CN113972025A - Preparation and interconnection process of multi-size micro-nano mixed silver paste - Google Patents
Preparation and interconnection process of multi-size micro-nano mixed silver paste Download PDFInfo
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- CN113972025A CN113972025A CN202111255439.5A CN202111255439A CN113972025A CN 113972025 A CN113972025 A CN 113972025A CN 202111255439 A CN202111255439 A CN 202111255439A CN 113972025 A CN113972025 A CN 113972025A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 150
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- 239000004332 silver Substances 0.000 title claims abstract description 144
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000012046 mixed solvent Substances 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 239000000084 colloidal system Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 20
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 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 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 10
- 229940071536 silver acetate Drugs 0.000 claims description 10
- 229910001923 silver oxide Inorganic materials 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 8
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 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
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 9
- 238000004100 electronic packaging Methods 0.000 abstract description 4
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the field of electronic packaging interconnection materials, in particular to a preparation process of multi-size micro-nano mixed silver paste. The preparation process comprises the following steps: adding a silver source into an alcohol-containing mixed solvent for dissolving; obtaining an initial solution; adding a dispersing agent and a reducing agent into the initial solution, and reacting to obtain mixed silver colloid; and (4) obtaining the multi-size micro-nano mixed silver paste through concentration operation. The preparation process adjusts the particle size of the generated silver particles through the slightly solubility of the silver source, and influences the dispersibility of the particles by controlling the power of ultrasonic and the proportion of the silver source and the dispersing agent; by using a clean silver source, a reducing agent and a dispersing agent, ionic impurities and high molecular organic matters are not left after the silver paste is sintered; controlling the solubility of the silver source and the dissolution and volatilization rate in the sintering process by controlling the components of the mixed solvent; the micro-nano silver material with mixed size is prepared by a one-pot method, and the in-situ mixed paste can be obtained by one step of concentration and can be immediately used for the interconnection process.
Description
Technical Field
The invention relates to the field of electronic packaging interconnection materials, in particular to a preparation and interconnection process of multi-size micro-nano mixed silver paste.
Background
The traditional electronic packaging interconnection materials can be divided into solder paste and conductive adhesive, but the traditional electronic packaging interconnection materials cannot meet the use requirements of high-power devices. The nano metal material has good electric and thermal conductivity; the material can be sintered at a lower temperature, and has the characteristics of melting point, electric conductivity and thermal conductivity close to those of bulk metals after sintering, so that the material can well meet the working environment of high-temperature service and is an ideal interconnection material of high-power devices.
At present, the process for preparing the multi-size micro-nano mixed silver paste mainly comprises two types: firstly, carrying out a series of pre-treatments such as cleaning and purification on commercial nano silver powder and commercial micron silver powder, removing redundant protective agents, then drying and storing, and dispersing in a solvent to obtain mixed silver paste; and secondly, preparing the multi-size micro-nano mixed silver colloid step by adopting a multi-pot method, and obtaining the mixed silver paste through a series of steps of separation, purification, drying, redispersion and the like. Commercial silver powders are not only costly but also require complex pre-treatments before use. The surface of commercial silver powder particles is usually coated with an organic layer, and the coating layer is damaged in the pretreatment process. As the nano material has high activity, nano silver particles can quickly agglomerate without a coating layer to form agglomerated masses with different shapes, and the mechanical property and the electrical property after sintering can be greatly influenced. The preparation of the multi-size micro-nano mixed silver particles by the multi-pot method has more defects: silver particles with different particle sizes need to be prepared step by step, and the process is complicated; it is difficult to control the particle size of the silver particles; the silver source, reducing agent and dispersing agent used can introduce more ionic impurities and high molecular impurities. The sintering difficulty is improved, and the mechanical property and the electrical property after sintering are greatly influenced.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a preparation and interconnection process of multi-size micro-nano mixed silver paste, which is simple in process and can ensure the preparation quality of the silver paste.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation process of multi-size micro-nano mixed silver paste comprises the following steps:
A. adding a plurality of different silver sources with different solubilities in the same solvent into an alcohol-containing mixed solvent at room temperature, and fully dissolving; an initial solution was obtained.
B. And under an ultrasonic environment, heating while adding a dispersing agent and a reducing agent into the initial solution, carrying out reaction operation to enable the dispersing agent to be coated on a silver source, and reducing Ag & lt + & gt in the initial solution into silver particles by the reducing agent to obtain the mixed silver colloid.
C. And concentrating the mixed silver colloid to obtain the multi-size micro-nano mixed silver paste.
Preferably, the silver source is one or more of silver carbonate, silver oxide, silver acetate, silver acetylacetonate; when the silver source is selected specifically, the silver source having a large difference in solubility in the same solvent is selected as much as possible, and no anionic impurities remain in the solution after the reaction with the reducing agent, or the anionic impurities can be removed by converting into a gas during the sintering.
Preferably, the alcohol-containing mixed solvent is a combination of at least two of ethanol, ethylene glycol, toluene, butylbenzene, diethyl ether, butyl ether, ethyl acetate, diethylene glycol, dipropylene glycol, glycerol, acetone, glycerol, and terpineol; when the alcohol-containing mixed solvent is specifically selected, an alcohol solvent with high polarity and good viscosity and wettability and a solvent with low polarity, which can be mutually soluble with the alcohol solvent, has different boiling points and slow decomposition and volatilization rate are selected. The two solvents are mutually soluble according to a certain proportion, can ensure the uniformity of a mixed silver colloid system, can effectively control the evaporation speed of dissolution in the sintering process, and improve the sintering performance.
Preferably, the operation mode of making the silver source fully dissolved in the alcohol-containing mixed solvent in the step A is a mechanical stirring method, ultrasonic vibration and/or increasing the pressure in the reaction vessel; helping the silver source to dissolve sufficiently in the solution.
Preferably, the temperature raising operation in step B is: the temperature rise range is between room temperature and 160 ℃, and the temperature rise rate is 0 to 10 ℃/min; the dissolution rate of the silver source can be effectively controlled by adjusting the temperature rise rate, and the reaction rate can be effectively controlled.
Preferably, the ultrasonic environment in the step B is: carrying out reaction in an ultrasonic environment of an ultrasonic oscillator with oscillation power of 10-200W; the ultrasonic treatment not only accelerates the diffusion of reactants and products, but also affects the dispersibility of the silver particles.
Preferably, the concentration operation is performed using one or more of a rotary evaporator, a vacuum drying oven, a centrifuge, or a filtration device or natural sedimentation.
Preferably, in the step B, the dispersing agent is PEG-200, PEG-400, PEG-600 or glucose; the reducing agent is ascorbic acid, hydrogen peroxide or hydrazine hydrate. The dispersant has the advantages of small molecular weight, capability of being removed at a low sintering temperature and no anionic impurities left; the reducing agent does not remain in solution as anionic impurities or can be removed during sintering.
Preferably, the molar ratio of the reducing agent to the silver source is from 0.5:1 to 4: 1; the molar ratio of the dispersing agent to the silver source is 0.25:1-2: 1.
An interconnection process of multi-size micro-nano mixed silver paste comprises the following steps:
uniformly coating the multi-size micro-nano mixed silver paste on the surface of a silver-plated copper plate with the thickness of 4x 4mm by using a screen printing, coating, spraying or dispensing mode to form a substrate; taking another silver-plated copper plate with a larger size as a bottom plate, covering the substrate above the upper bottom plate, and attaching the basic middle silver paste layer to the top surface of the bottom plate to obtain a sandwich structure; at H2Mixed with Ar or N2Sintering in mixed atmosphere at 20-350 deg.c and 0-5 MPa.
The embodiment of the invention has the following beneficial effects:
the preparation process utilizes the slightly solubility of the silver source to adjust the particle size of the generated silver particles, and adjusts the dissolution of the silver source in the solution by controlling the proportion of the silver source and the reducing agent and controlling the heating rate, thereby controlling the reaction speed; by controlling the power of the ultrasonic wave and the proportion of the silver source and the dispersing agent, the dispersibility of the silver particles in the reaction operation process can be further influenced; by using a clean silver source, a reducing agent and a dispersing agent, ionic impurities and high molecular organic matters are not left after the silver paste is sintered; controlling the solubility of the silver source and the dissolution and volatilization rate in the sintering process by controlling the components of the alcohol-containing mixed solvent; the micro-nano silver material with mixed sizes is prepared through the preparation process, the in-situ mixed paste can be obtained through one step of concentration, and the multi-size micro-nano mixed silver paste can be immediately used for the interconnection process. The preparation process not only greatly reduces the preparation process flow of the multi-size micro-nano mixed silver paste, but also effectively avoids agglomeration of the nano silver material, and the silver paste has good mechanical property and electrical property after sintering, low requirement on preparation equipment, good practicability, large economic benefit and wide application prospect.
Drawings
FIG. 1 is a schematic flow diagram of one embodiment of the present invention;
fig. 2 is a schematic flow diagram of another embodiment of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
As shown in fig. 1, a preparation process of a multi-size micro-nano mixed silver paste comprises the following steps:
A. adding a plurality of different silver sources with different solubilities in the same solvent into an alcohol-containing mixed solvent at room temperature, and fully dissolving; an initial solution was obtained.
B. And under an ultrasonic environment, heating while adding a dispersing agent and a reducing agent into the initial solution, carrying out reaction operation to enable the dispersing agent to be coated on a silver source, and reducing Ag & lt + & gt in the initial solution into silver particles by the reducing agent to obtain the mixed silver colloid.
C. And concentrating the mixed silver colloid to obtain the multi-size micro-nano mixed silver paste.
The preparation process utilizes the slightly solubility of the silver source to adjust the particle size of the generated silver particles, and adjusts the dissolution of the silver source in the solution by controlling the proportion of the silver source and the reducing agent and controlling the heating rate, thereby controlling the reaction speed; by controlling the power of the ultrasonic wave and the proportion of the silver source and the dispersing agent, the dispersibility of the silver particles in the reaction operation process can be further influenced; by using a clean silver source, a reducing agent and a dispersing agent, ionic impurities and high molecular organic matters are not left after the silver paste is sintered; controlling the solubility of the silver source and the dissolution and volatilization rate in the sintering process by controlling the components of the alcohol-containing mixed solvent; the micro-nano silver material with mixed sizes is prepared through the preparation process, the in-situ mixed paste can be obtained through one step of concentration, and the multi-size micro-nano mixed silver paste can be immediately used for the interconnection process. The preparation process not only greatly reduces the preparation process flow of the multi-size micro-nano mixed silver paste, but also effectively avoids agglomeration of the nano silver material, and the silver paste has good mechanical property and electrical property after sintering, low requirement on preparation equipment, good practicability, large economic benefit and wide application prospect.
Example 2
As shown in fig. 2, on the basis of embodiment 1, this embodiment provides an interconnection process of a multi-size micro-nano mixed silver paste, which includes the following steps:
uniformly coating the multi-size micro-nano mixed silver paste in the embodiment 1 on the surface of a silver-plated copper plate with the thickness of 4x 4mm by using a screen printing, coating, spraying or dispensing mode to form a substrate; taking another silver-plated copper plate with a larger size as a bottom plate, covering the substrate above the upper bottom plate, and attaching the basic middle silver paste layer to the top surface of the bottom plate to obtain a sandwich structure; at H2Mixed with Ar or N2Sintering in mixed atmosphere at 20-350 deg.c and 0-5 MPa.
Example 3
At room temperature, certain amounts of silver oxide and silver carbonate are used as silver sources, and ethylene glycol and diethyl ether are used in molMixing in a ratio of 2:1 to obtain an alcohol-containing mixed solvent, adding a silver source into the alcohol-containing mixed solvent, and increasing the pressure in the reaction vessel to fully dissolve the silver source in the alcohol-containing mixed solvent to obtain an initial solution; under the environment that the ultrasonic oscillation power is 120W and the heating rate is 0.5 ℃/min, according to the molar ratio of silver oxide to ascorbic acid of 1:2, the molar ratio of silver oxide to PEG-200 of 1:2 and the ratio of silver oxide to silver carbonate of 1:1.5, the ascorbic acid and the PEG-200 are poured into the initial solution to react for 60min to obtain mixed silver colloid; the silver in the mixed silver colloid consisted of silver particles of approximately 25nm and 150nm in size in a ratio of 1: 3. And pouring the mixed silver colloid into a centrifuge tube, centrifuging for 5min in a centrifuge under the condition of 12000r/min, and stirring to obtain the uniform mixed silver paste with the mass fraction of 90%. Coating the paste on a 4 × 4mm silver-plated copper plate to form a substrate, placing the substrate on a 10 × 10mm silver-plated copper plate, placing the substrate in a hot-pressing furnace, and heating in N2Sintering under the conditions of atmosphere, 260 ℃, 2MPa and the like; the shear force is 51MPa, and the conductivity is 2.6 multiplied by 10-5(Ω*cm)-1The interconnect structure of (1).
Example 4
At room temperature, taking a certain amount of silver oxide and silver acetate as silver sources, mixing terpineol and butyl ether in a molar ratio of 1:1 to obtain an alcohol-containing mixed solvent, adding the silver sources into the alcohol-containing mixed solvent, and increasing the pressure in a reaction vessel to fully dissolve the silver sources in the alcohol-containing mixed solvent to obtain an initial solution; under the environment that the ultrasonic oscillation power is 80W and the heating rate is 2 ℃/min, according to the molar ratio of silver oxide to hydrazine hydrate of 1:0.5, the molar ratio of silver oxide to PEG-400 of 1:1 and the molar ratio of silver oxide to silver acetate of 1:1, pouring hydrazine hydrate and PEG-400 into the initial solution, and reacting for 15min to obtain mixed silver colloid; the silver in the mixed silver colloid consisted of silver particles with a particle size of about 100nm and 2 μm in a ratio of 2: 1. Pouring the colloid into a rotary evaporator, evaporating for 30min under the conditions of the rotating speed of 160r/min, the evaporating temperature of 200 ℃ and the vacuum degree of 180Pa, taking out and stirring to obtain a micro-nano mixed silver paste with the mass fraction of 96%, coating the paste on a silver-plated substrate with the thickness of 4-4 mm, placing the substrate on a silver-plated copper plate with the thickness of 10-10 mm to form a substrate, and finally placing the substrate into a hot-pressing furnaceSintering at the conditions of N2 atmosphere, 200 ℃, 1MPa and the like; the shear force is 46MPa, and the conductivity is 2.1 multiplied by 10-5(Ω*cm)-1The interconnect structure of (1).
Example 5
At room temperature, taking a certain amount of silver acetate and silver acetylacetonate as silver sources, mixing glycerol and acetone in a molar ratio of 1:1 to obtain an alcohol-containing mixed solvent, adding the silver sources into the alcohol-containing mixed solvent, and performing ultrasonic oscillation operation to fully dissolve the silver sources in the alcohol-containing mixed solvent to obtain an initial solution; under the environment that the ultrasonic oscillation power is 100W and the heating rate is 1 ℃/min, according to the molar ratio of silver acetate to hydrogen peroxide of 1:2, the molar ratio of silver acetate to glucose of 1:1.5 and the molar ratio of silver acetate to silver acetylacetonate of 2:1, ascorbic acid and glucose are poured into the initial solution to react for 50min to obtain mixed silver colloid; the silver in the mixed silver colloid consisted of silver particles with a particle size of about 600nm and 3 μm in a 2:3 ratio. Filtering the colloid with microfiltration membrane to obtain silver paste with mass fraction of 78%, coating the paste on a silver-plated substrate of 4 × 4mm to form a substrate, placing the substrate on a silver-plated copper plate of 20 × 20mm, placing the substrate in a hot-pressing furnace, and heating in H2Sintering in a mixed atmosphere of/Ar at 300 ℃ and 2 MPa; the shear force is 32MPa, and the conductivity is 7.8 multiplied by 10-6(Ω*cm)-1The interconnect structure of (1).
Example 6
At room temperature, taking a certain amount of silver carbonate and silver acetate as silver sources, mixing the silver sources according to the molar ratio of 2:1 of ethylene glycol to acetone to obtain an alcohol-containing mixed solvent, adding the silver sources into the alcohol-containing mixed solvent, and fully dissolving the silver sources in the alcohol-containing mixed solvent by a mechanical stirring method to obtain an initial solution; under the environment that the ultrasonic oscillation power is 140W and the heating rate is 1 ℃/min, according to the molar ratio of silver carbonate to ascorbic acid of 1:2, the molar ratio of silver carbonate to PEG-600 of 1:1 and the molar ratio of silver carbonate to silver acetate of 1.5:1, the ascorbic acid and the PEG-600 are poured into the initial solution to react for 40min to obtain mixed silver colloid; the silver in the mixed silver colloid consisted of silver particles with a particle size of about 150nm and 2 μm in a ratio of 2: 1. Pouring the colloid into a rotary evaporator at a rotation speed of 160r/min and an evaporation temperature of 200 deg.C under vacuumEvaporating for 30min under the conditions of the temperature of 180Pa and the like, taking out and stirring to obtain a uniform micro-nano mixed silver paste with the mass fraction of 96%, coating the paste on a silver-plated substrate with the thickness of 4mm, placing the substrate on a silver-plated copper plate with the thickness of 10mm, and finally placing the substrate into a hot pressing furnace to be sintered under the conditions of the atmosphere of N2, the temperature of 200 ℃, the pressure of 2MPa and the like; the shear force is 38MPa, and the conductivity is 1.1 multiplied by 10-5(Ω*cm)-1The interconnect structure of (1).
The mass fraction of silver in the multi-size micro-nano mixed silver paste can reach 30-99%.
The preparation process adjusts the particle size of the generated silver particles through the slightly solubility of the silver source, adjusts the dissolution of the silver source in the solution by controlling the proportion of the silver source and the reducing agent and controlling the heating rate, and further controls the reaction speed; the dispersibility of the particles is influenced by controlling the power of the ultrasonic waves and the proportion of the silver source to the dispersing agent; by using a clean silver source, a reducing agent and a dispersing agent, ionic impurities and high molecular organic matters are not left after the silver paste is sintered; controlling the solubility of the silver source and the dissolution and volatilization rate in the sintering process by controlling the components of the mixed solvent; the micro-nano silver material with mixed size is prepared by a one-pot method, and the in-situ mixed paste can be obtained by one step of concentration and can be immediately used for the interconnection process.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. A preparation process of multi-size micro-nano mixed silver paste is characterized by comprising the following steps:
A. adding a plurality of different silver sources with different solubilities in the same solvent into an alcohol-containing mixed solvent at room temperature, and fully dissolving; obtaining an initial solution;
B. under an ultrasonic environment, heating while adding a dispersing agent and a reducing agent into the initial solution, and carrying out reaction operation to enable the dispersing agent to be coated on a silver source, wherein the reducing agent reduces Ag + in the initial solution into silver particles to obtain a mixed silver colloid;
C. and concentrating the mixed silver colloid to obtain the multi-size micro-nano mixed silver paste.
2. The preparation process of the multi-size micro-nano mixed silver paste according to claim 1, wherein the silver source is one or a combination of silver carbonate, silver oxide, silver acetate and silver acetylacetonate.
3. The process for preparing multi-size micro-nano mixed silver paste according to claim 1, wherein the alcohol-containing mixed solvent is a combination of at least two of ethanol, ethylene glycol, toluene, butylbenzene, diethyl ether, butyl ether, ethyl acetate, diethylene glycol, dipropylene glycol, glycerol, acetone, glycerol, and terpineol.
4. The process for preparing the multi-size micro-nano mixed silver paste according to claim 1, wherein the operation mode of fully dissolving the silver source in the alcohol-containing mixed solvent in the step A is a mechanical stirring method, ultrasonic oscillation and/or increase of pressure in a reaction vessel.
5. The preparation process of the multi-size micro-nano mixed silver paste according to claim 1, wherein the heating operation in the step B is: the temperature rise range is between room temperature and 160 ℃, and the temperature rise rate is 0 to 10 ℃/min.
6. The preparation process of the multi-size micro-nano mixed silver paste according to claim 1, wherein the ultrasonic environment in the step B is as follows: and reacting in an ultrasonic environment of an ultrasonic oscillator with oscillation power of 10-200W.
7. The process for preparing the multi-size micro-nano mixed silver paste according to claim 6, wherein the concentration operation is one or more of a rotary evaporator, a vacuum drying oven, a centrifuge, or a filtering device or natural sedimentation.
8. The preparation process of the multi-size micro-nano mixed silver paste according to claim 1, wherein in the step B, the dispersing agent is PEG-200, PEG-400, PEG-600 or glucose; the reducing agent is ascorbic acid, hydrogen peroxide or hydrazine hydrate.
9. The preparation process of the multi-size micro-nano mixed silver paste according to claim 1, wherein the molar ratio of the reducing agent to the silver source is 0.5:1-4: 1; the molar ratio of the dispersing agent to the silver source is 0.25:1-2: 1.
10. An interconnection process of multi-size micro-nano mixed silver paste is characterized by comprising the following steps:
uniformly coating the multi-size micro-nano mixed silver paste in any one of claims 1-9 on the surface of a silver-plated copper plate with the thickness of 4x 4mm by using a screen printing, coating, spraying or dispensing mode to form a substrate;
taking another silver-plated copper plate with a larger size as a bottom plate, covering the substrate above the upper bottom plate, and attaching the basic middle silver paste layer to the top surface of the bottom plate to obtain a sandwich structure;
at H2Mixed with Ar or N2Sintering in mixed atmosphere at 20-350 deg.c and 0-5 MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116313223A (en) * | 2023-03-28 | 2023-06-23 | 深圳市众诚达应用材料科技有限公司 | Silver colloid and preparation method thereof |
| CN116532841A (en) * | 2023-06-01 | 2023-08-04 | 徐州得驰电子科技有限公司 | Silver soldering paste and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107848037A (en) * | 2015-07-24 | 2018-03-27 | 国立大学法人大阪大学 | Argent grain manufacture method, Argent grain and silver paste |
| CN111558728A (en) * | 2020-05-13 | 2020-08-21 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Multi-size composite nano silver paste and preparation method thereof |
| WO2021164613A1 (en) * | 2020-02-20 | 2021-08-26 | 广东工业大学 | Multi-grade micro-nano mixed metal paste and preparation method therefor |
| CN113385857A (en) * | 2021-06-15 | 2021-09-14 | 广东工业大学 | Multi-size micro-nano metal particle soldering paste in-situ interconnection process and product thereof |
-
2021
- 2021-10-27 CN CN202111255439.5A patent/CN113972025B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107848037A (en) * | 2015-07-24 | 2018-03-27 | 国立大学法人大阪大学 | Argent grain manufacture method, Argent grain and silver paste |
| WO2021164613A1 (en) * | 2020-02-20 | 2021-08-26 | 广东工业大学 | Multi-grade micro-nano mixed metal paste and preparation method therefor |
| CN111558728A (en) * | 2020-05-13 | 2020-08-21 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Multi-size composite nano silver paste and preparation method thereof |
| CN113385857A (en) * | 2021-06-15 | 2021-09-14 | 广东工业大学 | Multi-size micro-nano metal particle soldering paste in-situ interconnection process and product thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG YU ET AL: "Study on conductivity of silver/conductivity ceramic composite electrode paste", 《ELECTRONIC COMPONENTS & MATERIALS》, vol. 24, no. 12, 31 December 2005 (2005-12-31) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116313223A (en) * | 2023-03-28 | 2023-06-23 | 深圳市众诚达应用材料科技有限公司 | Silver colloid and preparation method thereof |
| CN116313223B (en) * | 2023-03-28 | 2024-05-28 | 深圳众诚达应用材料股份有限公司 | Silver colloid and preparation method thereof |
| CN116532841A (en) * | 2023-06-01 | 2023-08-04 | 徐州得驰电子科技有限公司 | Silver soldering paste and preparation process thereof |
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