WO2022061834A1 - Pâte à braser à particules de cuivre, ainsi que son procédé de préparation et son procédé de frittage - Google Patents

Pâte à braser à particules de cuivre, ainsi que son procédé de préparation et son procédé de frittage Download PDF

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Publication number
WO2022061834A1
WO2022061834A1 PCT/CN2020/118173 CN2020118173W WO2022061834A1 WO 2022061834 A1 WO2022061834 A1 WO 2022061834A1 CN 2020118173 W CN2020118173 W CN 2020118173W WO 2022061834 A1 WO2022061834 A1 WO 2022061834A1
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solder paste
copper
copper particle
particle solder
copper particles
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PCT/CN2020/118173
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English (en)
Chinese (zh)
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刘志权
高悦
孙蓉
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深圳先进技术研究院
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Priority to PCT/CN2020/118173 priority Critical patent/WO2022061834A1/fr
Publication of WO2022061834A1 publication Critical patent/WO2022061834A1/fr

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    • 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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • 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
    • 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
    • B23K35/40—Making wire or rods for soldering or welding

Definitions

  • the present application relates to the technical field of electronic manufacturing, and in particular, to a copper particle solder paste, a preparation method thereof, and a sintering method.
  • microelectronics technology leads the development of current electronic technology. With the rapid upgrading of electronic technology, the attention of microelectronics packaging technology is increasing day by day. At present, the emergence of third-generation solid-state power semiconductor devices is expected to greatly improve the utilization rate of electric energy while reducing power transmission losses, and can control more power in the same area, which is conducive to the miniaturization of devices.
  • the heating problem brought about by high integration restricts the application of third-generation semiconductors. Due to the mismatch of thermal expansion coefficients, the connection layer between the substrate and the chip is constantly subjected to thermal stress cycles during the operation of the device, while traditional tin (Sn)-based solders often generate heat under such cyclic stress due to their low melting point. Cracking, peeling and other failures.
  • nano-metal solder paste is a new type of packaging material in recent years, which can meet the packaging requirements of "low temperature sintering, high temperature service”.
  • the small size effect of nano-metal materials can promote the diffusion of atoms on the surface of metal particles, enabling welding at a lower temperature, while the size effect of particles in the bulk formed after welding disappears, and the remelting temperature returns to The melting point of the bulk metal ensures the high-temperature reliability of the nano-metal solder paste, so that it can meet the needs of the rapidly developing electronics industry.
  • Elemental copper has excellent thermal conductivity and electrical conductivity, and is cheap, easy to prepare into micro-nano copper particles, and is an ideal low-temperature sintering filler.
  • the copper layer is not easy to be thermally decomposed, which not only hinders the diffusion of copper atoms, but also increases the sintering temperature, which increases the difficulty of low-temperature sintering of copper particles.
  • the main technical problem to be solved by the present application is to provide a copper particle solder paste, a preparation method and a sintering method thereof.
  • a reducing agent to the copper particle solder paste, the copper particle solder paste is prevented from being oxidized during storage and use.
  • a technical solution adopted in the present application is to provide a copper particle solder paste, the solder paste includes copper particles with good dispersibility, a dispersant and a solvent, and also includes a reducing agent, wherein the weight of the reducing agent is The serving is 0.5 to 5 servings.
  • the reducing agent includes at least one of ascorbic acid, copper formate, formic acid, acetic acid and acetone oxime.
  • the particle diameter of the copper particles is 100 to 300 nm.
  • the copper particles are spherical.
  • the dispersing agent includes any one of polyvinylpyrrolidone K30, polyvinylpyrrolidone K90 and polyethylene glycol 1000.
  • the solvent includes at least one of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, 2-amino-2-methyl-propanol and 1-amino-2-propanol.
  • the preparation method includes: dispersing copper particles to obtain copper particles with good dispersibility; Prepare the following raw materials in parts by weight: copper particles with good dispersibility, a dispersant, a solvent and a reducing agent, wherein the weight part of the reducing agent is 0.5 to 5 parts; the reducing agent, the dispersing agent and the solvent are mixed and stirred according to the ratio of the raw materials Evenly, a paste is obtained; the paste is added to the copper particles with good dispersibility according to the raw material ratio and stirred evenly to obtain a copper particle solder paste.
  • the step of dispersing the copper particles to obtain copper particles with good dispersibility specifically includes: preparing the following raw materials according to a preset weight: copper particles, anhydrous ethanol, and a dispersant; The mixture is added into anhydrous ethanol according to the ratio of the raw materials to obtain a mixed liquid; the mixed liquid is ultrasonically dispersed for at least 30 minutes to obtain a dispersion; the dispersion is vacuum-dried to obtain copper particles with good dispersibility.
  • the step of vacuum-drying the dispersion to obtain copper particles with good dispersibility further includes: controlling the degree of vacuum to be no greater than 0.1 MPa.
  • the step of vacuum drying the dispersion to obtain copper particles with good dispersibility further comprises: controlling the drying temperature to be no more than 60°C.
  • ultrasonically dispersing the mixed liquid for at least 30 minutes and the step of obtaining the dispersion liquid specifically includes: placing the mixed liquid in an ultrasonic field and performing ultrasonic dispersion for at least 30 minutes to obtain the dispersion liquid.
  • the step of obtaining the copper particle solder paste specifically includes: adding the paste into the copper particles with good dispersibility according to the ratio of raw materials , and use mixing equipment to stir the copper particles and the paste until uniform, so as to obtain the copper particle solder paste.
  • the mixing equipment includes a planetary mixer.
  • the mixing speed of the mixing device is 2000 rpm.
  • the preparation method includes: dispersing copper particles to obtain copper particles with good dispersibility;
  • the following raw materials are prepared in parts by weight: copper particles with good dispersibility, a dispersant, a solvent and a reducing agent, wherein the weight part of the reducing agent is 0.5 to 5 parts;
  • Forming paste adding paste and dispersant to copper particles with good dispersibility according to the raw material ratio and stirring evenly to obtain copper particle solder paste.
  • the sintering method includes: preparing the following raw materials according to a preset weight: copper particles with good dispersibility, a dispersant , a solvent and a reducing agent, wherein the weight of the reducing agent is 0.5 to 5 parts; the reducing agent, the dispersing agent and the solvent are mixed according to the ratio of the raw materials and stirred evenly to obtain a paste; the paste is added according to the ratio of the raw materials.
  • the copper particles with good dispersibility are mixed evenly to obtain copper particle solder paste; pure nitrogen is pre-passed, and the copper particle solder paste is reflowed under nitrogen atmosphere to obtain a dense and continuous sintered layer.
  • the step of pre-passing pure nitrogen gas and reflow soldering the copper particle solder paste in a nitrogen atmosphere to obtain a dense and continuous sintered layer includes: controlling the heating rate to be 1-20° C./min.
  • the step of pre-passing pure nitrogen and reflow soldering the copper particle solder paste in a nitrogen atmosphere to obtain a dense and continuous sintered layer further includes: controlling the sintering temperature to be 250-300°C.
  • the step of pre-passing pure nitrogen gas and reflow soldering the copper particle solder paste in a nitrogen atmosphere to obtain a dense and continuous sintered layer further includes: controlling the sintering time to be 30 minutes.
  • the step of pre-passing pure nitrogen and reflow soldering the copper particle solder paste in a nitrogen atmosphere to obtain a dense and continuous sintered layer further includes: controlling the applied pressure to be 0.3-1 MPa.
  • the present application provides a copper particle solder paste and a preparation method and a sintering method thereof.
  • a certain amount of reducing agent to the copper paste, not only the oxidation on the surface of the copper particles can be removed It can also prevent the copper particle solder paste from being oxidized again during storage and use; and because the added reducing agent and its oxidation products are easily thermally decomposed, they will not hinder the sintering process, so that the copper particle solder paste can be used at low temperatures.
  • Sintering is performed without reducing gas protection during sintering, which not only reduces the production cost, but also improves the application range of the copper particle solder paste.
  • the present application solves the problems of complex process and high preparation cost, so that the produced copper particle solder paste meets the application requirements of "low temperature sintering, high temperature service", and can replace nano silver sintered solder paste or sintered nano silver paste Suitable for electronic packaging and micro-connection fields.
  • FIG. 1 is a schematic flowchart of an embodiment of a method for preparing copper particle solder paste of the present application
  • Fig. 2 is a detailed flow chart of an embodiment of step S11 in Fig. 1;
  • FIG. 3 is a schematic flowchart of an embodiment of the sintering method of the copper particle solder paste of the present application
  • 4a and 4b are SEM images of copper particles at different stages in Example 1 of the present application.
  • Fig. 5a and Fig. 5b are schematic diagrams comparing the SEM images of the connection joints obtained after the copper particle solder paste is sintered in Example 1 and Comparative Example 1 of the present application;
  • FIG. 6a and FIG. 6b are schematic diagrams showing the comparison of SEM images of the connection joints obtained after the copper particle solder paste is sintered in Example 3 and Example 4 of the present application.
  • the third-generation wide-bandgap semiconductor materials are widely used in high-power electronic devices because of their stable performance at a high temperature of 500 °C.
  • High temperature resistant and stable packaging interconnect materials are one of the important factors driving the development of power devices.
  • Traditional tin-lead solder paste can withstand high temperature, but because lead will pollute the environment and cause serious harm to human health, it does not meet the development trend of energy saving, environmental protection and green manufacturing, and is rarely used in electronic equipment.
  • common lead-free solders can meet high temperature resistance requirements, they all have their own shortcomings, such as high cost of silver and gold-based solders, easy corrosion of tin-based solders, and greater brittleness of bismuth-based solders.
  • nano-metal solder paste is a new type of packaging material in recent years, which can meet the packaging requirements of "low temperature sintering, high temperature service”.
  • the small size effect of nano-metal materials can promote the diffusion of atoms on the surface of metal particles, enabling welding at a lower temperature, while the size effect of particles in the bulk formed after welding disappears, and the remelting temperature returns to The melting point of the bulk metal ensures the high-temperature reliability of the nano-metal solder paste, so that it can meet the needs of the rapidly developing electronics industry.
  • Elemental copper has excellent thermal conductivity and electrical conductivity, and is cheap, easy to prepare into micro-nano copper particles, and is an ideal low-temperature sintering filler.
  • the copper particle solder paste currently produced due to the intrinsic oxidizing property of the copper particles, will be oxidized to varying degrees during the preparation and storage process, and the oxides formed on the surface of the copper particles will not only lead to the sintering of the copper particle solder paste Incomplete, it will significantly increase the interconnection temperature, reduce the sintering performance and connection strength; and in order to avoid further oxidation of the copper particle solder paste during the sintering process, it is necessary to add a reducing gas for protection, and sintering at high temperature and high pressure.
  • These auxiliary The method not only complicates the manufacturing process, but also greatly increases the manufacturing cost, which is not conducive to industrialized production.
  • the existing methods to prevent the oxidation of copper particle solder paste for example, use organic acid to corrode the surface of copper particles, and there is a certain probability to remove the oxide layer on the copper surface.
  • the treated copper particles have good sintering performance as fillers, but due to The surface of the corroded copper particles is unstable and is still easily re-oxidized, so this method will greatly reduce the storage time of the copper particle solder paste and limit its use range.
  • the present application provides a copper particle solder paste and a preparation method and a sintering method thereof.
  • a reducing agent added to the copper particle solder paste, the copper particle solder paste is prevented from being oxidized during storage and use.
  • the copper particle solder paste provided by the present application includes copper particles with good dispersibility, a dispersant and a solvent, and also includes a reducing agent, wherein the weight part of the reducing agent is 0.5-5 parts.
  • the produced copper particle solder paste can meet the application requirements of "low temperature sintering, high temperature service", and can replace nano silver sintering solder paste or sintered nano silver paste, which is suitable for electronic packaging and micro-connection fields.
  • the copper particle solder paste provided by the present application includes copper particles with good dispersibility, a dispersant and a solvent, and also includes a reducing agent, wherein the weight part of the reducing agent is 0.5-5 parts.
  • the copper particle solder paste includes the following raw materials in parts by weight: copper particles with good dispersibility, 75-90 parts; dispersant, 1-5 parts; solvent, 10-15 parts; reducing agent, 0.5 parts ⁇ 5 servings.
  • the total number of the above components is 100 parts.
  • the reducing agent includes at least one of ascorbic acid, copper formate, formic acid, acetic acid, and acetone oxime.
  • the reducing agents used in this application are all low-toxicity reagents, and both the reducing agent itself and its oxidation products are easily thermally decomposed.
  • Ascorbic acid also known as vitamin C, is an acidic polyhydroxy compound containing 6 carbon atoms. It has strong reducibility and is easily oxidized to dehydroascorbic acid, and ascorbic acid and its oxidation products are more than 80. It can be decomposed under the temperature environment of °C.
  • the particle diameter of the copper particles is 100 to 300 nm, and the copper particles are spherical.
  • the dispersing agent includes any one of polyvinylpyrrolidone K30, polyvinylpyrrolidone K90 and polyethylene glycol 1000.
  • the solvent includes at least one of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, 2-amino-2-methyl-propanol and 1-amino-2-propanol A sort of.
  • the copper particle solder paste in this embodiment includes a certain amount of reducing agent, which can not only remove the oxide layer on the surface of the copper particle, but also prevent the copper particle solder paste from being oxidized again during storage and use. It has a shelf life equivalent to that of ordinary lead-free solder, and can be refrigerated after opening to ensure its sintering performance within a certain period of time (for example, 24 hours).
  • the present application provides a preparation method of copper particle solder paste.
  • FIG. 1 is a schematic flowchart of an embodiment of a method for preparing a copper particle solder paste of the present application. As shown in Figure 1, in this embodiment, the method includes:
  • S11 Disperse copper particles to obtain copper particles with good dispersibility.
  • the particle diameter of the copper particles is 100 to 300 nm, and the copper particles are spherical.
  • nano-copper particles can promote the diffusion of atoms on the surface of copper metal particles, enabling welding at lower temperatures, but due to the extremely high activity of metal nano-copper particles, and the In the presence of various adsorption forces, it is easy to form agglomerates between nanoparticles. Therefore, it is necessary to disperse copper particles to obtain copper particles with good dispersibility to achieve more prominent physical properties.
  • the following raw materials are prepared in parts by weight: copper particles with good dispersibility, 75-90 parts; dispersant, 1-5 parts; solvent, 10-15 parts; reducing agent, 0.5-5 parts.
  • the total number of the above components is 100 parts.
  • the reducing agent includes at least one of ascorbic acid, copper formate, formic acid, acetic acid, and acetone oxime.
  • the dispersing agent includes any one of polyvinylpyrrolidone K30, polyvinylpyrrolidone K90 and polyethylene glycol 1000.
  • the solvent includes at least one of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, 2-amino-2-methyl-propanol and 1-amino-2-propanol A sort of.
  • the reducing agent and the solvent can be selected according to different materials of gold on the substrate and gold on the chip (eg, gold, silver, nickel, etc.).
  • the dispersing agent is polyvinylpyrrolidone K90 or polyethylene glycol 1000
  • the reducing agent, the dispersing agent and the solvent are mixed according to the ratio of raw materials and stirred uniformly to obtain a paste.
  • the dispersant is polyvinylpyrrolidone K30
  • the reducing agent and the solvent are mixed according to the raw material ratio and stirred uniformly to obtain a paste, which is not limited in this application.
  • the dispersant is polyvinylpyrrolidone K90 or polyethylene glycol 1000
  • the paste containing polyvinylpyrrolidone K90 or polyethylene glycol 1000 is added to the copper particles with good dispersibility according to the ratio of raw materials And stir evenly to obtain copper particle solder paste.
  • the paste and dispersant are added to copper particles with good dispersibility according to the raw material ratio and stirred evenly to obtain copper particle solder paste.
  • a mixing device is used to stir the copper particles and the paste to obtain a copper particle solder paste.
  • the mixing equipment includes a planetary mixer.
  • the mixing speed was 2000 rpm.
  • the planetary mixer refers to a device that uniformly mixes materials through the relative countercurrent motion among the suspension wheel, the planetary shovel and the side scraper in the grinding disc.
  • the device has low energy consumption, good sealing performance and is easy to use. Its working principle is that the motor drives the suspension wheel, the planetary shovel and the side scraper to revolve clockwise in the grinding disc through the pulley, the reduction box and the planetary gear box. The shovel rotates counterclockwise at the same time, so that the material can be fully stirred and kneaded in the grinding disc, so as to achieve the purpose of mixing and kneading.
  • the obtained copper particle solder paste can be used for coating, chip mounting and sintering, and by controlling the viscosity, connection layers with different thicknesses can be obtained, for example, the viscosity of the solder paste is controlled to be low, so that the thickness of the connection layer can be reduced low to meet different connection requirements.
  • adding a reducing agent to the copper particle solder paste can not only remove the oxide layer on the surface of the copper particle, but also prevent the copper particle solder paste from being oxidized again during storage and use; further , Because the preparation process is simple, and the added reducing agents are all low-toxicity reagents, the purpose of cost saving and stable production can also be achieved.
  • FIG. 2 is a detailed flowchart of an implementation manner of step S11 in FIG. 1 .
  • the method includes:
  • the following raw materials in parts by weight are prepared: copper particles, 1 part; absolute ethanol, 50 parts; dispersant, 0.5 part.
  • the dispersing agent includes any one of polyvinylpyrrolidone K30, polyvinylpyrrolidone K90 and polyethylene glycol 1000.
  • the mixed liquid is placed in an ultrasonic field, and the nanoparticle suspension is treated with ultrasonic waves of appropriate frequency and power.
  • the mechanism of ultrasonic dispersion is related to cavitation, which can generate high temperature and high pressure locally on the copper particles, and is accompanied by a micro-jet with a huge impact force, thereby producing a micro-pulverization effect on the copper particles and breaking the agglomerates. Thereby, copper particles with more uniform dispersion are obtained.
  • the degree of vacuum is controlled to be no greater than 0.1 MPa, and the drying temperature is controlled to be no greater than 60°C.
  • the present application can obtain copper particles with more uniform and better monodispersity, so as to achieve more outstanding physical properties. Soldering at low temperature to meet the packaging requirements of "low temperature sintering".
  • FIG. 3 is a schematic flowchart of an embodiment of a method for sintering copper particle solder paste of the present application. As shown in Figure 3, in this embodiment, the method includes:
  • the following raw materials are prepared in parts by weight: copper particles with good dispersibility, 75-90 parts; dispersant, 1-5 parts; solvent, 10-15 parts; reducing agent, 0.5-5 parts.
  • the total number of the above components is 100 parts.
  • the reducing agent includes at least one of ascorbic acid, copper formate, formic acid, acetic acid, and acetone oxime.
  • the dispersing agent includes any one of polyvinylpyrrolidone K30, polyvinylpyrrolidone K90 and polyethylene glycol 1000.
  • the solvent includes at least one of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, 2-amino-2-methyl-propanol and 1-amino-2-propanol A sort of.
  • the dispersing agent is polyvinylpyrrolidone K90 or polyethylene glycol 1000
  • the reducing agent, the dispersing agent and the solvent are mixed according to the raw material ratio and stirred to obtain a paste.
  • the dispersant is polyvinylpyrrolidone K30
  • the reducing agent and the solvent are mixed according to the raw material ratio and stirred uniformly to obtain a paste, which is not limited in this application.
  • the dispersant is polyvinylpyrrolidone K90 or polyethylene glycol 1000
  • the paste containing polyvinylpyrrolidone K90 or polyethylene glycol 1000 is added to the copper particles with good dispersibility according to the ratio of raw materials And stir evenly to obtain copper particle solder paste.
  • the paste and dispersant are added to copper particles with good dispersibility according to the raw material ratio and stirred evenly to obtain copper particle solder paste.
  • the heating rate is controlled to be 1-20° C./min
  • the sintering temperature is controlled to be 250-300° C.
  • the sintering time is controlled to be 30 minutes.
  • the applied pressure is controlled to be 0.3-1 MPa.
  • the obtained sintering strength is about 20MPa-35MPa, which is equivalent to the sintering strength of traditional tin-lead solder paste.
  • Reflow refers to remelting the paste solder pre-distributed to the printed board pads to achieve mechanical and Soldering of electrical connections.
  • Reflow soldering relies on the circulating flow of gas in the welding machine to generate high temperature, thereby acting on the solder joints, so that the gelatinous flux undergoes a physical reaction under a certain high temperature airflow to achieve the welding of Surface Mounted Devices (SMD).
  • SMD Surface Mounted Devices
  • the copper particle solder paste since the copper particle solder paste includes a reducing agent, it can not only remove the oxide layer on the surface of the copper particle, but also prevent the copper particle solder paste from being oxidized again during storage and use. There is no need to add reducing gases such as hydrogen or formic acid for protection during the sintering process; and since there is no oxide layer on the surface of the copper particles that hinders the sintering process, it is not necessary to sinter under high temperature and high pressure.
  • reducing gases such as hydrogen or formic acid for protection during the sintering process
  • the copper Application range of particle solder paste By reducing the requirements for the sintering environment, the copper Application range of particle solder paste; further, the sintering strength obtained by the copper particle solder paste in this application after sintering is equivalent to that of traditional tin-lead solder paste, which meets the packaging requirements of "low temperature sintering, high temperature service", and can replace nano-silver sintering Solder paste or sintered nano-silver paste is suitable for electronic packaging and micro-connection fields.
  • SEM Scanning electron microscope
  • FIG. 4a and FIG. 4b are SEM images of copper particles at different stages in Example 1 of the present application; wherein, FIG. Figure 4b is the SEM image of the connection joint obtained after the copper particle solder paste is sintered in Example 1 of the present application.
  • the small size effect of nano-copper particles can promote the diffusion of atoms on the surface of copper metal particles, enabling it to be welded at a lower temperature to meet the requirements of "low temperature sintering"; adding reduction After sintering, the copper particle solder paste is sintered at a lower temperature.
  • the joint structure formed after sintering is dense, the particle size effect disappears, and the remelting temperature returns to the melting point of the bulk metal, ensuring the high temperature of the copper particle solder paste. Reliability, to meet the packaging requirements of "high temperature service”.
  • the following raw materials by weight were prepared: copper particles with good dispersibility, 85 parts, wherein the copper particles had a particle size of 300 nm; polyvinylpyrrolidone K90, 1 part; ethylene glycol, 14 parts; Diols are mixed according to the ratio of raw materials and stirred evenly to obtain a paste; the paste is added to the copper particles with good dispersibility according to the ratio of raw materials and stirred evenly to obtain a copper particle solder paste; the copper particle solder paste is used for For chip bonding of copper-backed silicon wafer and copper substrate, pure nitrogen is pre-passed, and the copper particle solder paste is reflowed under nitrogen atmosphere, and the pressure is increased to 0.4MPa, and the temperature is controlled to 300 °C to obtain the connection strength (shear stress) 8MPa connection joint.
  • FIG. 5a and FIG. 5b are schematic diagrams showing the comparison of the SEM images of the connection joints obtained after the copper particle solder paste is sintered in Example 1 and Comparative Example 1 of the present application; wherein, FIG. 5a is a The SEM image of the connection joint obtained after the copper particle solder paste is sintered in Example 1 of the present application, and FIG. 5b is the SEM image of the connection joint obtained after the copper particle solder paste is sintered in Comparative Example 1 of the present application.
  • Copper particles with good dispersibility 80 parts, wherein the copper particles have a particle size of 100 nm; polyethylene glycol 1000, 1 part; triethanolamine, 14 parts; formic acid, 5 parts; , polyethylene glycol 1000 and triethanolamine are mixed according to the ratio of raw materials and stirred evenly to obtain a paste; the paste is added to the copper particles with good dispersibility according to the ratio of raw materials and stirred evenly to obtain copper particle solder paste;
  • SEM Scanning electron microscope
  • Copper particles with good dispersibility 82 parts, wherein the particle size of the copper particles is 300 nm; polyethylene glycol 1000, 1 part; triethylene glycol, 15 parts; ascorbic acid, 2 parts; Mix ascorbic acid, polyethylene glycol 1000 and triethylene glycol according to the ratio of raw materials and stir evenly to obtain a paste; add the paste into copper particles with good dispersibility according to the ratio of raw materials and stir evenly to obtain copper Particle solder paste; copper particle solder paste is used for the connection between silicon carbide (SiC) chips and ceramic copper clad laminates (Direct Bonding Copper, DBC), and pure nitrogen is pre-passed, and the copper particle solder paste is reflowed under nitrogen atmosphere. , the pressure is 0.7MPa, and the temperature is controlled at 300°C to obtain a connection joint with a connection strength (shear stress) of 34MPa.
  • SiC silicon carbide
  • DBC Direct Bonding Copper
  • Copper particles with good dispersibility 82 parts, wherein the particle size of the copper particles is 300 nm; polyethylene glycol 1000, 1 part; triethylene glycol, 15 parts; ascorbic acid, 2 parts; Mix ascorbic acid, polyethylene glycol 1000 and triethylene glycol according to the ratio of raw materials and stir evenly to obtain a paste; add the paste into copper particles with good dispersibility according to the ratio of raw materials and stir evenly to obtain copper Particle solder paste; copper particle solder paste is used for the connection between silicon carbide (SiC) chips and ceramic copper clad laminates (Direct Bonding Copper, DBC), and the copper particle solder paste is reflowed under formic acid atmosphere, and the low pressure is 0.7MPa , control the temperature to 300 °C, and obtain the connection joint with the connection strength (shear stress) of 30MPa.
  • SiC silicon carbide
  • DBC Direct Bonding Copper
  • Example 3 and Example 4 scanning electron microscopy (SEM) was used to observe the microscopic features of the connection joints obtained after sintering the copper particle solder paste in Example 3 and Example 4, respectively.
  • FIG. 6a and FIG. 6b are schematic diagrams showing the comparison of the SEM images of the connection joints obtained after the copper particle solder paste is sintered in Example 3 and Example 4 of the present application; wherein, FIG. 6a is a The SEM image of the connection joint obtained after the copper particle solder paste is sintered in Example 3 of the present application, and FIG. 6b is the SEM image of the connection joint obtained after the copper particle solder paste is sintered in Example 4 of the present application.
  • connection joints formed after the copper particle solder pastes in Example 3 and Example 4 are sintered have dense structures, indicating that after adding a reducing agent to the copper particle solder paste, the solder paste During sintering, a connection structure with comparable strength can be formed without reducing gas protection.

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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

La présente invention porte sur une pâte à braser à particules de cuivre, ainsi que sur son procédé de préparation et sur son procédé de frittage La pâte à braser à particules de cuivre comprend des particules de cuivre présentant une bonne dispersion, un dispersant et un solvant, et comprend en outre un agent réducteur, la quantité de l'agent réducteur étant comprise entre 0,5 et 5 parties en poids. L'agent réducteur comprend l'acide ascorbique et/ou le formiate de cuivre et/ou l'acide formique et/ou l'acide acétique et/ou l'oxime d'acétone. En ajoutant l'agent réducteur à la pâte à braser à particules de cuivre, non seulement la couche d'oxyde sur la surface des particules de cuivre peut être éliminée, mais également la pâte à braser à particules de cuivre ne peut pas être à nouveau oxydée pendant le stockage et l'utilisation ; de plus, étant donné que l'agent réducteur ajouté et un produit d'oxydation de celui-ci sont susceptibles d'être décomposés thermiquement, et ne gênent pas le processus de frittage, la pâte à braser à particules de cuivre peut être frittée à basse température sans réduire la protection gazeuse pendant le frittage, ce qui permet non seulement de réduire les coûts de production, mais également d'élargir la plage d'application de la pâte à braser à particules de cuivre.
PCT/CN2020/118173 2020-09-27 2020-09-27 Pâte à braser à particules de cuivre, ainsi que son procédé de préparation et son procédé de frittage WO2022061834A1 (fr)

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