CN111618314A - Preparation method of nano silver-coated copper solder based on sonochemistry - Google Patents
Preparation method of nano silver-coated copper solder based on sonochemistry Download PDFInfo
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- CN111618314A CN111618314A CN202010412418.9A CN202010412418A CN111618314A CN 111618314 A CN111618314 A CN 111618314A CN 202010412418 A CN202010412418 A CN 202010412418A CN 111618314 A CN111618314 A CN 111618314A
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- silver
- sonochemistry
- coated copper
- copper
- filler metal
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- 239000010949 copper Substances 0.000 title claims abstract description 120
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 106
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 105
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 100
- 229910052709 silver Inorganic materials 0.000 claims abstract description 65
- 239000004332 silver Substances 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 238000005476 soldering Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- 150000001879 copper Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 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 claims abstract description 13
- 239000003223 protective agent Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 11
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 11
- 230000010355 oscillation Effects 0.000 claims description 9
- 239000001856 Ethyl cellulose Substances 0.000 claims description 7
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 7
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 7
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001249 ethyl cellulose Polymers 0.000 claims description 7
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 7
- 229940116411 terpineol Drugs 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 6
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 238000005219 brazing Methods 0.000 claims 15
- 239000000945 filler Substances 0.000 claims 15
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 238000003805 vibration mixing Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000006872 improvement Effects 0.000 description 16
- 239000000843 powder Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000004907 flux Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012995 silicone-based technology Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- -1 and the like Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a preparation method of a sonochemistry-based nano silver-coated copper solder, which comprises the following steps: mixing organic solvent solution of copper salt and organic solvent solution of sodium phosphite and protective agent, applying horn-type pulse ultrasonic wave directly downwards to the solution, heating and reacting to obtain copper nanoparticle dispersion liquid, cooling, centrifuging and washing to obtain Cu nanoparticles; adding Cu nanoparticles and a reducing agent into deionized water, uniformly mixing, adding a silver salt solution at 30-50 ℃ for reaction to obtain a silver-coated copper nanoparticle dispersion liquid, and centrifuging and washing the silver-coated copper nanoparticle dispersion liquid to obtain silver-coated copper nanoparticles; and uniformly mixing the silver-coated copper nanoparticles with the soldering paste by using an organic solvent to obtain the silver-coated copper nanoparticle soldering paste. The silver-coated copper nanoparticle solder prepared by the technical scheme of the invention has the characteristics of high reliability, low-temperature connection and high-temperature service, does not need protective gas in the preparation process, and is simple in process, green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a sonochemistry-based nano silver-coated copper solder.
Background
Since the new century, the trend of light weight and miniaturization of electronic products is more and more obvious, and the nanometer conductive particles are very important components as interconnection materials in microelectronic products. After the nano conductive particles are prepared into the conductive slurry in a dispersion mode, the requirements of processes such as micro-nano connection in a high-power device and the like on a bonding material are well met. Meanwhile, with the continuous development of the semiconductor industry and the introduction of the post-Mole era, concepts such as the combination of silicon-based technology and non-silicon-based technology are provided, higher requirements are provided for packaging materials, the sintering of nano particles becomes the packaging trend of high-power devices, and whether efficient preparation can be realized becomes an important factor in the development process.
Metals commonly used as conductive fillers are: gold, platinum, silver, copper, nickel, tin, and the like, and mixtures of two or more thereof. Gold and platinum solder pastes are commonly used in the military electronic field, and silver solder pastes are commonly used in high-end commercial electronic products, but the prices of the gold and platinum solder pastes are too high, so that the industrial popularization of the silver and silver solder pastes is greatly limited. Under the precondition of ensuring the main performance of the product, the material cost is reduced as much as possible, and the copper material is most likely to replace silver to become the common soldering paste in industry. However, the nano-scale copper particles are very easy to oxidize, so a layer of silver is required to cover the surface of the copper particles after the copper particles are prepared, so that the raw material has the characteristic of ensuring cost economy and also has good oxidation resistance and electrical conductivity. The key points for preparing the silver-coated copper soldering paste are the particle size and the dispersity of the nano particles and the efficient and simple preparation flow. At present, the preparation of nano silver-coated copper particles mainly comprises a microwave-assisted method, a weak reducing agent liquid phase method, a multi-step metal replacement method, a pulse line evaporation method and the like. The silver-coated copper nanoparticles prepared by the microwave-assisted method and the pulse line evaporation method have the characteristics of high efficiency and excellent oxidation resistance, but the equipment cost is too high, the particle dispersibility is poor, and the difference of the performance is large due to the instability of materials in the practical process; the weak reducing agent liquid phase method and the multi-step metal replacement method are developed based on a chemical reduction method, and have the advantages that the prepared nanoparticles have good dispersibility and low cost, but have the greatest defects of extremely low efficiency and unsuitability for large-scale production. Therefore, the method for preparing the silver-coated copper nanoparticles which is low in cost, stable in process, excellent in performance and capable of being efficiently prepared is very important, and the method brings very potential application prospects for the nano soldering paste for high-power device packaging.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of a sonochemistry-based nano silver-coated copper solder, which utilizes the special action effect of ultrasonic waves in a liquid phase, ensures stable performance, greatly shortens reaction time, and realizes simple and efficient preparation process, thereby obtaining nano silver-coated copper solder paste with the characteristics of low-temperature connection and high-temperature service, and solving the problems of poor reliability caused by high cost, serious electromigration, unstable nano copper paste and the like of the nano silver paste in industrial application.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of a nano silver-clad copper solder based on sonochemistry comprises the following steps:
step S1, preparing organic solvent solution of copper salt and organic solvent solution of sodium phosphite and protective agent; mixing an organic solvent solution of copper salt and an organic solvent solution of sodium phosphite and a protective agent, applying direct downward pulse ultrasonic waves to the solutions, heating to 60-90 ℃, and reacting to obtain a copper nanoparticle dispersion liquid; cooling, centrifuging and washing the copper nanoparticle dispersion liquid to obtain Cu nanoparticles;
step S2, adding the Cu nanoparticles obtained in the step S1 and a reducing agent into deionized water, mixing uniformly, adding a silver salt solution at 30-50 ℃ for reaction to obtain a silver-coated copper nanoparticle dispersion liquid, and centrifuging and washing the silver-coated copper nanoparticle dispersion liquid to obtain silver-coated copper nanoparticles;
and step S3, uniformly mixing the prepared silver-coated copper nanoparticles with an organic solvent for soldering paste, and further uniformly mixing by adopting ultrasonic oscillation to obtain the silver-coated copper nanoparticle soldering paste.
Ultrasonic wave is used as a carrier of energy, has the characteristics of high strength, good directivity, large vibration frequency and the like, and provides a special chemical environment which is incomparable with other systems when being used for chemical synthesis. According to the technical scheme, by applying direct downward pulse ultrasonic waves, ultrasonic pulse waves are mutually interfered and superposed in a liquid phase environment, so that a uniform sound field with high energy and high chemical activity is generated, along with continuous generation and growth of cavitation bubbles in a liquid phase until implosion disappears, a local area is continuously subjected to rapid heating and cooling in the process, a high-temperature and high-pressure (micro-flame) environment is generated around the local area, and the activity and energy of reactants are greatly improved; on the other hand, the implosion of the cavitation bubbles can generate high-speed shock waves in a liquid phase environment and extremely high-speed jet flow on the surface of a solid, so that strong stripping and stirring effects are caused, the metal particles have good dispersibility, and in addition, the effects can also remove inactive coatings on the surface of the solid particles, so that great help is brought to sintering and particle size control; finally, the ultrasonic can increase the reactivity of the metal, improve the energy of metal bonds and accelerate the reaction process, and the ultrasonic effect is very suitable for a synthesis system of metal nano-particles.
Further, weighing a proper amount of copper salt, adding the copper salt into the organic solvent, uniformly mixing, continuously stirring, heating to 40-60 ℃, and obtaining an organic solvent solution of the copper salt after complete dissolution.
Further, weighing a proper amount of sodium hypophosphite, adding the sodium hypophosphite and a protective agent polyvinylpyrrolidone into an organic solvent, uniformly mixing, continuously stirring, heating to 40-60 ℃, and obtaining an organic solvent solution of the sodium hypophosphite and the protective agent after complete dissolution.
Further, reacting for 10-30 min in step S1 to obtain a copper nanoparticle dispersion liquid.
Further, in step S1, the copper nanoparticle dispersion liquid is cooled to room temperature and then centrifuged, and then washed and centrifuged for a plurality of times by using a washing solution in which one or more than two of absolute ethyl alcohol, acetone, and ionic water thereof are mixed.
Further, in step S1, the copper salt is a compound in which the cation that can be dissolved in water is copper ion, and is preferably one or a mixture of two or more of copper chloride, copper sulfate, and copper nitrate.
As a further improvement of the present invention, in step S1, the pulse ultrasonic wave in the radial downward direction is a horn pulse ultrasonic wave in the radial downward direction.
As a further improvement of the invention, the power of the ultrasonic wave is 200W-1000W, and the ultrasonic frequency is 20-60 kHz. Furthermore, the power of the ultrasonic wave is 200-700W.
As a further improvement of the invention, the pulse ultrasonic wave is a symmetrical pulse, and the pulse period is 2-8 s.
In a further improvement of the present invention, in step S1, the protective agent is one or a mixture of two or more of polyvinylpyrrolidone, sodium dodecyl sulfate, polyacrylamide, polyethylene glycol (PEG), and span.
As a further improvement of the invention, the polyvinylpyrrolidone is one or a mixture of more than two of K-15, K-30 and K-60 in molecular weight.
As a further improvement of the invention, in step S1, the molar ratio of the copper salt to the sodium hypophosphite is 1: 2-4; the mass ratio of the copper salt to the polyvinylpyrrolidone is 0.1-0.25; the organic solvent is one or a mixture of more than two of isopropanol, ethylene glycol and diethylene glycol.
As a further improvement of the method, the Cu nanoparticles obtained in the step S1 and a reducing agent are added into deionized water, and the mixture is uniformly mixed by ultrasonic for 3-5 min.
As a further improvement of the present invention, in step S2, the silver salt solution is prepared by the following steps: weighing a certain amount of silver salt, adding into deionized water, continuously stirring, and completely dissolving to obtain the silver salt.
As a further improvement of the method, in step S2, slowly adding a silver salt solution at a reaction temperature of 30-50 ℃, and reacting for 30 min-2 h to obtain the silver-coated copper nanoparticle dispersion liquid.
As a further improvement of the present invention, in step S2, the silver-coated copper nanoparticle dispersion is cooled to room temperature and then centrifuged, and then washed and centrifuged several times with one or more washing solutions of absolute ethyl alcohol, acetone, and ionized water thereof.
In a further improvement of the present invention, in step S2, the molar ratio of the silver salt to the copper is 0.05 to 0.2.
As a further improvement of the invention, in step S2, the reducing agent is one or a mixture of two of ascorbic acid (VC) and sodium citrate;
as a further improvement of the invention, the silver salt is one or a mixture of two of silver nitrate and silver sulfate.
As a further improvement of the invention, in step S3, the mass ratio of the silver-coated copper nanoparticles to the organic solvent for the solder paste is 7-10: 1; the organic solvent for the soldering paste is one or a mixture of at least two of ethanol, glycol, glycerol, terpineol and ethyl cellulose.
As a further improvement of the invention, in the soldering paste, the particle size of the silver-coated copper nanoparticles is less than 100 nm, and further, the average particle size is about 55-60 nm.
As a further improvement of the invention, in step S3, the time of ultrasonic oscillation is 5-10 min, and in the process of ultrasonic oscillation mixing, stirring is continuously performed by a paste mixing machine, and the rotation speed of the paste mixing machine is 100-1000 r/min. More preferably, the paste mixing times are 4-6 times.
Preferably, in the solder, the mass fraction of the silver-coated copper nanoparticles is 40-80%, and the mass fraction of the organic solvent for the solder paste is 20-60%.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the silver-coated copper nanoparticle solder prepared by the technical scheme integrates the advantages of silver paste and copper paste, has higher reliability, and the obtained nano-grade silver-coated copper solder paste has the characteristics of low-temperature connection and high-temperature service, does not need protective gas in the preparation process, is easy to obtain raw materials, has a simple process, and is green and environment-friendly.
Secondly, the technical scheme of the invention leads the system to better perform solid-phase synthesis reaction in a liquid phase environment by introducing vertical downward ultrasonic waves, greatly improves the activity and energy of reactants, and the implosion of cavitation bubbles can generate high-speed shock waves in the liquid phase environment and high-speed jet flow on the surface of a solid, so that metal particles have good dispersibility, and inactive coating on the surface of the solid particles can be removed, thereby being greatly helpful for sintering and particle size control; finally, the ultrasound can increase the reactivity of the metal, improve the energy of metal bonds, accelerate the synthesis of copper nanoparticles, and further obtain silver-coated copper nanoparticles with the particle size of less than 100 nm and better dispersibility, which have lower sintering temperature and higher service temperature and meet the urgent requirements of low-temperature connection and high-temperature service of third-generation semiconductor devices.
Thirdly, aiming at the problems of poor tissue compactness, poor reliability, unstable performance and the like after the sintering of common nano particles, the preparation process of the soldering paste in the technical scheme of the invention adopts a unique formula and fine process steps, and particularly adds a special organic solvent to remove surface coating substances of the nano particles, thereby greatly reducing the sintering temperature, further increasing the weldability of the soldering paste, obtaining a compact joint with silver and copper interwoven, and realizing that the joint has excellent performances of electromigration resistance, high electric conduction and heat conduction, high reliability and the like at low temperature.
Drawings
FIG. 1 is a schematic representation of the ultrasonic sonochemical reaction of the present invention.
Fig. 2 is an XRD pattern of the nano silver-coated copper particles obtained in example 1 of the present invention.
Fig. 3 is a TEM image of the nano silver-coated copper particles obtained in example 1 of the present invention, wherein (a) is a TEM image, and (b) is a line scan image corresponding to Cu and Ag elements.
Fig. 4 is SEM images of silver-coated copper nanoparticles obtained in example 1 of the present invention and comparative example 1, wherein (a) is in horn ultrasonic mode of example 1, and (b) is in bath ultrasonic mode of comparative example 1.
FIG. 5 is an SEM cross-sectional view of a joint using as a solder a nano silver copper-clad solder paste obtained in examples 1 to 3 of the present invention and comparative example 2, wherein (a) is an SEM image of example 1 (ultrasonic power of 200W); (b) SEM image of example 2 (ultrasonic power 400W); (c) is SEM picture of example 3 (ultrasonic power is 600W); (d) is SEM image of example 4 with ultrasonic power of 800W; wherein (a 1), (b 1), (c 1) and (d 1) are partial enlarged views of (a), (b), (c) and (d).
FIG. 6 is a graph showing UV contrast during the process of preparing nano silver-coated copper particles of example 1 and comparative example 2 of the present invention, wherein (a) is that of comparative example 2; (b) is that of example 1.
Fig. 7 is a SEM cross-sectional view of a joint of a nano silver copper-clad solder paste as a solder obtained under ultrasonic conditions of example 1 and comparative example 3 of the present invention at different pulse ratios, wherein (a) the pulse ratio of example 1 is 1:1, and (b) the pulse ratio of comparative example 3 is 5: 1.
Detailed Description
In view of the incompleteness of the prior art, the specific technical route of the invention is as follows: copper nanoparticles with good particle size, morphology and dispersibility are efficiently prepared under the assistance of pulse ultrasonic waves and are used as precursors, then nano silver-coated copper particles are prepared by adopting a composite method of displacement and chemical reduction, and finally the nano silver-coated copper particles and soldering flux are prepared into soldering paste according to a certain mass ratio. Wherein, the copper nano-particles are introduced with ultrasonic action, the pulse sound wave can be equivalent to the combination of a plurality of resonant waves with different frequencies, and the interaction and the superposition are carried out in a liquid phase environment, so that the whole reaction container is filled with a uniform, high-activity and high-energy ultrasonic field; cavitation bubbles generated by cavitation are generated in a very short time and grow until implosion disappears, and the process can provide local instantaneous extreme high temperature and high pressure (micro flame) under the condition of not changing the ambient temperature and pressure; the cavitation bubbles interact with the solid phase to generate high-speed jet flow and shock wave on the surface of the solid phase, so that the prepared nano particles are dispersed more strongly under the action of stirring and stripping. The special effects brought by the ultrasound are beneficial to the chemical synthesis of the nano particles to a certain extent, and are also the key points of the invention.
A silver-coated copper nanoparticle soldering paste for high-power device packaging is prepared by the following steps:
(1) weighing a proper amount of copper salt, adding the copper salt into an organic solvent, uniformly mixing, continuously stirring, heating to 40-60 ℃, and obtaining a solution A after complete dissolution. And weighing a proper amount of sodium hypophosphite, adding the sodium hypophosphite and a protective agent polyvinylpyrrolidone into the organic solvent, uniformly mixing, continuously stirring, heating to 40-60 ℃, and obtaining a solution B after complete dissolution.
(2) Adding the freshly prepared solution A into the freshly prepared solution B, applying horn pulse ultrasonic waves which act directly downwards, heating to 60-90 ℃, and reacting for 10-30 min to obtain a copper nanoparticle dispersion liquid; the reaction device is shown in figure 1 and comprises a double-layer beaker 1, an ultrasonic generator 2, an ultrasonic transducer 3 and a titanium alloy amplitude transformer 4, wherein constant-temperature circulating water is introduced into the double-layer beaker 1 for heating, the ultrasonic generator 2 is connected with the titanium alloy amplitude transformer 4 through the ultrasonic transducer 3, and the titanium alloy amplitude transformer 4 extends into a reaction solution 5 containing reactants 6 in the double-layer beaker 1 to generate a pulse sound field 7, so that a large amount of cavitation bubbles 8 are generated to promote and accelerate the reaction.
(3) And (3) cooling the copper nanoparticle dispersion liquid obtained in the step (2) to room temperature, performing centrifugal separation, and performing multiple washing and centrifugation by using a washing liquid mixed with one or more of absolute ethyl alcohol, acetone and ionized water thereof.
(4) And (3) weighing a certain amount of the Cu nano particles obtained in the step (3) and a proper amount of reducing agent, adding the Cu nano particles and the reducing agent into deionized water, and performing ultrasonic treatment for 3-5 min to uniformly mix the Cu nano particles and the reducing agent to obtain a solution C. And weighing a certain amount of silver salt, adding the silver salt into deionized water, continuously stirring, and completely dissolving to obtain a solution D.
(5) Slowly dripping the solution D into the solution C at the reaction temperature of 30-50 ℃ to react for 30 min-2 h to obtain the silver-coated copper nanoparticle dispersion liquid.
(6) And (3) cooling the silver-coated copper nanoparticle dispersion liquid obtained in the step (5) to room temperature, then carrying out centrifugal separation, and washing and centrifuging for multiple times by using one or more mixed washing liquids of absolute ethyl alcohol, acetone and ionized water thereof to obtain the silver-coated copper nanoparticles.
(7) Uniformly mixing the silver-coated copper nanoparticles and soldering flux such as ethylene glycol, terpineol, ethyl cellulose and the like by ultrasonic oscillation according to a certain mass ratio, and continuously stirring by using a paste mixer in the process to finally obtain the silver-coated copper nanoparticle soldering paste.
The technical solution of the present invention is further described below with reference to several examples.
Example 1
(1) 10 g of copper sulfate pentahydrate powder is weighed and added into 100 ml of ethylene glycol, heated to 70 ℃, stirred for 15 min and completely dissolved to obtain solution A. In addition, 8g of sodium hypophosphite powder and 5g of polyvinylpyrrolidone are weighed and added into 200 ml of ethylene glycol, heated to 70 ℃, stirred for 20 min and completely dissolved to obtain a solution B.
(2) Adding the freshly prepared solution A into the freshly prepared solution B, applying horn type (horn) pulse ultrasonic waves (with the power of 200W and the pulse ratio of 2 s-2 s) acting directly downwards, heating to 70 ℃, and reacting for 15 min to obtain the copper nanoparticle dispersion liquid.
(3) Cooling the copper nanoparticle dispersion obtained in step (2) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: the mixed solution was washed 3 times at a volume ratio of 1.
(4) Weighing 2g of the Cu nanoparticles obtained in the step (3) and 2g of sodium citrate, adding into 100 ml of deionized water, and carrying out ultrasonic treatment for 5 min to uniformly mix to obtain a solution C. In addition, 0.5 g of silver sulfate powder is weighed and added into 200 ml of deionized water, and the solution D is obtained after stirring for 15 min and full dissolution.
(5) And slowly dropwise adding the solution D into the solution C at the reaction temperature of 40 ℃ to react for 1.5 h to obtain the silver-coated copper nanoparticle dispersion liquid.
(6) Cooling the silver-coated copper nanoparticle dispersion obtained in step (5) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: and washing the mixed solution with the volume ratio of 1 for 3 times to obtain the silver-coated copper nanoparticles.
(7) Uniformly mixing the silver-coated copper nanoparticles and soldering flux such as ethylene glycol, terpineol, ethyl cellulose and the like by ultrasonic oscillation according to a certain mass ratio, and continuously stirring by using a paste mixer in the process to finally obtain the silver-coated copper nanoparticle soldering paste.
The XRD pattern and TEM pattern of the nano silver-coated copper particles obtained in example 1 of the present invention are shown in fig. 2 and 3, respectively, which shows that the copper surface is coated with a thin layer of silver.
Example 2
(1) 10 g of copper sulfate pentahydrate powder is weighed and added into 100 ml of ethylene glycol, heated to 70 ℃, stirred for 15 min and completely dissolved to obtain solution A. In addition, 8g of sodium hypophosphite powder and 5g of polyvinylpyrrolidone are weighed and added into 200 ml of ethylene glycol, heated to 70 ℃, stirred for 20 min and completely dissolved to obtain a solution B.
(2) Adding the freshly prepared solution A into the freshly prepared solution B, applying horn type (horn) pulse ultrasonic waves (400W, the pulse ratio is 2 s-2 s) which act directly downwards, heating to 70 ℃, and reacting for 15 min to obtain the copper nanoparticle dispersion liquid.
(3) Cooling the copper nanoparticle dispersion obtained in step (2) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: the mixed solution was washed 3 times at a volume ratio of 1.
(4) Weighing 2g of the Cu nanoparticles obtained in the step (3) and 2g of sodium citrate, adding into 100 ml of deionized water, and carrying out ultrasonic treatment for 5 min to uniformly mix to obtain a solution C. In addition, 0.5 g of silver sulfate powder is weighed and added into 200 ml of deionized water, and the solution D is obtained after stirring for 15 min and full dissolution.
(5) And slowly dropwise adding the solution D into the solution C at the reaction temperature of 40 ℃ to react for 1.5 h to obtain the silver-coated copper nanoparticle dispersion liquid.
(6) Cooling the silver-coated copper nanoparticle dispersion obtained in step (5) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: the mixed solution was washed 3 times at a volume ratio of 1.
(7) Uniformly mixing the silver-coated copper nanoparticles and soldering flux such as ethylene glycol, terpineol, ethyl cellulose and the like by ultrasonic oscillation according to a certain mass ratio, and continuously stirring by using a paste mixer in the process to finally obtain the silver-coated copper nanoparticle soldering paste.
Example 3
(1) 10 g of copper sulfate pentahydrate powder is weighed and added into 100 ml of ethylene glycol, heated to 70 ℃, stirred for 15 min and completely dissolved to obtain solution A. In addition, 8g of sodium hypophosphite powder and 5g of polyvinylpyrrolidone are weighed and added into 200 ml of ethylene glycol, heated to 70 ℃, stirred for 20 min and completely dissolved to obtain a solution B.
(2) Adding the freshly prepared solution A into the freshly prepared solution B, applying horn type (horn) pulse ultrasonic waves (600W, the pulse ratio is 4 s-2 s) which act directly downwards, heating to 70 ℃, and reacting for 15 min to obtain the copper nanoparticle dispersion liquid.
(3) Cooling the copper nanoparticle dispersion obtained in step (2) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: the mixed solution was washed 3 times at a volume ratio of 1.
(4) Weighing 2g of the Cu nanoparticles obtained in the step (3) and 2g of sodium citrate, adding into 100 ml of deionized water, and carrying out ultrasonic treatment for 5 min to uniformly mix to obtain a solution C. In addition, 0.5 g of silver sulfate powder is weighed and added into 200 ml of deionized water, and the solution D is obtained after stirring for 15 min and full dissolution.
(5) And slowly dropwise adding the solution D into the solution C at the reaction temperature of 40 ℃ to react for 1.5 h to obtain the silver-coated copper nanoparticle dispersion liquid.
(6) Cooling the silver-coated copper nanoparticle dispersion obtained in step (5) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: the mixed solution was washed 3 times at a volume ratio of 1.
(7) Uniformly mixing the silver-coated copper nanoparticles and soldering flux such as ethylene glycol, terpineol, ethyl cellulose and the like by ultrasonic oscillation according to a certain mass ratio, and continuously stirring by using a paste mixer in the process to finally obtain the silver-coated copper nanoparticle soldering paste.
Example 4
On the basis of example 1, in step (2) of this example, horn (horn) pulsed ultrasonic waves (800W, pulse ratio of 2 s-2 s) acting directly downward were applied, heated to 70 ℃, and reacted for 15 min to obtain a copper nanoparticle dispersion. The other steps are the same as in example 1.
The welding experiments are respectively carried out on the solders of the examples 1 to 4, the structure morphology graph of the joint is analyzed, and the comparison graph is shown in fig. 5, and as can be seen from fig. 5, the joint particles with the ultrasonic powers of 200W, 400W and 600W are fused together, the specific power is better than 800W, and the effect of 600W is best.
Comparative example 1
(1) 10 g of copper sulfate pentahydrate powder is weighed and added into 100 ml of ethylene glycol, heated to 70 ℃, stirred for 15 min and completely dissolved to obtain solution A. In addition, 8g of sodium hypophosphite powder and 5g of polyvinylpyrrolidone are weighed and added into 200 ml of ethylene glycol, heated to 70 ℃, stirred for 20 min and completely dissolved to obtain a solution B.
(2) Adding the freshly prepared solution A into the freshly prepared solution B, applying bath type (bath) pulse ultrasonic waves (800W, with the pulse ratio of 2 s-2 s) acting directly downwards, heating to 70 ℃, and reacting for 15 min to obtain the copper nanoparticle dispersion liquid.
(3) Cooling the copper nanoparticle dispersion obtained in step (2) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: the mixed solution was washed 3 times at a volume ratio of 1.
(4) Weighing 2g of the Cu nanoparticles obtained in the step (3) and 2g of sodium citrate, adding into 100 ml of deionized water, and carrying out ultrasonic treatment for 5 min to uniformly mix to obtain a solution C. In addition, 0.5 g of silver sulfate powder is weighed and added into 200 ml of deionized water, and the solution D is obtained after stirring for 15 min and full dissolution.
(5) And slowly dropwise adding the solution D into the solution C at the reaction temperature of 40 ℃ to react for 1.5 h to obtain the silver-coated copper nanoparticle dispersion liquid.
(6) Cooling the silver-coated copper nanoparticle dispersion obtained in step (5) to room temperature, centrifuging (5000 rmp, 15 min), and using absolute ethanol: deionized water according to the weight ratio of 3: and washing the mixed solution with the volume ratio of 1 for 3 times to obtain the silver-coated copper nanoparticles.
(7) Uniformly mixing the silver-coated copper nanoparticles and soldering flux such as ethylene glycol, terpineol, ethyl cellulose and the like by ultrasonic oscillation according to a certain mass ratio, and continuously stirring by using a paste mixer in the process to finally obtain the silver-coated copper nanoparticle soldering paste.
The morphology of the silver-coated copper nanoparticles obtained in the two ultrasonic modes of the embodiment 3 and the comparative example 1 is analyzed, and as a result, as shown in fig. 4, it can be seen that the morphology of the silver-coated copper nanoparticles obtained in the embodiment 3 adopting the horn (horn) type pulse ultrasonic mode is approximately spherical and has better dispersibility, while the morphology of the silver-coated copper nanoparticles obtained in the comparative example 1 adopting the bath type pulse ultrasonic mode is thorn-shaped, and the silver-coated copper nanoparticles prepared in the horn type pulse ultrasonic mode of the embodiment 3 have large specific surface area and higher surface energy, and are easier to sinter at low temperature, so that the morphologies are easier to fuse with each other in joint connection to form a whole, and the goal of low-temperature connection and high-temperature service is achieved.
Comparative example 2
In the comparative example, UV comparative analysis is performed on the copper-clad silver nanoparticles obtained by a conventional alcohol reduction method in the process of cladding the copper nanoparticles with the silver-clad nanoparticles of example 1, and the result is shown in FIG. 6.
Comparative example 3
The comparative example differs from example 1 in the pulse ratio, which is 10s to 2s, i.e., 5: 1. the solders of example 1 and comparative example 3 were subjected to soldering experiments, respectively, and the structure morphology of the joints were analyzed, and the comparison graph is shown in fig. 7, and it can be seen from fig. 7 that the joint morphology of the solder with the pulse ratio of 1:1 of example 1 is continuous, and the pulse ratio of comparative example 3 is 5: the solder joint of 1 had voids and the joint strength was inferior to that of example 1.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of a nano silver-clad copper solder based on sonochemistry is characterized by comprising the following steps:
step S1, preparing organic solvent solution of copper salt and organic solvent solution of sodium phosphite and protective agent; mixing an organic solvent solution of copper salt and an organic solvent solution of sodium phosphite and a protective agent, applying horn-type pulse ultrasonic waves in a straight downward direction to the solution, heating to 60-90 ℃, and reacting to obtain a copper nanoparticle dispersion liquid; cooling, centrifuging and washing the copper nanoparticle dispersion liquid to obtain Cu nanoparticles;
step S2, adding the Cu nanoparticles obtained in the step S1 and a reducing agent into deionized water, mixing uniformly, adding a silver salt solution at 30-50 ℃ for reaction to obtain a silver-coated copper nanoparticle dispersion liquid, and centrifuging and washing the silver-coated copper nanoparticle dispersion liquid to obtain silver-coated copper nanoparticles;
and step S3, uniformly mixing the prepared silver-coated copper nanoparticles with an organic solvent for soldering paste, and further uniformly mixing by adopting ultrasonic oscillation to obtain the silver-coated copper nanoparticle soldering paste.
2. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to claim 1, wherein the sonochemistry-based nano-silver-clad brazing filler metal comprises the following steps: in the step S1, the power of the ultrasonic wave is 200W-700W, and the ultrasonic frequency is 20-60 kHz.
3. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to claim 2, wherein the sonochemistry-based nano-silver-clad brazing filler metal comprises the following steps: the pulse ultrasonic wave is a symmetrical pulse, and the pulse period is 2-8 s.
4. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to claim 3, wherein the sonochemistry-based nano-silver-clad brazing filler metal comprises the following steps: in step S1, the protective agent is one or a mixture of two or more of polyvinylpyrrolidone, sodium lauryl sulfate, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, and span.
5. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to any one of claims 1 to 4, wherein the method comprises the following steps: the polyvinylpyrrolidone is one or a mixture of more than two of K-15, K-30 and K-60 in molecular weight.
6. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to any one of claims 1 to 4, wherein the method comprises the following steps: in the step S1, the molar ratio of the copper salt to the sodium hypophosphite is 1: 2-4; the mass ratio of the copper salt to the polyvinylpyrrolidone is 0.1-0.25;
the organic solvent is one or a mixture of more than two of isopropanol, ethylene glycol and diethylene glycol;
the copper salt is one or a mixture of more than two of copper chloride, copper sulfate and copper nitrate.
7. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to claim 6, wherein the sonochemistry-based nano-silver-clad brazing filler metal comprises the following steps: in step S2, the molar ratio of the silver salt to the copper is 0.05-0.2.
8. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to claim 7, wherein the sonochemistry-based nano-silver-clad brazing filler metal comprises the following steps: in step S2, the reducing agent is one or a mixture of two of ascorbic acid and sodium citrate;
the silver salt is one or a mixture of two of silver nitrate and silver sulfate.
9. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to any one of claims 1 to 4, wherein the method comprises the following steps: in the step S3, the mass ratio of the silver-coated copper nanoparticles to the organic solvent for the soldering paste is 7-10: 1, and the particle size of the nanoparticles in the solder is smaller than 100 nm; the organic solvent for the soldering paste is one or a mixture of at least two of ethanol, glycol, glycerol, terpineol and ethyl cellulose.
10. The method for preparing the sonochemistry-based nano-silver-clad brazing filler metal according to claim 9, wherein the sonochemistry-based nano-silver-clad brazing filler metal comprises the following steps: in step S3, the ultrasonic vibration time is 5-10 min, and the paste mixer is continuously used for stirring during the ultrasonic vibration mixing process, wherein the rotation speed of the paste mixer is 100-1000 r/min.
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| CN114378474A (en) * | 2022-01-13 | 2022-04-22 | 北京工业大学 | Nano-silver coated micron copper soldering paste and preparation method thereof |
| CN114713836A (en) * | 2022-03-02 | 2022-07-08 | 上海电力大学 | Synthetic method of Cu-Ag sheet-shaped nano composite material |
| CN114603153A (en) * | 2022-03-19 | 2022-06-10 | 昆明理工大学 | Preparation method of bimetallic particles formed by self-assembly of nano copper and silver |
| CN114603153B (en) * | 2022-03-19 | 2024-01-23 | 昆明理工大学 | Preparation method of bimetal particles formed by self-assembly of nano copper and silver |
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