powder used for low temperature pressureless sintering of silver paste;
FIG. 3b is a scanning electron microscope image of the low temperature pressureless sintered silver paste after sintering is completed;
fig. 4 is an enlarged view of a partial cut of an interlayer structure between a silver paste layer and a substrate in a package structure.
Detailed Description
So that the objects, advantages and features of the present invention can be more clearly and specifically set forth, a more particular description of the preferred embodiments will be rendered by the following non-limiting description thereof. The embodiment is only a typical example of the technical scheme of the invention, and all technical schemes formed by adopting equivalent substitution or equivalent transformation fall within the scope of the invention.
It is also stated that, in the description of the aspects, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "front", "rear", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of description and simplification of description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like in this description are used for descriptive purposes only and are not to be construed as indicating or implying a ranking of importance, or as implicitly indicating the number of technical features shown. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the present invention, the meaning of "plurality" means two or more, unless specifically defined otherwise.
The invention discloses low-temperature pressureless sintered silver paste, which comprises the following materials in parts by weight:
17-24 parts of short-chain fatty acid copper salt;
69-76 parts of silver powder;
3-7 parts of ethylene glycol;
0-0.2 parts of auxiliary agent;
wherein the particle size range of the short-chain fatty acid copper salt is 2um-5um in the D50, and the decomposition temperature is less than or equal to 300 ℃; the silver powder adopts flake silver powder with better extensibility and conductivity, the particle size of the silver powder is 2um-5um in the D50 particle size range, and the maximum particle size D max <15um, tap density>4.0g/cm 3 The particle fineness of the short-chain fatty acid copper salt and the silver powder is controlled, so that the overall fineness of the silver paste is improved, and small-particle copper salt can be fully reduced in the sintering process, so that the filling rate of copper crystals in gaps of the silver powder is further improved, and the compactness of the silver paste after sintering and the bonding performance between the silver paste and a base material are improved; meanwhile, as shown in fig. 1a and 1b, the silver powder with high tap density is adopted in fig. 1a, so that the dispersion performance of the silver powder and the leveling property of the silver paste can be improved, and the leveling property of the silver paste after being printed on a substrate is further improved.
In some embodiments, the number of carbon atoms of the short-chain fatty acid in the short-chain fatty acid copper salt is less than or equal to 4, wherein the short-chain fatty acid copper salt is one of short-chain fatty acid copper oxalate/copper acetate/copper formate tetrahydrate, and in a preferred embodiment, the short-chain fatty acid copper salt adopts copper oxalate with a decomposition temperature of less than 300 ℃ and a higher copper mass fraction.
Wherein, the preferable weight part of the auxiliary agent is 0.1-0.2 part, the auxiliary agent comprises a wetting agent and a thickening agent, and the mass ratio of the thickening agent to the wetting agent is 1:3 to 1:5.
in some embodiments, the wetting agent comprises one or more of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and the thickener comprises one or more of polyethylene wax, polypropylene wax, and palm wax.
By controlling the particle size of the short-chain fatty acid copper salt and silver powder, the tap density of the silver powder and the types of the short-chain fatty acid copper salt, the viscosity of the low-temperature pressureless sintering silver paste is less than or equal to 80Kcps, the scraping fineness is less than 10 mu m, the decomposition temperature is less than or equal to 250 ℃, and the low-temperature pressureless sintering silver paste can realize high flatness and high adhesive force on a substrate in a low-temperature pressureless state while having high conductivity.
According to the above materials for low temperature pressureless sintering silver paste, examples 1 to 7 were provided while comparative examples 1 to 4 were provided, and the compounding data of examples 1 to 7 and comparative examples 1 to 4 were as follows:
the materials of each example and comparative example in the above table were first prepared as silver paste, and the preparation process was as follows:
heating, stirring and dispersing the auxiliary agent and the reducing agent at 90 ℃ to be uniform, cooling to room temperature, adding silver powder and copper salt (only silver powder is added in comparative example 1), and grinding the slurry until the scraping fineness is less than 10 mu m;
silver pastes prepared in each example and comparative example were respectively screen-printed on test substrates, which were chips: 2mm gold-plated chip, chip substrate: copper/silver plated, PPF (Pre-Plating frame Finish Pre-electroplated) nickel palladium gold/nickel platinum gold substrate, obtaining a sample after sintering and curing, wherein the sintering and curing process comprises the following steps: heating the room temperature to 150 ℃ at a heating rate of 15 ℃/min; preserving heat at a temperature of 150 ℃ for 45 ℃/min; then continuously heating to 200-250 ℃ with the heating rate of 25 ℃/min.
The samples prepared in each of the above examples and comparative examples were subjected to post-curing performance tests including volume resistivity, adhesion at room temperature, adhesion at high temperature (260 ℃) and thermal conductivity tests of a silver paste layer cured on a test substrate; the performance test after aging is to test the bonding performance of the sample at normal temperature and the bonding performance at high temperature (260 ℃) after high and low temperature impact, wherein the high and low temperature impact is set to be between-55 ℃ and 150 ℃ and 1000 times of high and low temperature cycle test are carried out within 30 minutes; the test results are as follows:
as is clear from comparative example 1 and comparative example 1, comparative example 1 was extremely poor in the electrical conductivity, thermal conductivity, adhesion property and aging resistance on the test substrate without the addition of copper salt, because of poor compatibility of silver and copper, and the adhesion of the conductive silver paste, to which silver powder was added alone, on the copper substrate was insufficient without the addition of a material having an adhesive effect; even when applied to silver substrates, as shown in fig. 3a, the compactness cannot be ensured due to the larger gaps between silver powders, the adhesion force between the conductive layers formed after sintering and the substrates is limited, and gaps are easily formed between the conductive layers, so that the conductive effect is affected.
As is clear from comparative examples 1 and 2, the adhesion performance of comparative example 2 is superior to that of comparative example 1 without adding silver powder, because copper crystals formed by reduction reaction of copper salt during sintering have good adhesion performance on both silver and copper substrates; however, as is clear from comparative examples 2 and 2, comparative example 2 has inferior electric conductivity, heat conductivity, adhesion property and aging resistance on the test substrate without adding silver powder, on the one hand, since copper has inferior electric conductivity as silver, the electric conductivity of the paste is improved after adding silver powder; on the other hand, in the embodiment 2, by optimizing the silver-copper ratio, the aging resistance attenuation caused by the fact that copper is easily oxidized in the air can be effectively avoided.
As is clear from comparative example 3 and comparative example 3, comparative example 3 is inferior in electric conductivity, heat conductivity, adhesion property and aging resistance on the test substrate without adding the reducing agent ethylene glycol, because ethylene glycol dibutyl ether cannot be used as a reducing agent and dispersion property can be improved only as an organic solvent in silver paste, and therefore, the copper salt in comparative example 3 cannot sufficiently undergo a reduction reaction at the time of sintering, and thus crystallization effect is inferior to that of example 3.
As is apparent from comparative example 4 and comparative example 4, comparative example 4 has relatively high volume resistivity but poor heat conductive property, adhesion property and aging resistance property, because no additive is added in comparative example 4, thus no organic residue exists and the conductivity is increased, however, since no additive improves dispersibility when silver powder and copper salt are mixed, thus being unfavorable for filler dispersion, leveling property of silver paste is relatively poor, and it can be observed in connection with fig. 1a and 1c that in fig. 1c, uniformity, temperature difference resistance effect and stability after sintering of silver paste are poor, because no additive is added.
In example 6 and example 7, compared with examples 1 to 5, examples 1 to 5 use short-chain fatty acid copper oxalate, example 6 uses short-chain fatty acid copper acetate, example 7 uses short-chain fatty acid copper formate tetrahydrate, and since both use short-chain fatty acid copper salt with lower decomposition temperature, the decomposition temperature of the short-chain fatty acid copper oxalate is below 270 ℃, and the decomposition temperature of the short-chain fatty acid copper acetate and the decomposition temperature of the short-chain fatty acid copper formate tetrahydrate are both less than 300 ℃, and simultaneously, after adding ethylene glycol, the decomposition temperature of silver paste during sintering can be further reduced, so that the decomposition temperature of the silver paste prepared in examples 1 to 7 is reduced to below 250 ℃, therefore, compared with example 2, example 6 and example 7, under the condition that other materials are identical in proportion, the test effect difference is small.
Comparing fig. 2a and fig. 2b, wherein fig. 2a is a DSC curve of the silver paste prepared in example 2, fig. 2b is a DSC curve of the silver paste prepared by replacing copper salt in example 2 with nano silver powder of the same mass part, respectively showing thermal property change of the two during sintering, in the DSC curve, the unit of ordinate mW/mg represents power (milliwatt) flowing to each milligram of sample, wherein, as shown in fig. 2a and fig. 2b, when the curve rises, heat is released, the curve falls, heat is absorbed, the abscissa T represents temperature, a section of exothermic peak is formed in the DSC curve due to heat release when the sample is converted from liquid state to solid state, and the crystallization temperature or curing temperature of the sample can be obtained according to the position of the exothermic peak on the abscissa in the DSC curve; according to the position of the heat release peak in FIG. 2a, the silver paste prepared in example 2 is sintered and crystallized at 200-250 ℃, so that the silver paste can be crystallized at the temperature (less than or equal to 250 ℃) without damaging components and integrated circuit boards, and the adhesiveness between the silver paste and a substrate and the compactness of the silver paste are improved; as can be seen from the position of the heat release peak in fig. 2b, the sintering solidification temperature of the silver paste can be reduced to about 350 ℃ by adding the nano silver powder relative to the micro silver powder with the melting temperature of more than 700 ℃, but the sintering temperature is still higher than 250 ℃, so that components and integrated circuit boards are easily damaged; although the curing temperature can be reduced by further increasing the proportion of the nano silver powder, the nano silver powder is easy to agglomerate at room temperature, the process stability is poor at room temperature, and the problems of silver migration, oxidation and the like are easy to occur.
The invention discloses a preparation method of low-temperature pressureless sintered silver paste, which uses the low-temperature pressureless sintered silver paste as described above and comprises the following steps:
step S1: heating, stirring and dispersing ethylene glycol and an auxiliary agent uniformly at the temperature of 90 ℃ to form a first mixed solution;
step S2: and (3) cooling the first mixed solution to room temperature, adding silver powder and short-chain fatty acid copper salt into the first mixed solution, grinding until the fineness of the scraping plate is less than 10um, and preparing the low-temperature pressureless sintered silver paste.
The invention also discloses an application method of the low-temperature pressureless sintering silver paste, which comprises the following steps:
step one: a low temperature pressureless sintered silver paste according to any one of claims 1 to 7 applied to the surface of a substrate coated with a copper or silver layer.
Step two: the substrate coated with the silver paste was placed in an oven and warmed from room temperature to 150 ℃ at a rate of 15 ℃/min.
Step three: the substrate coated with the silver paste was incubated at a temperature of 150℃for 45min.
In the second step, the auxiliary agent in the silver paste begins to volatilize, in the third step, the auxiliary agent continuously accelerates to volatilize, so that organic residues are reduced after two times of sintering, compactness of a bonding phase is guaranteed, and meanwhile, the silver paste can be well leveled in the curing process through long-time low-temperature sintering.
Step four: and continuously heating the substrate coated with the silver paste to 200-250 ℃ at a heating rate of 25 ℃/min to finish sintering the silver paste.
The sintering temperature in the fourth step reaches 200-250 ℃, when the sintering temperature reaches 200 ℃ or higher, copper salt in silver paste starts to crystallize, along with further temperature rise, the crystallization speed is increased, and the crystallization effect of copper salt at the silver powder gap and at the joint between the silver paste and the base material is further improved, so that the compactness of the silver paste and the bonding effect between the silver paste and the base material are improved, as shown in fig. 3b, the silver paste is a schematic structural diagram between silver powder and copper crystals after sintering of the silver paste, and compared with fig. 3a, the structural gap is obviously reduced, and the compactness of the silver paste is improved; meanwhile, the silver paste is sintered in a gradient heating mode in the second to fourth steps, so that the influence on the bonding performance due to cracking of the silver bonding layer is avoided.
The invention discloses a packaging structure, as shown in fig. 4, comprising a base material 1 and a silver paste layer sintered on the base material 1, wherein the silver paste layer is prepared by low-temperature pressureless sintered silver paste according to the application method of the low-temperature pressureless sintered silver paste, a copper-silver conductive network structure is formed in the silver paste layer, the copper-silver conductive network structure comprises silver powder areas 2 and copper crystallization areas 3 formed between the silver powder areas 2, and the copper crystallization areas 3 of the silver paste layer are bonded with the base material 1.
The invention has various embodiments, and all technical schemes formed by equivalent transformation or equivalent transformation fall within the protection scope of the invention.
Claims (7)
1. The low-temperature pressureless sintering silver paste is characterized in that: comprises the following materials by weight:
17-24 parts of short-chain fatty acid copper salt;
69-76 parts of silver powder;
3-7 parts of ethylene glycol;
0-0.2 parts of auxiliary agent;
the particle size range of the short-chain fatty acid copper salt is 2um-5um in the D50, and the decomposition temperature is less than or equal to 300 ℃; the silver powder is flake silver powder, the particle size of the silver powder is 2um-5um in the D50 range, and D max <15um, tap density>4.0g/cm 3 The auxiliary agent comprises a wetting agent and a thickening agent, wherein the mass ratio of the thickening agent to the wetting agent is 1:3 to 1:5, the wetting agent comprises one or more of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid, and the thickening agent comprises one or more of polyethylene wax, polypropylene wax and palm wax.
2. The low temperature pressureless sintered silver paste of claim 1, wherein: the carbon number of the short-chain fatty acid in the short-chain fatty acid copper salt is less than or equal to 4.
3. The low temperature pressureless sintered silver paste as recited in claim 2, wherein: the short-chain fatty acid copper salt is one of short-chain fatty acid copper oxalate/copper acetate/copper formate tetrahydrate.
4. The low temperature pressureless sintered silver paste of claim 1, wherein: the viscosity of the low-temperature pressureless sintered silver paste is less than or equal to 80Kcps, the scraper fineness is less than 10um, and the decomposition temperature is less than or equal to 250 ℃.
5. The preparation method of the low-temperature pressureless sintered silver paste is characterized by comprising the following steps of: use of a low temperature pressureless sintered silver paste according to any of claims 1-4, comprising the steps of:
step S1: heating, stirring and dispersing ethylene glycol and an auxiliary agent uniformly at the temperature of 90 ℃ to form a first mixed solution;
step S2: and (3) cooling the first mixed solution to room temperature, adding silver powder and short-chain fatty acid copper salt into the first mixed solution, grinding until the fineness of the scraping plate is less than 10um, and preparing the low-temperature pressureless sintered silver paste.
6. The application method of the low-temperature pressureless sintering silver paste is characterized by comprising the following steps of: the method comprises the following steps:
step one: coating the low-temperature pressureless sintered silver paste according to any one of claims 1 to 4 on the surface of a substrate plated with copper or silver layer;
step two: placing the substrate coated with the silver paste into an oven, and heating the substrate to 150 ℃ from room temperature at a heating rate of 15 ℃/min;
step three: the substrate coated with the silver paste is kept at the temperature of 150 ℃ for 45min;
step four: and continuously heating the substrate coated with the silver paste to 200-250 ℃ at a heating rate of 25 ℃/min to finish sintering the silver paste.
7. Packaging structure, including substrate (1) and sintering silver thick liquid layer on substrate (1), its characterized in that: the silver paste layer is prepared according to the application method of the low-temperature pressureless sintering silver paste as claimed in claim 6, a copper-silver conductive network structure is formed in the silver paste layer, the copper-silver conductive network structure comprises silver powder areas (2) and copper crystallization areas (3) formed between the silver powder areas (2), and the copper crystallization areas (3) of the silver paste layer are bonded with the base material (1).
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| CN111334129A (en) * | 2020-03-30 | 2020-06-26 | 善仁（浙江）新材料科技有限公司 | Preparation method of low-temperature sintered nano-silver conductive ink |
| CN113327721A (en) * | 2021-08-04 | 2021-08-31 | 西安宏星电子浆料科技股份有限公司 | Preparation method of low-temperature cured conductive copper paste |
| CN113409985A (en) * | 2021-06-21 | 2021-09-17 | 中科检测技术服务(重庆)有限公司 | Preparation and application of nano-copper conductive slurry |
| CN114429830A (en) * | 2022-02-22 | 2022-05-03 | 中南大学 | Metal slurry with good fluidity and uniformity and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111334129A (en) * | 2020-03-30 | 2020-06-26 | 善仁（浙江）新材料科技有限公司 | Preparation method of low-temperature sintered nano-silver conductive ink |
| CN113409985A (en) * | 2021-06-21 | 2021-09-17 | 中科检测技术服务(重庆)有限公司 | Preparation and application of nano-copper conductive slurry |
| CN113327721A (en) * | 2021-08-04 | 2021-08-31 | 西安宏星电子浆料科技股份有限公司 | Preparation method of low-temperature cured conductive copper paste |
| CN114429830A (en) * | 2022-02-22 | 2022-05-03 | 中南大学 | Metal slurry with good fluidity and uniformity and preparation method thereof |
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