CN113523649A - Preparation method of composite soldering paste - Google Patents
Preparation method of composite soldering paste Download PDFInfo
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- CN113523649A CN113523649A CN202110824377.9A CN202110824377A CN113523649A CN 113523649 A CN113523649 A CN 113523649A CN 202110824377 A CN202110824377 A CN 202110824377A CN 113523649 A CN113523649 A CN 113523649A
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- silver
- nano
- copper core
- particles
- coated copper
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- 238000005476 soldering Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 84
- 229910052802 copper Inorganic materials 0.000 claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 78
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 58
- 229910052709 silver Inorganic materials 0.000 claims abstract description 51
- 239000004332 silver Substances 0.000 claims abstract description 51
- 239000011258 core-shell material Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 230000004907 flux Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 36
- 229910000679 solder Inorganic materials 0.000 claims description 19
- 235000019198 oils Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011859 microparticle Substances 0.000 claims description 6
- 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 description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 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 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 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 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 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
- 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 Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004100 electronic packaging Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000007747 plating Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IYKURAQZRPLCHL-UHFFFAOYSA-K C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].O.NN.[Na+].[Na+] Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].O.NN.[Na+].[Na+] IYKURAQZRPLCHL-UHFFFAOYSA-K 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Composite Materials (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a preparation method of composite soldering paste, and belongs to the technical field of electronic packaging connecting materials. The composite soldering paste comprises the following raw materials in parts by weight: 80-90 parts of silver-coated copper core-shell micro/nano mixed particles, 2-8 parts of a dispersing agent A, 2-8 parts of a binder, 2-8 parts of a diluent and 2-8 parts of a soldering flux. The silver-coated copper core-shell micro/nano mixed particles are prepared into micron and nano mixed copper particles by adopting a one-step liquid phase reduction method, and then are prepared by chemical plating.
Description
Technical Field
The invention relates to the technical field of electronic packaging connecting materials, in particular to a preparation method of composite soldering paste.
Background
With the vigorous development of the integrated circuit industry in various countries, not only the semiconductor is required to be in service under the conditions of high temperature, high power, high pressure and the like, but also higher requirements are provided for the packaging density of the semiconductor, but the existing packaging connecting material basically cannot meet the requirements, on one hand, the traditional solder cannot be in service at high temperature, for example, the melting point of the tin-based solder is less than 300 ℃, and at higher temperature, intermetallic compounds between the solder and the metal substrate can generate cracks and even melt; on the other hand, other high temperature solders, such as gold-based solder, are not only energy consuming and expensive, but also cause high residual stress and even damage to the package system, and are not suitable for large-scale commercial production, so the conventional package connecting material needs to be updated.
Research results in recent years show that the nano material has ultrahigh specific surface area and surface energy, so that the nano material can be sintered and fused at low temperature (far lower than the melting point of a corresponding block material), and the fused nano material has the characteristics of the nano material but the block material. The material can work at high temperature (higher than sintering temperature, even up to 400 ℃), namely the nano material has the obvious advantages of low-temperature sintering and high-temperature service, and can be used for multi-stage packaging connection and semiconductor packaging connection in service at high temperature.
Silver nano solder and copper nano solder are most likely to be used as packaging connecting materials in high-temperature and high-density semiconductors, but silver nanoparticles have the problems of high cost and poor electromigration and chemical migration resistance, and are not beneficial to large-scale commercial application; the copper nano particles have the advantages of price, accordance with the industrial sustainable development requirement, and strong electromigration resistance, and joints obtained by sintering have physical properties similar to those of sintered nano silver, but the joints are easy to oxidize, so that the problems of high storage difficulty, harsh sintering conditions and the like are caused. How to realize simple and rapid preparation of the solder and effectively improve the performance of the solder becomes a difficult problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a preparation method of composite soldering paste, which aims to solve the problems in the prior art, and the silver-coated copper core-shell micro/nano mixed particles are prepared by a two-step method, so that the composite soldering paste taking the silver-coated copper core-shell micro/nano mixed particles as main components is prepared.
In order to achieve the purpose, the invention provides the following scheme:
one of the technical schemes of the invention is as follows: the silver-coated copper core-shell micro/nano mixed particle comprises silver-coated copper core-shell micro particles and silver-coated copper core-shell nano particles, wherein the molar ratio of copper to silver in the silver-coated copper core-shell micro/nano mixed particle is 10: 1-1: 10.
Further, the volume ratio of the silver-coated copper core-shell micro particles to the silver-coated copper core-shell nano particles in the mixed particles is 1: 1-1: 6.
The second technical scheme of the invention is as follows: a preparation method of silver-coated copper core-shell micro/nano mixed particles comprises the following steps:
(1) dropwise adding a metal copper salt solution into a mixed solution of a dispersing agent and a reducing agent, continuously performing oil bath stirring reaction after dropwise adding is finished, and centrifuging to obtain a precipitate product A;
(2) and adding the precipitate product A into the aqueous solution again, adding a reducing agent, heating and stirring for a period of time in an oil bath pot, then dropwise adding a silver salt solution, continuously stirring and reacting for 5-30 min after dropwise adding is finished, and centrifuging to obtain the silver-coated copper core-shell micro/nano mixed particles.
Further, the copper metal salt includes CuCl2、Cu(NO3)2And CuSO4One or more of; the dispersing agent comprises one or more of sodium citrate, polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide;
the reducing agent comprises one or more of hydrazine hydrate, sodium hypophosphite, ascorbic acid and sodium borohydride;
the silver salt comprises at least one of silver nitrate, silver acetate and silver sulfate;
the reaction time of the continuous oil bath stirring reaction in the step (1) is 0.5-2.5 h, and the stirring speed is 300-500 r/min;
the oil bath temperature is 60-90 ℃.
The reaction time of the continuous stirring reaction in the step (2) is 30min, and the stirring speed is 300 r/min-500 r/min.
Furthermore, the molecular weight of the polyvinylpyrrolidone is 1000-40000.
Further, the twice centrifugation specifically includes: and (4) alternately cleaning the precipitate obtained by centrifugation with deionized water and absolute ethyl alcohol, and centrifuging for multiple times.
Further, the concentration of the silver salt in the silver salt solution in the step (2) is 0.1 mol/L-0.3 mol/L.
Further, the concentration of the reducing agent in the step (2) is 0.05 mol/L-0.5 mol/L.
Further, in the step (1), the volume ratio of the metal copper salt solution to the mixed solution of the dispersing agent and the reducing agent is 1: 2-1: 10; the mass ratio of the dispersing agent to the reducing agent is 1: 1-5: 1.
Further, the rotation speed adopted by the centrifugation in the step (1) and the step (2) is 4000r/min to 8000 r/min.
The third technical scheme of the invention is as follows: an application of silver-coated copper core-shell micro/nano mixed particles in composite soldering paste.
The fourth technical scheme of the invention is as follows: a composite soldering paste comprises the silver-coated copper core-shell micro/nano mixed particles.
Further, the composite soldering paste comprises the following raw materials in parts by weight: 80-90 parts of silver-coated copper core-shell micro/nano mixed particles, 2-8 parts of an additive, 2-8 parts of a binder, 2-8 parts of a diluent and 2-8 parts of a soldering flux.
Further, the additive comprises one or more of deionized water, absolute ethyl alcohol and acetone; the binder comprises one or more of glycerol, polyethylene glycol, isobutanol, isopropanol, isopropanolamine and fish oil; the diluent comprises at least one of alcohol and terpineol; the soldering flux comprises one or more of rosin resin and rosin resin derivative.
The fifth technical scheme of the invention is as follows: the preparation method of the composite soldering paste is characterized by comprising the following steps of: and mixing the silver-coated copper core-shell micro/nano mixed particles, a dispersing agent, a binder, a diluent and a soldering flux, performing ultrasonic treatment, and heating to prepare the composite soldering paste.
The invention discloses the following technical effects:
the composite soldering paste is prepared by taking the silver-coated copper core-shell micro/nano mixed particles, the dispersing agent, the binder, the diluent and the soldering flux as raw materials, effectively solves the problem of high cost of silver nano solder, solves the problems of high storage difficulty, harsh sintering conditions and the like caused by easy oxidation of micro/nano copper, and has huge development potential and application scenes. (since copper is easily oxidized, silver is not easily oxidized, and silver is coated on the surface of copper to prevent copper from being oxidized).
The invention adopts a liquid phase reduction method to prepare nano-copper particles, then in the heating and stirring process of the nano-copper particles in an oil bath pot, part of the nano-copper particles grow into submicron or micron copper particles through Ostwald curing, finally, the single nano-copper particles form micron/nano mixed copper particles, and the volume ratio of the obtained micron copper to the nano-copper is different according to the different heating and stirring time. The silver-coated copper core-shell micro/nano mixed particles are prepared by chemical plating, the preparation method is simple, the cost is relatively low, and the production efficiency is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of the present invention for preparing a composite solder paste;
FIG. 2 is an SEM image of silver-coated copper core-shell micro/nano hybrid particles prepared in example 1 of the present invention;
FIG. 3 is a comparison graph of XRD before and after heating micro/nano copper particles at 150 deg.C for 30 min;
FIG. 4 is a comparison of XRD of silver-coated copper core-shell micro/nano hybrid particles prepared in example 1 of the present invention before and after heating at 150 ℃ for 30 min;
FIG. 5 is a graph of the results of linear scanning of nano-silver coated copper;
fig. 6 is a graph of the results of a linear scan of micron silver coated copper.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
A preparation method of composite solder paste comprises the following steps:
(1) adding 150mL of deionized water into (3) g of PVP and (3) g of sodium hypophosphite to dissolve, and dropwise adding (0.1mol/L) copper Cl2And (3) adding 10mL of aqueous solution (50) at a dropping rate, keeping constant-temperature oil bath stirring in the dropping process, keeping a stirring rate of 300r/min after the dropping is finished, continuously reacting for 2.5 hours, keeping the temperature of an oil bath kettle at 60-65 ℃, carrying out liquid-solid separation by using a high-speed centrifuge under the condition of 4000r/min after the reaction is finished, and alternately cleaning and centrifuging the obtained precipitate by using deionized water and absolute ethyl alcohol for three times to obtain a product A.
(2) Dissolving the product A with deionized water, heating in a water bath and stirring for 5min, then adding 0.1mol/L sodium citrate (20) mL, uniformly mixing, dropwise adding 0.1mol/L silver nitrate solution (20) mL, continuously stirring in the dropwise adding process, keeping the stirring speed of 300r/min after the dropwise adding is finished, continuously reacting for 1.5h, after the reaction is finished, performing liquid-solid separation by using a high-speed centrifuge under the condition of 4000r/min, alternately cleaning and centrifuging the obtained precipitate with deionized water and absolute ethyl alcohol for three times, and drying the cleaned and centrifuged precipitate for 6h under the condition of vacuum 70 ℃ to obtain the silver-coated copper core-shell micro/nano mixed particle.
(3) Uniformly mixing 80g of mixed particles consisting of micron silver-coated copper and nano silver-coated copper, 5g of absolute ethyl alcohol, 5g of glycerol, 4g of terpineol and 6g of rosin resin, stirring for 100min by 120W ultrasonic oscillation to uniformly mix the soldering paste, ensuring good dispersibility of the particles, heating for 30min at 60 ℃ in a vacuum drying oven, and removing redundant organic reagents to prepare the composite soldering paste.
The preparation flow chart is shown in figure 1.
Example 2
A preparation method of composite solder paste comprises the following steps:
(1) adding 200mL of deionized water into (6) g of sodium citrate and (3) g of hydrazine hydrate for dissolving, heating and stirring in an oil bath for 10min, and then dropwise adding (0.1mol/L) CuCl2And (3) adding 15mL of aqueous solution (50) at a dropping rate, keeping constant-temperature oil bath stirring in the dropping process, keeping a stirring rate of 400r/min after the dropping is finished, continuously reacting for 1.5h, keeping the temperature of an oil bath pot at 75-80 ℃, carrying out liquid-solid separation by using a high-speed centrifuge under the condition of 6000r/min after the reaction is finished, and alternately cleaning and centrifuging the obtained precipitate by using deionized water and absolute ethyl alcohol for three times to obtain a product A.
(2) Dissolving the product A with deionized water, adding sodium citrate hydrazine hydrate (20) mL with the concentration of 0.2mol/L, uniformly mixing, dropwise adding silver nitrate solution (20) mL with the concentration of 0.2mol/L, continuously stirring in the dropwise adding process, keeping the stirring speed of 400r/min after the dropwise adding is finished, continuously reacting for 1h, after the reaction is finished, carrying out liquid-solid separation by using a high-speed centrifuge under the condition of 6000r/min, alternately cleaning and centrifuging the obtained precipitate with deionized water and absolute ethyl alcohol for three times, and drying the cleaned and centrifuged precipitate for 8h under the condition of vacuum 60 ℃ to obtain the silver-coated copper core-shell micro/nano mixed particle.
(3) Uniformly mixing 80g of mixed particles consisting of micron silver-coated copper and nano silver-coated copper, 4g of absolute ethyl alcohol, 6g of glycerol, 4g of terpineol and 6g of rosin resin, stirring for 80min by 120W ultrasonic oscillation to uniformly mix the soldering paste, ensuring good dispersibility of the particles, heating for 30min at 60 ℃ in a vacuum drying oven, and removing redundant organic reagents to prepare the composite soldering paste.
The preparation flow chart is shown in figure 1.
Example 3
A preparation method of composite solder paste comprises the following steps:
(1) adding 250mL of deionized water into (9) g of sodium citrate and (3) g of hydrazine hydrate for dissolving, and dropwise adding (0.1mol/L) CuCl2And (3) adding 20mL of aqueous solution (50) at a dropping rate, keeping constant-temperature oil bath stirring in the dropping process, keeping a stirring rate of 500r/min after the dropping is finished, continuously reacting for 0.5h, keeping the temperature of an oil bath pot at 85-90 ℃, carrying out liquid-solid separation by using a high-speed centrifuge under the condition of 8000r/min after the reaction is finished, and alternately cleaning and centrifuging the obtained precipitate by using deionized water and absolute ethyl alcohol for three times to obtain a product A.
(2) Dissolving the product A with deionized water, heating and stirring for 15min in an oil bath, then adding 0.3mol/L sodium citrate hydrazine hydrate (20) mL, uniformly mixing, dropwise adding 0.3mol/L silver nitrate solution (20) mL, continuously stirring in the dropwise adding process, keeping the stirring speed of 500r/min after the dropwise adding is finished, continuously reacting for 1h, after the reaction is finished, performing liquid-solid separation by using a high-speed centrifuge under the condition of 8000r/min, alternately cleaning and centrifuging the obtained precipitate with deionized water and absolute ethyl alcohol for three times, and drying the cleaned and centrifuged precipitate for 10h under the condition of vacuum 50 ℃ to obtain the silver-coated copper core-shell micro/nano mixed particle.
(3) Uniformly mixing 80g of mixed particles consisting of micron silver-coated copper and nano silver-coated copper, 6g of absolute ethyl alcohol, 5g of glycerol, 4g of terpineol and 5g of rosin resin, stirring for 60min by 120W ultrasonic oscillation to uniformly mix the soldering paste, ensuring good dispersibility of the particles, heating for 30min at 50 ℃ in a vacuum drying oven, and removing redundant organic reagents to prepare the composite soldering paste.
The micro/nano mixing proportions of the composite soldering paste prepared in the embodiments 1-3 of the invention are different, after the product A in the step (2) is dissolved by the deionized water, the influence on the heating and stirring time of the oil bath is the largest, and the longer the heating and stirring time is, the more the content of the micron particles is.
The preparation flow chart is shown in figure 1.
Effect example 1
The micro/nano silver-coated copper particles prepared in example 1 are subjected to morphology characterization, and the result is shown in fig. 2, and it can be seen from fig. 2 that the micro and nano particles are mixed uniformly, and the particle size difference between the nano particles and the micro particles is large.
The micro/nano silver-coated copper particles prepared in example 1 were subjected to oxidation resistance analysis, and the results shown in FIG. 3 were obtained, and it can be seen from FIG. 3 that Cu appeared after the copper particles were heated at 150 ℃ for 30min2O and CuO, indicating that copper is readily oxidized; while fig. 4 shows that no copper oxide appears after the micro/nano silver-coated copper particles are heated at 150 ℃ for 30min, comparing fig. 3 and fig. 4 can show that the micro/nano silver-coated copper has good oxidation resistance compared with the copper particles.
The micro/nano silver-coated copper particles prepared in example 1 were dissolved in an absolute ethanol solution, ultrasonically dispersed, and then dropped on a molybdenum mesh for drying, and then subjected to linear scanning by a TEM method, and the results are shown in fig. 5 to 6.
The nanometer can be seen from fig. 5 and 6
FIG. 5 shows the results of linear scanning of the nano-silver coated copper, and it can be seen from FIG. 5 that the distribution of copper element is more in the middle and less on both sides; the distribution of the silver element is less in the middle and more on two sides, which proves that the prepared silver-coated copper core-shell structure.
Fig. 6 shows the linear scanning result of the micron silver-coated copper, and as shown, the particles of the micron silver-coated copper are hexagonal, and the linear scanning result shows that the silver element is not much relative to the copper element, because the micron particles have large size and small surface energy, so that the silver layer on the surface of the copper particles is thinner, but the micron copper particles can be observed to be wrapped by the silver element.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The silver-coated copper core-shell micro/nano mixed particle is characterized by comprising silver-coated copper core-shell micro particles and silver-coated copper core-shell nano particles, wherein the molar ratio of copper to silver in the silver-coated copper core-shell micro/nano mixed particle is 10: 1-1: 10.
2. The silver-clad copper core-shell micro/nano hybrid particle according to claim 1, wherein the volume ratio of the silver-clad copper core-shell micro particles to the silver-clad copper core-shell nano particles in the hybrid particle is 1: 1-1: 6.
3. the preparation method of the silver-coated copper core-shell micro/nano mixed particle as claimed in any one of claims 1 to 2, which comprises the following steps:
(1) dropwise adding a metal copper salt solution into a mixed solution of a dispersing agent and a reducing agent, continuously performing oil bath stirring reaction after dropwise adding is finished, and centrifuging to obtain a precipitate product A;
(2) adding the precipitate product A into an aqueous solution, adding another reducing agent, curing by using Ostwald, heating and stirring in an oil bath pan for a period of time to promote the growth of the nano particles, then dropwise adding a silver salt solution, continuously stirring and reacting for 5-30 min after dropwise adding is finished, and centrifugally washing to obtain the silver-coated copper core-shell micro/nano mixed particles.
4. The method for preparing silver-coated copper core-shell micro/nano hybrid particles according to claim 3,
the copper metal salt comprises CuCl2、Cu(NO3)2And CuSO4One or more of; the dispersing agent comprises one or more of sodium citrate, polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide;
the reducing agent comprises one or more of hydrazine hydrate, sodium hypophosphite, ascorbic acid and sodium borohydride;
the silver salt comprises at least one of silver nitrate, silver acetate and silver sulfate;
the reaction time of the continuous oil bath stirring reaction in the step (1) is 0.5-2.5 h, and the stirring speed is 300-500 r/min;
the oil bath temperature is 60-90 ℃.
The reaction time of the continuous stirring reaction in the step (2) is 30min, and the stirring speed is 300 r/min-500 r/min.
5. The method for preparing silver-coated copper core-shell micro/nano hybrid particles according to claim 3, wherein in the step (1),
the volume ratio of the metal copper salt solution to the mixed solution of the dispersing agent and the reducing agent is 1: 2-1: 10;
the mass ratio of the dispersing agent to the reducing agent is 1: 1-5: 1.
6. Use of the silver-coated copper core-shell micro/nano hybrid particle according to claim 1 in a composite solder paste.
7. A composite solder paste comprising the silver-clad copper core-shell micro/nano hybrid particle according to claim 1.
8. The composite solder paste according to claim 7, wherein the raw materials comprise the following components in parts by weight: 80-90 parts of silver-coated copper core-shell micro/nano mixed particles, 2-8 parts of an additive, 2-8 parts of a binder, 2-8 parts of a diluent and 2-8 parts of a soldering flux.
9. The composite solder paste of claim 8, wherein the additive comprises one or more of deionized water, absolute ethanol, and acetone; the binder comprises one or more of glycerol, polyethylene glycol, isobutanol, isopropanol, isopropanolamine and fish oil; the diluent comprises at least one of alcohol and terpineol; the soldering flux comprises one or more of rosin resin and rosin resin derivative.
10. A method for preparing a composite solder paste according to any one of claims 8 to 9, comprising the steps of: and mixing the silver-coated copper core-shell micro/nano mixed particles, a dispersing agent, a binder, a diluent and a soldering flux, performing ultrasonic treatment, and heating to prepare the composite soldering paste.
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